Er^A-560/6-77-016
ENVIRONMENTAL MONITORING
NEAR INDUSTRIAL SITES:
CHROMIUM
JUNE 1977
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
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EPA-560/6-77-016
ENVIRONMENTAL MONITORING
NEAR INDUSTRIAL SITES:
CHROMIUM
by
Arthur D. Snyder
Daryl G. DeAngelis
Edward C. Eimutus
David M. Haile
Joseph C. Ochsner
Richard B. Reznik
Harlan D. Toy
MONSANTO RESEARCH CORPORATION
DAYTON LABORATORY
Dayton, Ohio 45^07
EPA Contract No. 68-01-1980
EPA Project Officer: Vincent DeCarlo
June 1977
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20^60
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EPA REVIEW NOTICE
This report has been reviewed by the Office of Toxic Substances,
U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents
necessarily reflect the views and policy of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement of recommendation for use.
ii
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CONTENTS
Section Page
1 Summary 1
2 Identification of Sampling Locations 3
2.1 Possible Sources of Chromium Emissions 3
in Industry
2.1.1 Incidental Chromium Emissions 3
2.1.2 Emissions From the Chromium 4
Industry
2.2 Results of Presampling Surveys and Choice 11
of Sampling Sites
2.2.1 Chrome Pigment Producers 14
2.2.2 Electroplating Plants 15
2.2.3 Ferrochromium Plants 16
2.2.4 Leather Tanneries 17
2.2.5 Sodium Bichromate/Chromic(VI) 17
Acid Producers
2.3 Final Selection of Sampling Sites 20
3 Sampling Sites 21
3.1 Air Sampling Sites 21
3.2 Water Sampling Sites 29
3.3 Soil Sampling Sites 29
4 Sampling Methods and Equipment 31
4.1 Air Sampling 31
4.2 Water Sampling 33
4.3 Soil, Sediment, and Sludge Sampling 35
5 Sample Analysis Procedures 37
5.1 Analysis of Air Particulate Samples 37
5.2 Analysis of Soil, Sediment, and Sludge 39
Samples
5.3 Analysis of Water Samples 43
5.4 Analysis Procedure for Organo-Chromium 44
Compounds
5.4.1 Air and Water Samples 44
5.4.2 Sewage Treatment Plant Sludge 44
iii
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Section
5.5 Sample Preparation - Acid Extraction
Procedure
5.6 Methyl Isobutyl Ketone/Ammonia Pyrrolidine 49
Diethiocarbamate Extraction Procedure for
Chromium(VI)
5.7 Varian AA-6 Instrument Parameters for 50
Chromium
References 55
APPENDICES
A Sampling and Analysis of Chromium and Lead at A-l
Mineral Pigments Corporation, Beltsville,
Maryland
B Sampling and Analysis of Chromium at Hercules, B-l
Incorporated, Glens Falls, New York
C Sampling and Analysis of Chromium at Stolle C-l
Corporation, Dayton, Ohio
D Sampling and Analysis of Chromium at Brezner D-l
Tanning Company, Penacook, New Hampshire
E Sampling and Analysis of Chromium at Penacook E-l
Municipal Sewage Treatment Plant, Penacook,
New Hampshire
F Sampling and Analysis of Chromium at Guthrie F-l
Road Sewage Treatment Plant, Dayton, Ohio
iv
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LIST OF FIGURES
Number Page
1 Consumption and Uses for Chromium 5
2 Location of Leather Tanneries in Essex County, 19
Massachusetts
3 Ambient Air Sampling Arrangement 27
4 Flow Chart of Atmospheric Stability Class 28
Determination
5 High-Volume Sampler with Propane Fuel Generator 32
6 Porous Polymer Vapor Sampling Method 34
7 Photographs of "Toolbox11 Sampler 36
8 Liquid Extraction Scheme for Organic Compounds 45
9 Acid Extraction Apparatus 48
10 Calibration Curve for Total Chromium by 51
Atomic Absorption (Air/C2H2 Flame)
11 Calibration Curve for Cr(VI) by Atomic 52
Absorption (N20/C2H2 Flame)
v
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LIST OF TABLES
Table Page
1 Ferrochromium Plants 7
2 Sodium Bichromate Plants 8
3 Chromic(VI) Acid Plants 8
4 Chrome Pigment Plants 10
5 Bibliography: Chromium Emission Sources 12
6 Selected Large Tanning Facilities and Locations 18
7 List of Final Sampling Sites by Industrial 20
Category
8 Listings for Air Diffusion Computer Model 22
9 Recovery of Chromium(VI) and Chromium(III) 38
Spikes From High-Volume Filters
10 Recovery of 0.2 mg of Chromium(VI) Through a 4l
Cation Exchange Column as a Function of pH
11 Recovery of Chromium(VI) Ion Exchange 42
Separation Procedure
12 Recovery of Chromium(VI) and Chromium(III) 42
Spikes for Soil Sample
13 Preextraction Routine for XAD Resin 44
14 Typical Ashing Times for Environmental Samples 47
15 Instrument Parameters for Varian AA-6 53
VI
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1. SUMMARY
A sampling and analysis program was conducted to determine
concentrations of chromium in the air, water and soil in the
environs of industrial sites and sewage treatment plants. Five
industrial categories - chrome pigments producers, electro-
plating plants, ferrochromium plants, leather tanneries, and
sodium dichromate/chromic acid producers - were presurveyed to
select the final sampling sites.
Samples were gathered at two chrome pigment plants, an electro-
plating plant, a leather tannery and two sewage treatment plants.
The protocol for sampling air utilized high-volume samplers in
either a downwind array or in a plant perimeter geometry.
Composite 24-hour water samples were taken and soil core samples
were obtained.
The techniques employed for analysis of the environmental samples
were intended to differentiate between the two most common
chromium valence states (III and VI). This was accomplished
for water samples but not for air, soil or sediment samples
because acid digestion converted chromium (VI) to chromium (III).
All analyses were obtained on a Varian AA-6 atomic absorption
spectrometer.
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2. IDENTIFICATION OF SAMPLING LOCATIONS
2.1 POSSIBLE SOURCES OF CHROMIUM EMISSIONS IN INDUSTRY
Industrial emission of chromium occurs during activities
directly associated with the rendering of chromium ores and
their subsequent fabrication or chemical conversion into useful
products, and during high-volume processes such as combustion
of coal. The importance of these types of emissions to the
local, regional or global environment depends on the chemical
and physical form of the chromium in the emission, the environ-
mental medium (air, water, soil) into which the emission occurs,
the average and peak concentration of emission, the geographical
relationship of the emission site to populations of organisms,
especially humans, and other factors. Lists of likely sampling
sites were prepared based on an analysis of the industrial flux
of chromium. A manageable number of sites was selected for
sampling through a process of site visits and telephone con-
tacts .
2.1.1 Incidental Chromium Emissions
The combustion of coal (1) and the production of iron are two
Industrial activities in which large volumes of minerals are
processed. Trace elements are frequently released in large
(1) Suprenant, Norman, Robert Hall, Steven Slater, Thomas Suza,
Martin Sussman and Charles Young. "Preliminary Emissions
Assessment of Conventional Stationary Combustion Systems,"
EPA 600/2-76-046b, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, January 1976, p. 79
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quantities to the environment during these processes. In the
case of volatile elements like mercury these processes represent
a major mechanism for release of the elements from the litho-
sphere to the biosphere (i.e., atmosphere). Refractory elements
such as chromium are also released, usually in the form of glassy
fly ash where metals are bound as counterions for the polysili-
cate matrix.
The highly diluted nature of these incidental emissions and the
wide geographic dispersal of these industries tend to preclude
the exposure of any population group to serious levels of any
one trace element. For example, the exact form of chromium in
fly ash is unknown; as noted above, it is likely to have low bio-
availability. Assume that all of the chromium in fly ash was in
the form of the rather toxic and corrosive chromic(VI) acid for
which the threshold limit value (TLV®) is 0.1 mg/m3. A sample
calculation (2) for a coal-fired utility boiler (capacity =
400 MW, stack height = 82 m, chromium content of coal = 15 ppm,
uncontrolled chromium emission factor = 90% of chromium content,
control efficiency = 80%, plant heat rate = 2.98 J(coal input)/
J(power output), coal heat content = 25.8 x 106 J/kg) yields a
maximum chromium ground level concentration (x ) of 1 yg/m3.
max
This is a factor of 100 below the TLV for chromic(VI) acid.
Thus, incidental emissions will not be considered because they
do not present a critical situation which demands immediate
concern.
2.1.2 Emissions From the Chromium Industry
The consumption and uses of chromium in the U.S. economy are
shown in Figure 1. Symbols are used in Figure 1 to designate
(2) Reznik, Richard B. "Source Assessment: Flat Glass Manu-
facturing Plants," EPA 6oO/2-76-032b, March 1976, pp 122-126,
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operations which give rise to air emissions (o), water emissions
«), and solid wastes (D). A number (3 or 6) indicates whether
chromium is present in the trivalent or hexavalent form.
Chromium is one of the few elements for which the U.S. is almost
totally dependent upon imports. Imported chromite ore (Cr203.PeO) is
converted into three primary products: ferrochromium (68%), re-
fractory brick (16$), and sodium dichromate (17$). Ferrochromium
is converted primarily to steel (92$) or other alloys. The
chrome refractories are used as linings in high temperature
furnaces or kilns. Sodium dichromate finds direct use in some
applications, while in other cases it is first converted to
another chromium compound. Some of the more significant emission
sources based on Figure 1 are listed below.
• Metallurgical Industries
Chromite ore is reduced with coke in an electric arc furnace
to give ferrochromium. Uncontrolled emissions have been
reported from 100 g/kg to 415 g/kg, but the majority of the
industry (>80$) has installed controls (typically 95$
efficient). Ferrochromium plants are listed in Table 1.
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Table 1. FERROCHROMIUM PLANTS
Company Plant Location
Airco Alloys and Carbide Div., Calvert City, Ky.
Air Reduction Co. Inc. Niagara Falls, N.Y,
Charleston, S.C.
Chromium Mining and Smelting Corp. Woodstock, Tenn.
Foote Mineral Co. Graham, W. Va.
Interlake Inc. Beverly, Ohio
Ohio Ferro-Alloys Corp. Brilliant, Ohio
Shieldalloy Corp. Newfield, N.J.
Union Carbide Corp. Niagara Falls, N.Y,
Marietta, Ohio
Ferrochromium is used primarily in the production of stain-
less steels. Uncontrolled furnace emissions from this process
average 12 g/kg. The level of control is similar to that in
the ferrochromium industry.
In the metallurgical industries, chromium is emitted to the
atmosphere as Chromium(III) oxide along with other metal oxides,
and particulates are often below 1 micron in size. Wet scrubbers
used for emissions control produce a water effluent containing
chromium.
Refractories Industries
Chromite grinding will generate fugitive dust, but particles
in the respirable range should amount to ^1 g/kg or less
compared to emissions of ^100 g/kg from ferrochrome
furnaces.
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The Chemical Industries
(A) Sodium Dichromate - Chromite ore is roasted in a
rotary kiln with soda ash or lime to form a soluble
chromate. This is leached, precipitated, and dried
as sodium dichromate. The compound is made at three
plants, listed in Table 2, which have controls for
air and water emissions.
Table 2. SODIUM DICHROMATE PLANTS
Company
Allied Chemical Corp.
Diamond Shamrock Corp.
PPG Industries, Inc.
Plant Location
Baltimore, Md.
Castle Haynes, N.C.
Corpus Christ!, Tex.
Capacity
(metric tons/yr)
68,000
64,000
27,000
(B) Chromic(VI) Acid - Chromic(VI) acid has been produced
at four locations, listed in Table 3, by reacting sodium
dichromate with sulfuric acid. The waste solution
contains chromium ions. The ":wo operating plants
have controls.
Table 3. CHROMIC(VI) ACID PLANTS
Company
Allied Chemical Corp.
Diamond Shamrock Corp,
Essex
McGean
Plant Location
Baltimore, Md.
Castle Yanes, N.C
Kearny, N.J.
Cleveland, Ohio
Capacity
(metric tons/yr)
16,000
12,000
(standby)
1,800
(standby)
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(C) Chrome Pigments - In general, chrome pigments are made
by precipitation or crystallization from solution, fol-
lowed by filtration, drying, and possibly calcining.
Waste effluents contain chromium, while stack emissions
from dryers and calciners contain particulate chromium
compounds. Producing companies are listed in Table 4.
(D) Other Chemicals - The production of other chromium
compounds is expected to yield the same types of
emissions as the production of chrome pigments.
The low production level of these compounds elimi-
nated them from further consideration.
Electroplating
The major use for chromic(VI) acid is in chrome electroplating,
An aqueous solution of the acid is used, resulting in a
chromium-contaminated water discharge. Gas evolution during
plating also causes the formation of a chromium-containing
mist which must be vented to the outside.
There are several thousand electroplating facilities in the
U.S.; some are independent plants and some are captive to
such activities as automobile manufacture and the production
of electrical equipment. Larger operations are generally
controlled, but some smaller ones are not.
Leather Tanning
Most leather goods are tanned with a reduced sodium di-
chromate solution. Effluents from the process contain
chromium ions.
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Table
CHROME PIGMENT PLANTS
Company
Location
Allied Chemicals Corp.
Hercules, Inc .
Marcus Hook, Pa.
Glen Falls, N.Y.
Products
Kewanee Oil Co.
Mineral Pigments Corp.
Louisville, Ky,
Beltsville, Md.
Minnesota Mining & Mfg. Copley, Ohio
Pfizer, Inc. Lehigh Gap, Pa.
Reichold Chemicals, Inc. Brooklyn, N.Y.
Richardson-Merrill Phillipsburg, N.J.
Rockwood Industries, Inc. S. Plainfield, N.J,
Shepherd Chemical Co. Cincinnati, Ohio
Lead chromate
Chromium oxide
Lead chromate
Molybdate orange
Zinc chromate
Compounded chrome
pigment s
Lead chromate
Chromium oxide
Lead chromate
Molybdate orange
Zinc chromate
Chromium oxide
Chromium oxide &
hydroxide
Molybdate orange
Zinc chromate
Compounded chrome
pigments
Lead chromate
Chromium oxide
Chromium oxide &
hydroxide
10
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• Metal Treatment, Wood Treatment, and Corrosion Control
A number of metals and woods are treated with a chromium
solution to Inhibit corrosion and decay. Recirculating
water systems often contain chromium compounds to pre-
vent corrosion. In all cases, the waste discharge will
contain chromium in solution.
• Textiles and Dyes
Certain dyes and pigments employ a chrome mordant.
Since the dyeing operation is carried out in a water
solution, the water effluent is contaminated with
chromium.
References utilized in compiling the analysis presented in
Section 2.1 are listed in Table 5.
2.2 RESULTS OF PRESAMPLING SURVEYS AND CHOICE OF SAMPLING SITES
A presurvey effort was scheduled for plants in the following five
industrial categories:
• Chrome pigment producers
• Electroplating plants
• Ferrochromium plants
• Leather tanneries
• Sodium dichromate/chromic acid producers
The surveys included determination of the present state of con-
trol technology, actual air and water emission points, accessi-
bility of sampling sites, presence of interfering structures,
other possible sources of chromium emissions in the area, and
the cyclic nature of plant operations. Previous experience has
proven that sampling without consideration of these factors can
11
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Table 5. BIBLIOGRAPHY: CHROMIUM EMISSION SOURCES
National Emissions Inventory of Sources and Emissions of Chromium, prepared for
the EPA by GCA Corporation, EPA-450/3-74-012, May 1973, 4l pages.
Morning, J. L., Chromium, in Minerals Yearbook 1972, Vol I., Metals, Minerals
and Fuels, US Bureau of Mines, Washington, (1974) pp 289-299.
Barrett, W. J., G. A. Morneau, and J. J. Roden III, Waterborne Wastes of the Paint
and Inorganic Pigments Industries, prepared for the EPA by Southern Research Insti-
tute, EPA-670/2-74-030, March 1971, 26 pages.
A State-of-the-Art Review of Metal Finishing Waste Treatment, Battelle Memorial
Institute, Columbus, Ohio, PB 203207, November 1968, 88 pages.
Diercks, P. W., Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Smelting and Slag Processing Segments of
the Ferroalloy Manufacturing Point Source Category, Environmental Protection
Agency, Washington, February 1975, PB 238650, 170 pages.
Martin, E. E., Development Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Major Inorganic Products Segment of the
Inorganic Chemicals Manufacturing Point Source Category, Environmental Protection
Agency, Washington, March 1971, PB 238611, 367 pages.
Krickenberger, K. R., Development Document for Effluent Limitations Guidelines
and New source Performance Standards for the Copper, Nickel, Chromium, and Zinc
Segment of the Electroplating Point Source Category, Environmental Protection
Agency, Washington, March 197", PB 23883*4, 220 pages.
Gallup, J. D., Developemtn Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Leather Tanning and Finishing Point Source
Category, Environmental Protection Agency, Washington, March 197'*, PB 238648,
161 pages.
Current Industrial Reports, Inorganic Chemicals 1972, US Department of Commer&e,
Washington, M28A(72)-14, December 1973, 28 pages.
Steam Electric Plant Factors, 1974 Ed., National Coal Association, Washington,
December 1974, p 54, 102.
Magee, E. M., H. J. Hall, and G. M. Varga, Jr., Potential Pollutants in Fossil
Fuels, ESSO Research and Engineering Company, Linden, Environmental Protection
Agency, Research Triangle Park, Publication No. EPA-R2-73-249, June 1973, P 67.
Chemical Profile: Sodium Bichromate, Chemical Mar/ceting Reporter, 3 September
1973, p. 9-
Chemical Profile: Chromic Acid, Chemical Marketing Reporter, 23 June 1975, P 9.
Pollution Control Shines in Chrome Chemicals Plant, Chemical Week, 110:77-78,
21 June 1972.
Danielson, J. A., Air Pollution Engineering Manual, Second Ed., Environmental
Protection Agency, Research Triangle Park, May 1973, PP 239-255, 829-832.
Bacon, F. E., Chromium and Chromium Alloys, Kirk-Othmer Encyclopedia of Chemical
Technology, Second Ed., Vol. V, Interscience Publishers, New York, 1964 pp 451-
472.
Hartford, W. H., and R. L. Cupson, Chromium Compounds, Kirk-Othir.er Encyclopedia
of Chemical Technology, Second Ed., Vol. V, Interscience Publishers, New York,
1964, pp. 473-516.
Lowenheim, F. A., Electroplating, Kirk-Othmer Encyclopedia of Chemical Technology,
Second Ed., Vol. VIII, Interscience Publishers, New York, 1965, pp. 36-74.
O'Flaherty, F., Leather, Kirk-Othmer Encyclopedia of Chemical Technology, Second
Ed., Vol. XII, Interscience Publishers, New York, 1967, PP • 303-343-
1975 Directory of Chemical Producers, Stanford Research Institute, Menlo Park,
California, 1975, 1050 pages.
12
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lead to meaningless results.
The five types of operations were included in the survey to
study the greatest variety of emissions. Since the sources of
chromium emissions encompass dissimilar processes, it was
necessary to survey several types of industries to gain a com-
prehensive understanding of possible problems.
To assess air and soil sampling potential, airports near the
plants were contacted for information on prevailing wind direc-
tion before the survey visits. Topographic maps of each site
were obtained. The local EPA or State Water Control Board was
contacted at the site to obtain NPDES permits and previous dis-
charge reports. Compliance schedules for air emissions were
obtained from local Agency personnel. The USGS eight-digit
STORET number was also obtained in order to assess information
from any river monitoring stations.
The following type of information concerning the basic process
descriDtion was solicited from plant personnel at each plant site
• emission points - air, water and solid
• solid waste handling practices
• operating cycle (batch, continuous, cyclic) - best
times to sample
• abnormal conditions that might affect sampling validity
• heights of air emission points and water discharge
locations
on-site treatment of process effluent or municipal
treatment
• expected chromium valence states at each emission
point
• fugitive emissions
• other sources of chromium emissions in the area
. age of facilities
13
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Additional information that was obtained by observation at
the plant sites included:
• nature of terrain surrounding the plant site espe-
cially in the direction of the prevailing wind
• ease of sampling (both air and water)
• receiving water characteristics (terrain, size, flow,
accessibility)
• air emissions (heights of stacks, location, color and
frequency of observed emissions, wind direction and
velocity, plume rise)
• location of community water supply with respect to
plant discharges
• presence of interferring structures
• other industries or emission sources nearby
2.2.1 Chrome Figment Producers
Chrome pigment producers were judged worthy of study since hexa-
valent chromium compounds are released into both air and water
by this industry. Control technology has been installed at most
plants because of environmental standards and the more recent
threat of carcinogenic activity by lead chromate. However, in-
organic pigments are typically produced in particle sizes of
0.1 to 10 ym, which are difficult to control. A dryer with
uncontrolled emissions of 10 g/kg may still have emissions of
0.5 g/kg after a control device is installed.
An attempt was made to arrange surveys at three plant sites in
cooperation with the Dry Color Manufacturers' Association (DCMA),
Mr. Gregory Bruxelles,a head of the lead chromate subcommittee
o
Director of Marketing Services, Coatings and Specialty Products
Department, Hercules Incorporated, 910 Market Street, Wilmington
Delaware 19899 '
14
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of the DCMA, was unable to furnish Information and suggested
that the individual chrome pigment producers should be contacted
directly. Based on the variety of compounds made, surveys
were conducted at the Mineral Pigments Corp. at Beltsville, Md.,
and at Hercules, Inc., at Glens Palls, N.Y. Details of the sam-
pling survey visits are presented in Appendices A and B with
the sampling and analyses results. The Hercules, Inc. plant
was chosen because the effluent discharge at the Beltsville,
Md., Mineral Pigments Corp. site was below the water level
of a creek tributary and, therefore, somewhat inaccessible
for sampling. Eventually, both sites were sampled on request
of the Project Officer, Dr. Vincent DeCarlo, when it was
learned that the Mineral Pigments factory had come under the
scrutiny of the Occupational Safety and Health Administration
for alleged violations of Federal Health and safety standards
due to work-place emissions of lead compounds. The sampling
and analysis efforts at Mineral Pigments included lead in
addition to chromium determinations.
2.2.2 Electroplating Plants
Electroplating operations discharge hexavalent chromium into the
air and water when uncontrolled. Defoaming agents are commonly
used to suppress the formation of chromic(VI) acid mist emis-
sions, while larger facilities also employ scrubbers. Water
treatment is not as extensive, and smaller operations may dis-
charge untreated wastes to the municipal water system.
Since plating plants number in the thousands, 13 sites in
the Dayton, Ohio area were considered. Miller Plating Company
and the Stolle Corporation were surveyed as potential sampling
sites. The Stolle Corporation was selected based upon the
accessibility of sampling locations and the fact that it is located
within 0.5 km of the Dayton Laboratory of MRC. The results of the
sampling and analysis effort at the Stolle Corp. facility are pre-
sented in Appendix C.
15
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2.2.3 Ferrochromlum Plants
Producers of ferrochromium were selected for presampling survey
in the metallurgical industry because the chromium content in their
emissions is higher than in related areas such as stainless
steel production. The ferrochromium plant sites surveyed in-
cluded the Chromium Mining and Smelting Corporation (Chromasco)
at Woodstock, Tennessee and the Interlake, Inc. plant at Beverly,
Ohio.
The Chromasco site was surveyed on September 1, 1976 but no
visit could be arranged with plant personnel. Discussions with
Shelby County (Tennessee) Health Department personnel responsi-
ble for air and stream pollution and a visual survey of the
plant site indicated no potential problems in sampling.
The Interlake, Inc. plant at Beverly, Ohio was not selected
for sampling for three reasons: (1) their present process
precludes the possibility of chromium-bearing wastewater,
(2) highly efficient baghouse particulate controls minimize
the probability of significant air emissions, and (3) the
plant site is located about 0.8 km from a 1400 MW coal-burning
power plant. The Interlake site is completely surrounded by
the power plant property, with its ash beds, ponds, and
chrome ore and slag piles, which would have invalidated soil
measurements for chromium.
16
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2.2.4 Leather Tanneries
There are some 500 leather tanneries in the U.S., and a number
of the larger ones are given in Table 6 (3). The greatest
concentration occurs in Essex County, Mass, (see Figure 2). Pre-
sampling survey visits were conducted at the R. J. Widden Tannery
in North Adams, Mass, and the Saco Tanning Co. in Saco, Maine.
Either of these sites would have qualified for sampling chromium,
but the Brezner Tanning Company in Penacook, New Hampshire was
selected since its water effluent is treated at a local muni-
cipal sewage treatment plant. This relationship furnished
the opportunity of sampling tannery effluent before and after
treatment. The survey reports for the tannery and the treatment
plant are presented in Appendices D and E of this report.
2.2.5 Sodium Dichromate/Chromic(VI) Acid Producers
At the present time, only three companies are actively manufac-
turing these chemicals (Tables 2 and 3). Visits were made to
the Allied Chemical Corp. site in Baltimore, Md. and the Diamond
Shamrock Corp. plant in Caste Haynes, N.C. The Allied site was
found to be unsuitable for sampling for three reasons: (1) the
plant is located in a highly industrialized and commercial area
just north of the Northwest Harbor of Chesapeake Bay, (2) the
potential for downwind air sampling is hampered by the prevailing
wind which is from the northwest to the harbor, and (3) collection
of soil samples is impossible due to the urban nature of the area.
The Diamond Shamrock facility opened in 1972 and is equipped with
the latest pollution control technology. All hot flue gases
pass through two electrostatic precipitators (99.8$ efficient).
(3) "Thomas Register, 1975" Thomas Publishing Co., New York,
N.Y., 1975, PP 8787-8788.
17
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Wastewaters and waste muds are treated to convert
chromium(VI) into an insoluble chromium(III) compound which
settles out in treatment lagoons. A complex monitoring system
samples ambient air in all directions around the plant and
tests the water effluent. It was judged that chromium
measurements at this modern and well-controlled complex would
not be representative of the industry.
2.3 FINAL SELECTION OF SAMPLING SITES
As a result of the surveys, sampling and analysis of chromium was
conducted at the four industrial sites and the two sewage treat-
ment plants listed in Table 7. The second sewage treatment
plant, not mentioned previously, is located on Guthrie Road in
Dayton, Ohio about 1.4 km from MRC's Dayton Laboratory and is
adjacent to the Stolle Corporation electroplating operation.
Although this treatment plant does not handle the Stolle Corpora-
tion wastewater, City of Dayton Water Department personnel stated
that the bulk of chromium they receive comes from chromium plating
operations in the area.
Table 7. LIST OF FINAL SAMPLING SITES
BY INDUSTRIAL CATEGORY
Report
Sampling Site Location Appendix
Chrome Pigments
Mineral Pigments Corp. Beltsville, Md. A
Hercules, Inc. Glens Falls, N.Y. B
Electroplating Plants
The Stolle Corp. Dayton, Ohio C
Leather Tanneries
Brenner Tanning Co. Penacook, N.H. D
Sewage Treatment Plants
Penacook Sewage Penacook, N.H. E
Treatment Plant
Guthrie Road Sewage Dayton, Ohio F
Treatment Plant
20
-------
3. SAMPLING SITES
3.1 AIR SAMPLING SITES
Diffusion models of the two chrome pigment plants and the
electroplating plant were developed based on the emission rates
and the effective heights of emissions as given by plant operat-
ing management or estimated by MRC personnel. The Gaussian
plume model as developed by Martin and TIkvart (4) employs annual
joint frequency distributions of atmospheric stability, and wind
speed and direction as obtained from the National Climatic
Center in Asheville, North Carolina. These data were employed
as input into MRC's computer program to calculate relative con-
centration or dosage isopleths surrounding each plant site of
interest. The listings from this program are presented in
Table 8. This procedure has been well documented by the EPA
in their descriptions of the Climatological Dispersion Model
(COM) (5). The result of the modeling effort was a definition of
potential chromium contents in air surrounding the plant sites
based primarily on the point source emissions defined in the
surveys. This result did not, however, account for fugitive
(4) Martin, D. 0. and J. A. Tikvart, "A General Atsmopheric
Diffusion Model for Estimating the Effects on Air Quality
of One or More Sources," presented at the 6lst Annual Meeting
of the Air Pollution Control Association, St. Paul,
Minnesota, June 23-27, 1968, 18 pp.
(5) Busse, A. D. and J. R. Zimmerman, "User's Guide for the
Climatological Dispersion Model" EPA-R4-73-024 U.S.
Environmental Protection Agency, Research Triangle Park,
North Carolina, December 1973.
21
-------
Table 8. LISTINGS FOR AIR DIFFUSION COMPUTER MODEL
C M-T DIFFUSION PROGRAM
C REVISED 9/10/76 - LB MOTE
C
DIMENSION SHOT (10) ,SVET<10> .HST(IO) .QSOT(IO) iGT( 10 ) » WT( 10 )
DIMENSION SC(6,16,6),A(18)»B(1S),C<18) ,WSA(6)
DIMENSION RHOR1180) ,RVER(180) , VAL(ISO) . ACCUM(ISO)
DATA A, B,C»WS A/. 00024,. 055,. 113, 1.26, 6. 738, 16. 05, . 0015, .038, .113,
1.222, .211,. 086,. 192.. 156 ..116, .079,. 063, .053.2.094,1.098, .911 ,
2. 516,. 30 5, .18 0,1. 941, 1.149,. 911,. 725,. 678,. 74, .936 ,.922, .905,
3. 881,. 871,. 81 4, -9. 6, 2., 0., -13., -34., -48. 6, 9. 27, 3. 3,0., -1.7, -1.3,
4-. 35, 6*0.,. 67, 2. 46, 4. 47, 6. 93, 9. 61, 12. 52/
LUR=1
LUW = 5
READ(LUR,174) DELTAX,HAXRAD 091076
READ(LUR,74) IRAD.XSTARTi YSTART
RE AD ( LUR , 73 ) GR I D , ALWT , DMIX , I SOR , IREC , K , IUR
READ(LUR,2) < <
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CX=.393*X
IF(CX-Y) 96,96,36
36 AR62=(CX-Y)/CX
60 T0<13,121) iIPT
121 IF«W/2.)-ABS) 122,122,1325
122 IF(W-.393*XP) 13,13,123
1225 Q=( . 1965* 131,131,99
123 Q=(.393*X-W)/W
XP=SQRT( (XP*XP)+(W*W/4) )
X=2.*XP
125 IF(Y-
-------
60 TO 2225
2221 F = SC(5,I\I, J)+SC(6,N,J)
2225 IF(F) 99,99,10
10 WS=WSA(J)
60 T0(20,201),IUR
20 IFUOOK-5) 201,2010,2010
2010 L=t
201 CC=L
H=HS+2*(tl.4-0.1*CC)*6)/WS
3<*10 IF(H-DM) 3H»3t,99
3t IF(XP-1000.) 28,21,21
28 IF(XP-100.) 128,261,281
128 L=L+12
60 TO 21
281 L=l>6
21 60 TO(321,211),IUR
321 IF(H-50.) 210,210,211
210 SI6I=50.0-H
IFISIGI-30.) 221,221,2101
2101 SIGI=30.
60 TO 221
211 SIGI=0.0
221 SI6Z=SQRT((A(L)*ABS(XP)**B
IF(ABS(ARG1)-60.0) 37,99,99
37 60 TO(371,27),IUR
371 IF(SI6Z-0.47*DM) 27,27,26
27 LL=1
XD=X
68 C1=(FREQ*2.03*Q*F*AR62*EXP(ARG1))/(SI6Z*WS*XD)
60 TOC*5,31),LU
H5 C3=C1
60 TO 990
26 DUH1=(,H7*DH)**2-SI6I**2
9991 DUM2=SQRT
X1=EXP(DUM3/B-C(L>
999t OUM3 = ALOG(DUM2/A(L) )
X1=EXP(DUM3/B(D)
60 IF(XP-2.0*X1) 6<4,63,63
63 XD=X
L l"i=l
67 C2=(2.55*FREQ*Q*F*AR62)/(DM*WS*XD)
GO T0(fe5,66) ,LI*I
65 C3=C2
GO TO 990
6t XD=2.0*Xl-Hn/.393
Ll*l=2
GO TO 67
66 XD=Xl+W/.393
LL=2
SI6Z=0.t7*DM
ARG1=(-.50*H*H)/(SI6Z*SIGZ)
-------
60 TO 68
31 C3=Cl-((XP-X1)/(X1))* IRAD
00 11512 M=1,IREC
K=2*M-1
11512 WRITE(LUW,105) K.RHOR(M>tRVER(M)iACCUM(M)
60 TO 710
799 CONTINUE
CALL EXIT
1 FORMAT <4Iif)
2 FORMAT<7X,6F7t5)
73 FORMAT
-------
emission points. For this reason, perimeter air sampling was
conducted at each plant site where air emissions were suspected.
The ambient air sampling arrangement employed is presented in
Figure 3. A portable meteorological station was used to determine
wind speed and direction. The logic chart shown in Figure 4
was employed to estimate atmospheric stability class. One 24-
hour sample was obtained at each of the three plant sites men-
tioned previously, employing a minimum of six high-volume samplers,
The results permit calculation of each plant's chromium emission
rates, including both point and fugitive source contributions.
Where no inorganic air emissions were suspected, such as the
tannery and sewage treatment plants, high-volume samplers were
not employed.
The tannery and the two sewage treatment plants were sampled to
determine "organic" chromium species in air. Here "organic"
chromium is used to mean any chromium compound which is volatile
or has affinity for nonpolar organic resins used to concentrate
materials from water or air. These would include chromium
organic compounds such as complexes of chromium with organic
ligands.
These types of chromium compounds are known to exist and if they
occur in nature they would be expected in tannery waste or
sewage since these media contain a wide variety of organic sub-
stances and support biological activity. For example, see the
work of Toepfor, et al. (6) on chromium in yeast extracts.
(6) Toepfor, E. W., W. Mertz, M. M. Polansky, E. E. Roginski,
and W. R. Wolf, "Preparation of Chromium-Containing Material
of Glucose Tolerance Factor Activity from Brewer's Yeast
Extracts and by Synthesis," Journal of Agricultural and
Food Chemistry 2_5_, 162-166 (1977).
26
-------
Angle of Wind /"
B
Source
Resultant
Wind
Direction
Figure 3- Ambient Air Sampling Arrangement
27
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3.2 WATER SAMPLING SITES
Water sampling sites varied from plant to plant depending upon
the body of water into which the plant effluent was discharged.
A 24-hour composite sample was taken at the outfall of each
plant. If the plant was discharged into a stream, one sample
was taken above the outfall, one at the outfall, and two at loca-
tions at staggered intervals downstream of the outfall.
Sediment samples in bodies of water were obtained where possible
to determine chromium accumulation. These samples were taken
in the same locations as the water samples. One sample above
the outfall and two at staggered locations below the outfall
were collected.
The specific sampling sites could only be determined as a result
of the survey visits. These sites for each plant are des-
cribed in the respective appendices.
The technology required to examine water or other media for
ionic (e.g., nonvolatile) chromium organic compounds does
not exist at present. It is believed that liquid chroma-
tography with on- or off-line atomic absorption detection would
be needed to study these systems in detail.
3.3 SOIL SAMPLING SITES
The soil sampling sites were selected based on the seasonal
concentration isopleths developed employing the Gaussian plume
model. The computer program employed at MRC Is capable of
locating points of maximum ground level concentration based
on the point-source data. Five samples were obtained at each
plant. Since the diffusion model predicted an area of maximum
29
-------
concentration and a secondary maximum concentration area, two
samples were taken in each of these areas (one close to the
plant boundaries and one farther away from the plant). The
fifth sample was taken as a background sample upwind of the
facility. Duplicate samples were obtained at each sample site
30
-------
4. SAMPLING METHODS AND EQUIPMENT
>4.1 AIR SAMPLING
O
High-volume samplers were used to collect particulates from
ambient air. These samplers have automatic flow controllers
that adjust the flow to a precalibrated flow setting. In this
case, 0.019 m3/s (40 cfm) was the flow rate used.
Sampling was conducted over a 24-hour period for perimeter
samples and for 4-6 hours using the downwind array. The parti-
culate was collected on 20.3 cm x 25-4 cm Millipore® filters.
These filters exhibit a chromium content of 0.002 yg Cr/cm2.
At the start of the program, small gasoline-powered generators
were employed to permit sampler operation in remote areas.
Later in the program the gasoline-powered generators were con-
verted to propane by employing liquid propane-gas carburetion
kits. Liquid propane-gas vapor withdrawal tanks containing
sixty pounds of fuel permitted 50 hours of continuous, un-
attended high-volume sampler running time. Plow controllers
(Accu-Vol Controller Model GMW-310) were employed to ensure a
constant sampling flow rate independent of voltage variation,
temperature or pressure changes and filter loading. The high
volume sampler arrangement employing the propane fuel genera-
tor is shown in Figure 5.
aGeneral Metal Works, Inc., 8368 Bridgetown Road, Cleves,
Ohio 45002.
31
-------
I *.,. „_.--""'*'
Figure 5- High-Volume Sampler with Propane
Fuel Generator.
32
-------
Air samples were also obtained at some locations for organic
chromium species. These samples were taken using the sampling
train shown in Figure 6. Ambient air was pumped through a
glass fiber filter and an XAD-2 resin tube at between 230 cm3/s
and 330 cm3/s over a period of four hours. The volume of
gas sampled in each run was measured by a dry test meter. After
sampling, the resin tubes were capped at either end for trans-
port back to the laboratory.
4.2 WATER SAMPLING
The water sampling methods and equipment employed depended on
the plant location, process operation, and characteristics of
the body of water to be sampled. However, some basic methodology
was established which could be used in the various sampling
situations.
Two types of commercial water samplers were used. These were
a b
the Manning water sampler and the ISCO water sampler . Both
samplers are capable of taking sequential and composite
samples either on a time or flow proportional basis. Since
these units are battery powered, they are useful for sampling
in remote locations.
a
'Manning Environmental Corp., 120 DuBois Street, P. 0. Box 1356
Santa Cruz, California 95061. '
Instrumentation Specialties Company (ISCO), P.O. Box 53^7,
4700 Superior Street, Lincoln, Nebraska 68505.
33
-------
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Another type of water sampler employed was designed by MRC to
fit in a Sears-Roebuck Craftsman toolbox (45.7 cm x 22.9 cm x 20.3 cm)
The apparatus consisted of a variable speed peristaltic pump
fitted with a Masterflux model 7016 pump head powered by a 12-
volt motorcycle battery. The pump speed was set so that a
4-liter polyethylene Cubitainer® was filled over a 24-hour
sampling period. Two views of the "toolbox" sampler are presented
in Figure 7.
Each water sample taken exceeded the required volume of approxi-
mately 2 liters. The samples were filtered through an 0.45-
micron Millipore® filter in the field to separate soluble and
suspended particles. It was preserved by adjusting the pH of
the sample to 3.5-5.0 using a field-determined amount of
6M HN03/3M H3P04.
Water samples for "organic" chromium species were obtained at one
location. They were pumped through an XAD-4 resin tube at a rate
of 200 ml/min using a variable speed peristaltic pump. Approxi-
mately 8 liters of sample were pumped through each tube.
Approximately 500 ml of 0.1M HC1 was then pumped through each
tube to rinse "inorganics" that may have been left on the resin.
The tubes were then sealed at the ends for transport back to the
lab.
4.3 SOIL, SEDIMENT, AND SLUDGE SAMPLING
Soil samples were obtained using a core-sampling device. Cores
8.3 cm in diameter and 7.6 cm deep were collected and placed
in plastic bags.
Sediment samples were taken by scooping sediment off the bottom
of the body of water being sampled. Sludge samples were taken
in much the same manner. These samples were placed In poly-
ethylene jars for transport to the laboratory.
35
-------
(a) External View of "Toolbox" Sampler
• J
(b) Internal View of "Toolbox" Sampler.
Figure 7. Photographs of "Toolbox" Sampler.
36
-------
5. SAMPLE ANALYSIS PROCEDURES
5.1 ANALYSIS OF AIR PARTICULATE SAMPLES
Immediately upon completion of the air sampling, the tared filter
o
(20.3 cm x 25.4 cm Gelman spectroquality glass fiber filter) on
which air contaminants were collected was placed between onionskin
paper and transported back to the laboratory in a sealed en-
velope. Upon arrival at the laboratory the filters were removed
from the envelope, desiccated for 24 hr, and the mass of par-
ticulate loading determined. After the unexposed portion of
the filter had been carefully trimmed, the exposed portion
was analyzed.
A segment of the filter O5-7 cm x 18 cm) was acid extracted
according to the procedure described in Section 5-5- chromium(VI)
analysis was performed using the ADPC/MIBK extraction procedure
described in Section 5.6.
Recovery studies were undertaken to verify the acid extraction-
analysis methodology. Portions of Gelman spectroquality glass
filters were spiked with standard solutions of chromium(VI) or
chromiumdll), dried, and processed through the low temperature
ash-acid extraction scheme (Section 5-5). Analyses were carried
out on the Varian AA-6 atomic absorption instrument as described
in Section 5.7 The results are presented in Table 9-
a
Gelman Instrument Company, P. 0. Box 1448, Ann Arbor, Michigan 48106
bParr Instrument Company, 211 Fifty-Third Street, Moline,
Illinois 61265.
37
-------
Table 9. RECOVERY OF CHROMIUM(VI) AND CHROMIUM(III)
SPIKES PROM HIGH-VOLUME FILTERS
Sample
1
2
3
4
5
6
7
8
Avg. total chromium recovery = 96.0 ±0.8%
Avg. chromium recovery = 96.0 ± 0.8%
These data indicate that while the recovery of total chromium,
regardless of species, is excellent, the recovery of chromium(VI)
through the extraction scheme is low and highly variable-
therefore, the only reliable air sample data are those for total
chromium. Chromium (VI) data should be regarded only as an
indication as to whether hexavalent chromium was present in the
original sample.
Spike !
1
1
1
1
.00
.00
.00
.00
mg
mg
mg
mg
Cr(VI)
Cr(VI)
Cr(VI)
Cr(VI)
Total Cr
£ Recovery
L03
104
104
103
.1
.1
.5
.1
Avg. total chromium recovery =
0
0
0
0
.500
.500
.500
.500
mg
mg
mg
mg
Cr(
III
)
Cr(III)
Cr(
Cr(
III
III
)
)
95
96
97
95
.4
.0
.1
.4
Percent
Recovery
by Species
6.
1.
26.
9.
103.7 ±
95.
96.
97.
95.
5
9
4
1
0.7%
4
0
1
4
38
-------
Chromium(VI) is the highest oxidation state of chromium. When
chromium(VI) oxide is dissolved in water, dichromate (C^Oy2")
is formed at low pH and chromate (CrO^2") is formed at high
pH (7). Dichromate is a powerful oxidizing agent
Cr2072~ + 14H+ + 6e~ >-2Cr3+ + 7 H20 E° = 1.33v
which readily oxidizes organic matter in water, soils and sedi-
ments (8). Chromate is a less powerful oxidizing agent.
CrOi,2" + 4H20 + 3e~ »Cr(OH)3(s) + 50H~ E° = 0.13v
Thus, chromium(VI) should not persist in any medium containing
organic matter at low pH, but it might be stable in natural
matrices at high pH (9). Apparently, there is enough organic
material or other oxidizable material available during the acid
extraction procedure to allow partial conversion of chromium(VT)
to chromium(III).
5.2 ANALYSIS OF SOIL, SEDIMENT, AND SLUDGE SAMPLES
Soil, sediment and sludge samples were transported back to the
laboratory in appropriately labeled plastic sampling bags or
acid-cleaned (1:1 HN03), wide-mouth polyethylene bottles. Upon
arrival at the Dayton Laboratory each sample was removed from
its container and carefully mixed to insure homogeneity. In-
organic and organic matter larger than ^2 mm was removed, and the
sample was placed in an acid-cleaned (1:1 HN03), 100 mm x 80 mm
Pyrex storage jar, and air dried for 48 hours.
(7) Cotton, F. A. and G. Wilkinson, "Advanced Inorganic Chemistry,"
Wiley-Interscience, New York, N.Y., 1966, pp 828-829.
(8) "APHA, Standard Methods for the Examination of Water and Waste-
water," 13th Ed., American Public Health Association, Washington,
D.C., 1971, PP 495-^99.
(9) Pankow, J. P., D. P. Leta, J. W. Lin, S. E. Ohl, W. P. Shum and
G. E. Janaver, "Analysis for Chromium Traces in the Aquatic
Ecosystem," The Science of the Total Environment 1, 17-26 (1977).
39
-------
A portion of the sample was acid extracted (Section 5.5). Total
chromium was determined directly by atomic absorption spectros-
copy (Section 5-7). Much difficulty was encountered when the
APDC/MIBK extraction procedure (Section 5.6) for chromium(VI)
was attempted on the soil extracts. The extremely high iron
matrix that resulted from the acid extraction made the pH adjust-
ment step in the MIBK extraction procedure impossible to perform
without precipitation of iron hydroxide. Initial precipitation
of the iron occurred at a pH between 1.5 and 2.0. APDC quanti-
tatively chelates and extracts iron(III) into MIBK at almost the
same pH as employed in the extraction procedure. Even if the
precipitation of iron hydroxide could be overcome, the large
excess of iron in the sample extract would tie up the majority
of the APDC chelate and thus prevent quantatation extraction
of chromium(VI) into the ketone layer.
In order to overcome this problem an alternate chromium(VI)
separation procedure was developed using a 15 cm x 2 cm Dowex
50W-x8 cation exchange column (Na form). At the low pH of the
sample extract, part of the chromium(VI) would oxidize the cation
exchange resin. The chromium(VT), in turn, would be reduced to
chromium(III) which would be retained by the column. If the
acid extract was first partially neutralized to a pH of 1.0 to
1.5, chromium(VI) would pass through the column (see Table 10).
Iron, chromium(III) and other cations present in the same extract
are retained on the column while chrorrium(VI) , present in solution
in the anionic forms, passes through the column.
-------
Table 10. RECOVERY OF 0.2 mg OP CHROMIUM(VI) THROUGH A
CATION EXCHANGE COLUMN AS A FUNCTION OF pH
Percent
pH Recovery
0.04 89.8
0.01 91.3
0.50 92.1
0.54 93.7
0.98 96.8
1.00 98.4
1.06 96.8
1.48 102.0
1.43 98.2
1.95 101.0
To verify the separation of chromium(VI) by the cation exchange
procedure, exactly 10.00 ml of Hercules soil extract and
10.00 ml of the same extract plus a 1.00-mg spike of chromium(VI)
were first partially neutralized to a pH of 1.0 to 1.5 and passed
through the cation exchange column at a flow rate of about 4
ml/min. Three bed volumes of distilled water followed the sample
through the column to ensure quantitative elution into an acid-
cleaned 100.0-ml volumetric flask. Table 11 summarizes the
recoveries observed for this separation technique.
41
-------
Table 11. RECOVERY OF CHROMIUM(VI) ION
EXCHANGE SEPARATION PROCEDURE
Sample
[Chromium(VI)] in Column
Effluent (mg/1)
Site 5, sample 1
Site 5, sample 1 plus spike
Site 5, sample 2
Site 5, sample 2 plus spike
Site 4, sample 1
Site 4, sample 1 plus spike
Site 4, sample 2
Site 4, sample 2 plus spike
0.21
9-79
2.73
12.5
0.09
10.0
0.36
10.22
Average Recovery =
Percent
Recovery
95.8
97.7
99.9
98.6
.0 ± 1.758
Once the ion exchange separation procedure had been verified,
recovery of chromium species through the acid extraction scheme
(Section 5.5) was determined. Six soil samples, of about 5 g
each, were spiked with chromium(vT) and chromium(III), four with
1.0 mg of chromium(VI), and two with 1.5 mg of chromium(III). The
samples were dried, low temperature ashed, digested for 3 hours
with HC1 and HNOs, filtered, reduced in volume to ^50 ml, and
diluted to 100 ml. A 10-ml aliquot was ion exchanged, then the
effluent was diluted to 100 ml and analyzed by atomic absorption.
The results are shown in Table 12.
Table 12.
Sample
1
2
3
4
5
6
RECOVERY OP CHROMIUM(VI) AND CHROMIUM(III)
SPIKES FOR SOIL SAMPLE
Spike
1.00 mg Cr(VI)
1.00 mg Cr(VI)
1.00 mg Cr(VI)
1.00 mg Cr(VI)
1.5 mg Cr(III)
1.5 mg Cr(III)
Percent Total
Chromium Recovery
89.0
112.3
84.0
121.0
Average = 102.0 ± 17
104.0
107.0
Average = 105-5 ± 1.0
42
Percent
Recovery
by Species
104.0
107.0
-------
The data indicate that total chromium recovery is good by the
procedure; however, the chromium(VI) species is not recovered.
As was shown earlier, the chromium(VI) form is not altered
during the ion exchange step. It must be concluded that the
procedure does result in good total chromium recovery from
soil. However, as with the high-volume filters, the determination
of chromium(VI) is unreliable. As a consequence, the analysis of
chromium(VT) in soil samples was abandoned.
5.3 ANALYSIS OF WATER SAMPLES
Prior to sampling, all glassware and polyethylene sample bottles
were rinsed with 3:1 t^SO^/HNOs or 1:1 HN03 before use. As soon as
possible upon completion of sampling the water samples were
pressure filtered through back-to-back tared 0.45-ym Millipore®
filters. The volume of sample passed through each filter was
measured. The filtrate was stored in the original sample
container which had been thoroughly rinsed, first with distilled
water and then with filtrate. The filtered sample was then
acidified to a pH of 3-5-5.0 with 6M HN03/3M H3PCV The sus-
pended particulate sample was carefully removed from the
Millipore® filtration apparatus and placed In a clean plastic
petri dish for storage until analysis.
Analysis of the water sample for total chromium was performed
directly by atomic absorption spectrometers using a nitrous
oxide-acetylene flame. The analysis for chromium(VI) was per-
formed by using the ADPC/MIBK procedure described in Section 5.6.
The suspended particulate samples were processed according to
the acid extraction procedure described In Section 5-5. In a
few instances, where the acid extraction scheme would not
dissolve the sample, a standard sodium carbonate fusion tech-
nique was employed.
43
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5.4 ANALYSIS PROCEDURE FOR ORGANO-CHROMIUM COMPOUNDS
5.4.1 Air and Water Samples
The XAD resins employed for air and water sampling for organic
chromium compounds were purified in a soxhlet extraction
apparatus prior to sampling. The order of solvents and the
extraction times for each solvent are given in Table 13.
Table 13. PREEXTRACTION ROUTINE FOR XAD RESIN
Solvent Time
Distilled water 24 hr
Methanol 24 hr
Ethyl ether 8 hr
After the extractions with ether, the XAD was transferred to a
vacuum desiccator and dried under vacuum for 24 hours. The XAD
resin was then placed into traps for field sampling.
Upon completion of sampling the XAD resin was removed from the
traps and placed in a previously extracted paper thimble. The
thimble and contents were then soxhlet extracted with 250 ml
of ethyl ether for 4 hours. The volume of ether remaining after
the extraction was determined and the XAD extract was placed in
a tightly sealed glass bottle. Analysis for chromium in the
ethyl ether extract was performed by flameless atomic absorption
spectroscopy.
5.4.2 Sewage Treatment Plant Sludge
Two sludges from sewage treatment plants were processed according
to the ether extraction scheme outlined in Figure 8. The in-
organic fraction was extracted with hydrochloric acid and nitric
44
-------
WEIGHED SAMPLE
add ether, filter
I
I
Ether Solution
extract with
Residue evaporate, weigh
INORGANIC FRACTION
extract with HCI & HN03
I
Ether Layer
extract with 0.1 N HCI
Water Layer
evaporate, weigh
WATER SOLUBLE FRACTION
Ether Layer
extract with 0.1 N NaHCOs
Water Layer
make basic,
extract with ether
I
Ether Layer dry,
evaporate
and weigh
BASE FRACTION
I
Water Layer
discard
Water Layer
make acid
extract with ether
Ether Layer dry, Water Layer
evaporate discard
and weigh
STRONG ACID FRACTION
Ether Layer
extract with 0.1 N NaOH
Water Layer
make acid
Ether La
evap
NEUTRAL
yer dry,
orate
FRACTION
1
1 1
Ether Layer dry, Water Layer
evaporate discard
and weigh
WEAK ACID FRACTION
Figure 8. Liquid Extraction Scheme
for Organic'. Compounds.
-------
acid as described in Section 5.5. Each organic fraction was di-
gested with a 3=1 mixture of H2S(\ and HN03. Pour milliliter of
acid mixture was added to each fraction. The fraction was heated
to fumes, quantitatively transferred to a 25.0-ml volumetric fla,;k,
diluted with distilled, deionized water, and analyzed by atomic
absorption.
5.5 SAMPLE PREPARATION - ACID EXTRACTION PROCEDURE
The procedure herein described is a modification of that des-
cribed by Thompson, Morgan and Perdue (10). This procedure was
used to extract chromium from soil, high-volume air filters and
water-insoluble suspended particulate.
Procedure
Soil (15 g), a portion of a high-volume filter (17.8 cm x 5.0 cm1,
or a filter containing water-insoluble particulate was dried at
60°C to constant weight, placed in a Pyrex boat and low tempera-
ture ashed at 425 watts in an LFE Corp.a LTA-505 Low Temperature
Asher until the plasma discharge reverted to a blue color,
indicating completion of ashing. The time required varied not
only from sample type to sample type but from sample to sample
within each type. Typical ashing times for each sample type are
given in Table 14.
(10) Thompson, R. J., G. B. Morgan, and L. J. Perdue, "Analysis
of Selected Elements in Atmospheric Particulate Matter by
Atomic Absorption," Atomic Absorption Newsletter 9, 53-57
(1970).
aLFE Corporation, Process Control Division, 1601 Trapelo Road,
Waltham, Massachusetts 02154.
46
-------
Table 14. TYPICAL ASHING TIMES FOR
ENVIRONMENTAL SAMPLES
Sample Typical Ashing Time (hr)
Soil 24
High-volume filters 2
Water-suspended particulate 1
Depending upon their physical state, the ashed samples were ex-
tracted by different methods using the apparatus shown in
Figure 9. Samples which were permeable to the refluxing acid
vapors (high-volume filters) were quantitatively transferred to
a 25-mm Pyrex extraction thimble (coarse grade). The extraction
thimble was then placed into the extraction apparatus shown in
Figure 9 which had been previously charged with 8 ml of 19$ HC1
and 32 ml of 40$ HN03. The flask was fitted with an Allihn
condenser. The acid was refluxed over the sample for 3 hours.
The Allihn condenser was removed and tbe acid extract was
concentrated to 20 ml on a hotplate. The samples which exhibited
a low permeability to the refluxing acid (soil, sediment) were
placed directly into the flask. After extraction was complete
these samples were quantitatively filtered prior to the concentra-
tion step. After cooling, the acid concentrates of all samples
were quantitatively transferred to 100-ml volumetric flasks,
diluted with distilled water, and transferred to 200-ml poly-
ethylene sample bottles for storage until analyzed.
47
-------
A
iAllihn Condenser
Glass Extraction Thimble
Coarse Porosity
Modified 250 ml Round
Bottom Flask
Figure 9. Acid Extraction Apparatus.
-------
5.6 METHYL ISOBUTYL KETONE/AMMONIA PYRROLIDINE DIETHIOCARBAMATE
EXTRACTION PROCEDURE FOR CHROMIUMTvT)
The procedure is a modification of that described by Midgett
and Fishman (11) where the major change was that the extraction
was carried out in ^60 ml bottles or screw-top test tubes. The
methyl isobutyl ketone (MIBK) was distilled in glass and ob-
tained from Burdick and Jackson Laboratories, Inc.a A 5$
solution of ammonium pyrrolidine dithiocarbamate (APDC) was
prepared fresh daily by dissolving 5.0 g of APDC in 100 ml of
distilled deionized water and extracting the solution with
successive portions of MIBK until the orgnic layer was clean.
Normal sodium hydroxide (NaOH) was prepared by dissolving 40 g
of NaOH in distilled deionized water and diluting to exactly
1 liter. Tenth normal NaOH was prepared by pipeting 10.0 ml of
l.ON NaOH into a 100.0-ml volumetric flask and diluting to the
mark with distilled deionized water. Tenth normal nitric acid
(HNOs) was prepared by pipeting 6.4 ml of concentrated nitric
acid into a 2-liter volumetric flask and diluting to the mark
with distilled deionized water. Methyl violet indicator (0.1$)
was prepared by dissolving 0.1 g of the indicator in 50 ml of
95$ ethanol and diluting to 100.0 ml with distilled deionized
water.
The determination of chromium(VI) in sample extracts or water was
accomplished by first pipetting exactly 20.0 ml of sample into
an acid-cleaned 60 ml bottle. After adding 2 drops of 0.1$
(11) Midgett, M. R. and M. J. Pishman, "Determination of Total
Chromium in Fresh Waters by Atomic Absorption," Atomic
Absorption Newsletter 6_, 128-131 (1967).
aBurdick and Jackson Laboratories, Inc., 1953 S. Harvey Street,
Muskegon, Michigan 49442.
49
-------
methyl violet indicator, either NaOH or HN03 was added until the in-
dicator changed from yellow to blue-blue green (pH - 2.4-2.6). Then,
5.0 ml of 5% APDC solution, 3.0 ml of saturated NajSO^ solution,
and 20.0 ml of MIBK were pipetted into the 60 ml bottle. The
bottle was tightly capped and shaken on a wrist-action shaker
for 3-5 minutes. The chromium(VI) was then determined by aspira-
tion of the top organic layer into the C2H2/air flame of the
Varian AA-6 atomic absorption spectrophotometer. The concentra-
tion of chromium(VI) was obtained from a suitable calibration
curve prepared by extracting standard solutions employing the
same procedure.
In some cases where low levels of chromium in water were suspected,
a 2-liter portion of the water sample was extracted by this pro-
cedure using a separatory funnel.
5.7 VARIAN AA-6 INSTRUMENT PARAMETERS FOR CHROMIUM
Chromium can be determined by atomic absorption spectroscopy em-
ploying either an air-acetylene or nitrous oxide-acetylene flame.
In this study air-acetylene flames were used except when a nitrous
oxide-acetylene flame was required to reduce interference by
cobalt, nickel, iron, copper, barium, aluminum, magnesium,
calcium, etc., which were present in some sample matrices. All
of the total chromium data for soil, water and filter samples
were obtained using the nitrous oxide-acetylene flame. An air-
acetylene flame was employed for the determination of chromium(VI)
via the MIBK/APDC extraction procedure. Figures 10 and 11 show
the typical calibration curves obtained by each technique.
Table 15 presents the instrument parameters employed on the
Varian AA-6 spectrometer.
50
-------
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Figure 11.
0.2 0.4 0.6 0.8
Cr (VI) Concentration, mq/t,
1.0
Calibration Curve for Cr(VI) by Atomic
Absorption (N20/C2H2 Flame).
-------
Table 15. INSTRUMENT PARAMETERS FOR VARIAN AA-6
Wavelength - 357-9 nm
Spectral band pass - 0.2 nm
Lamp current - 5 mA
Flame conditions: N20/C2H2 Alr/C2H2
Fuel setting (M-80 gas box) 6.5 1.5
Oxldant setting (M-80 gas box) 5.3 5.3
Detection limit 0.005 mg/1 0.005 mg/1
53
-------
6. REFERENCES
1. Suprenant, Norman, Robert Hall, Steven Slater, Thomas Suza,
Martin Sussman and Charles Young. "Preliminary Emissions
Assessment of Conventional Stationary Combustion Systems,"
EPA 600/2-76-046b, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, January 1976, p. 79.
2. Reznik, Richard B. "Source Assessment: Flat Glass Manufacturing
Plants," EPA 600/2-76-032b March 1976, pgs. 122-126.
3. "Thomas Register, 1975," Thomas Publishing Co., New York,
N.Y., 1975, PP 8787-8788.
4. Martin, D. 0. and J. A. Tikvart, "A General Atmospheric Diffusion
Model for Estimating the Effects of Air Quality of One or More
Sources," presented at the 6lst Annual Meeting of the Air
Pollution Control Association, St. Paul, Minnesota, June 23-27,
1968, 18 pp.
5. Busse, A. D. and J. R. Zimmerman, "User's Guide for the Clima-
tological Dispersion Model" EPA-R4-73-025 U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina,
December 1973.
6. Toepfor, E. W., W. Mertz, M. M. Polansky, E. E. Roginski, and
W. R. Wolf, "Preparation of Chromium-Containing Material of
Glucose Tolerance Factor Activity from Brewer's Yeast Extracts
and by Synthesis," Journal of Agricultural and Food Chemistry
25, 162-166 (1977).
7. Cotton, F. A. and G. Wilkinson, "Advanced Inorganic Chemistry,"
Wiley-Interscience, New York, N.Y., 1966, pp 828-829.
8. "APHA, Standard Methods for the Examination of Water and Waste-
water," 13th Ed. American Public Health Association, Washington,
D.C., 1971, PP ^95-499.
9. Pankow, J. F., D. P. Leta, J. W. Lin, S. E. Ohl, W. P. Shum and
G. E. Janaver, "Analysis for Chromium Traces in the Aquatic
Ecosystem," The Science of the Total Environment 1, 17-26 (1977).
55
-------
10. Thompson, R. J., G. B. Morgan, and L. J. Perdue, "Analysis
of Selected Elements in Atmospheric Particulate Matter by
Atomic Absorption," Atomic Absorption Newsletter 9, 53-57
(1970).
11. Midgett, M. R. and M. J. Fishman, "Determination of Total
Chromium in Fresh Waters by Atomic Absorption," Atomic
Absorption Newsletter 6_, 128-131 (1967).
-------
APPENDIX A
SAMPLING AND ANALYSIS OP CHROMIUM AND
LEAD AT MINERAL PIGMENTS CORPORATION,
BELTSVILLE, MARYLAND
Mineral Pigments Corporation
7011 Muirkirk Road
Beltsville, Maryland 20705
-------
1. PRESAMPLING SURVEY
Mineral Pigments Corporation, 7011 Muirkirk Road, Beltsville,
Maryland 20705, was chosen for a presampling survey as a typical
chromium pigment producer in accord with two criteria discussed
in the body of this report (2.2.1). A survey visit was con-
ducted on 18 and 19 August 1976 by MRC personnel. Mr. Fred
Wroczonski, Vice President and Mr. Hassan Allah, Plant Super-
intendent, were contacted and through-their cooperation a descrip-
tion of the processes inside the plant was obtained and the
emissions control system was observed. The plant makes chromium
oxide, lead chromate, molybdate orange and zinc chromate pigments.
Some processes are continuous but others are run by the batch.
Normally, the plant operates 24 hour/day, 6 days/week.
The plant site is about 3 km north of Beltsville, Maryland which
is in turn just north of the 1-495 beltway surrounding Washington,
B.C. The area surrounding the plant is wooded and the terrain
is that of rolling hills. The area is rural with little con-
centration of population in the immediate vicinity of the plant.
Beltsville itself is not heavily industrialized.
The plant consists of a collection of buildings, many of which
show stains of yellow or green pigments, especially on their
roofs. The buildings occupy a lot estimated to be 100 m x 200 m
which is bordered on the west by a railroad, on the north by a
two-laned paved road (Old Baltimore Pike), on the east by a
paved access street to an industrial park and on the south by an
unpaved alley which provides a driveway for three occupied homes.
The industrial park to the south of the plant site is mainly
warehouses and there is no industry which should constitute a
A-l
-------
a major chromium or lead emission. The railroad and adjacent
highways may cause some heavy metal (e.g. Pb) emissions. One of
two warehouses had dumped large amounts of vermiculite (discarded
packing material) in the area and this material may affect
some of the soil and sediment characteristics. The terrain to
the northeast of the plant is level and occupied by a junk car
lot, a brick manufacturing facility and a claypit. No visible
emission points were observed from the brick manufacturing
operation.
During the visit, no visible air emissions were observed. This
was also the case during the actual sampling period 28-29 October
but a clearly visible yellow plume was observed from a rooftop
steam vent for several days during an aborted sampling attempt on
21-22 October 1976. At this time, the air emission had prompted
D. W. Palmer of the Maryland Department of Health and Mental
Hygiene, Bureau of Air Quality, (331-383-3^7), to temporarily
halt that process within the plant while new scrubbers were
installed.
The plant has three air emission points, all of which are con-
trolled by scrubbers. Two of these are rooftop vents approxi-
mately 7-6 m from the ground and the third is a chromium oxide
kiln stack about 23 m in height. At the time of the 21-22 October
visit, the kiln was not in operation but it was in operation during
the sampling period.
Also during the aborted sampling visit of 21-22 October, Mr.
P. A. Sleeger of the Maryland Water Resources Administration,
(301-267-5551), showed the sampling party the liquid outfall from
the plant.
Wastewater treatment consists of double clarifying with alum and
flocculants and a sump at the southwest corner of the lot. The
A-2
-------
sump did not appear to be an integral part of the treatment
system but rather appeared to be used to hold runoff from the
yard and occasional gross discharges from the plant. The outfall
which is usually turbid and yellow in color passes over a V-notch
and falls into an underground storm drain at the southwest corner
of the lot. It follows the storm drain for about 150 m, past
one surface-access manhole, and empties just below the water
level into an unnamed stream which is nominally 2 to 3 m wide
and 5 to 10 cm deep. It is estimated that the outfall is
about 10% of the creek flow at this point. The creek runs to
the south parallel to the railroad in a broad, rocky streambed
with very little organic material or aquatic life. Approximately
1 km from the plant the stream flows into a broad, shallow pond/
marsh where cattails, grass, and algae scum are observed. Above
the plant outfall there is considerable organic material in the
water and on the bottom, but the stream below the outfall is not
inhabited by water plants and algae until the pond/marsh is
reached. Occasionally, yellow colored patches of sediment are
observed at points along the streambed over a kilometer below
the outfall.
Soon after the presampling survey articles published in the Wash-
ington Post (1) Indicated that the Mineral Pigments plant was under
close surveillance by the Occupational Safety and Health Admini-
stration for alleged violations of federal health and safety
standards for lead exposure. Dr. Vincent DeCarlo, the Contract
Project Officer, requested that the Beltsville, Md. site be sampled,
After one sampling trip (21-22 October) during which the plant was
shut down, sampling was accomplished on 28 and 29 October 1976.
(1) Washington Post, Monday, September 13, 1976 pp A1-A2,
A-3
-------
2. SAMPLING AND ANALYSIS
2.1 AIR SAMPLES
The air sampling tactics employed at this site involved setting
up a downwind array of high-volume samplers to sample the plume
during a period of steady wind conditions and the use of a group
of perimeter high-volume sampler to collect emissions over a
longer (24 hour) period during which wind conditions have a
larger variability. The array arrangements are shown in Figures 1
and 2. The downwind array (samplers 5-8, with sampler 1 serving
as a background sampler) was set up after observing the existing
wind patterns and assessing the atmospheric stability class
as discussed in Section 3.1 of the main report. These data were
used in the Martin-Tikvart (2) air diffusion model to calculate
the emission rate of the plant. From the observed plume sampling
results, the emission rates for Cr and Pb were 18 mg/s and 49 mg/s,
respectively. These values apply primarily to the rooftop vents
and do not include the Cr(III) emissions from the kiln stack.
During the plume sampling, the wind held strongly at 305 degrees
for 260 minutes with maximum deflections of +22° and -25°. The
wind velocity (10 m high) was 7.6 km/hr ranging from less than
5 to a maximum of 24 km/hr.
The plume sampling was discontinued after 260 minutes when the
wind direction drifted off the downwind sampler array. At that
point, the filters on samplers 1 and 8 were replaced and sam-
(2) Martin, D. 0., and J. A. Tikvart "A General Atmospheric Diffusion
Model for Estimating the Effects on Air Quality of One or More
Species," presented at the 6lst Annual Meeting of the Air Pollutio
Control Association, St. Paul, Minnesota June 25-27, 1968 18 pp.
A-4
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piers 1, 2, 4 and 8 represented the perimeter samplers for a
total sampling period of 24 hours. Results from the two filters
employed on samplers 1 and 8 were summed in order to obtain the
perimeter chromium and lead loading over the full 24-hour period.
(Note that sampler 8 was substituted for 3 in the ideal perimeter
array presented in Figure 2).
Each of the downwind plume array samplers collected 295 m3 of
air over the downwind sampling period while samplers 1, 2, 4 and
8 collected 1609 m3, 1736 m3, 1724 m3 and 1592 m3 of air,
respectively, over the perimeter sampling period. The average
barometric pressure during the sampling period was 1.01 atmospheres
and the wet and dry bulb temperatures were 4l°P and 49°F,
respectively.
Table 1 presented the lead and total chromium results in mg/m3
at each of the sampling locations. As one would expect, the
downwind array collected a much greater concentration of airborn
lead and chromium than did the perimeter samplers with the maxi-
mum concentration found on the centerline samplers (samplers #5
and #7). The upwind sampler (#1) did not collect a measurable
quantity of either lead or chromium. Since the total particulate
emissions include lead chromate, zinc chromate and chromic oxide,
no attempt has been made to further interpret the lead/chromium
ratios in the analysis of the airborne particulate. It should be
noted that the array was positioned so that emissions from the
roof vents would be collected rather than from the chromium
oxide kiln stack. The rationale employed in this decision was
that the emissions from the kiln stack would be primarily tri-
valent chromium and not hexavalent chromium or lead which are
of greater concern from a health hazards viewpoint.
The diffusion model predicts maximum ground level particulate
concentrations from the kiln stack at about 1.6 km from the
A-7
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A-8
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plant site. The roofline sources, on the other hand, would yield
maximum ground level concentrations less than 30 m from the
point of emission. One evidence for this effect can be noted in
the analysis results on the #5 and #7 filters where the lead
concentration is decreasing with distance from the plant while
the chromium concentration is increasing. From the diffusion
model one would expect a drop off in concentration by a factor of
19% from 120 m to 150 m for particulate emitted from the roof
vents. This compares with an experimental drop off of 17$ between
125 m and 150 m.
As discussed in the body of this report, the values for concentra-
tion of Cr(VI) are not meaningful since Cr(VI) was converted to
Cr(III) in the acid digestion step of the analysis. The values
for Cr(VT) are included here only as an indication that some
hexavalent chromium was present in the initial samples.
2.2 WATER SAMPLES
The water samplers were set up as shown in Figures 3 and 4. A
sample of the effluent was obtained before it entered the ground
(Site No. 1). Sites 2, 3 and 4 were taken in the stream before
it enters the pond. Site No. 5 was taken after the pond.
The water sampling results are listed in Table 2. Since acid
digestion was not required in this case, the Cr(VI) results
are valid. These results represent the soluble species while
the suspended species results are shown in Table 3. Examination
of the Pb/Cr atom ratio in the suspended particulate indicate that
this material is not PbCrO^ (Pb/Cr=1.0).
2.3 SEDIMENT SAMPLES
Samples of stream sediment were taken at the same location as the
water samples with the exception of the plant effluent sample
A-9
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Site #2
Site #3
Site #4
Site #5
Table 2
Water Sampling Results
Total Pb
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<0.05
<0.05
<0.05
<0.95
<0.05
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3-23
3.32
2.51
1.76
0.92
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0.85
0.21
0.82
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0.34
0.12
0.89
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Site #1
Site #2
Site #3
Site #4
Site #5
Table 3
Particulate in Water
Total Pb
mg/1
34.1
18.4
2.5
1.41
0.089
Total Cr
mg/1
59.6
3.98
6.98
1.31
0.084
Atom Ratio
Pb/Gr
1:7-0
1:0.9
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1:3.7
1:3.8
A-12
-------
site (#1). These locations are shown on the topographic map in
Figure 5, and on a sketch in Figure 6.
The results of the sediment sampling are listed in Table 4. These
results also indicate that chromium in the sediment is not in
the form of
Table 4
Sediment Sampling Results
Total Cr atom ratio
yg/g Pb/Cr _
43.8 1:6.6
568.3 1:3.0
64.9 1:2.3
64.66 1:3.8
Sample
Site #1
Site #2
Site #3
Site #4
2.4 SOIL
Total Pb
yg/g
26.4
750.2
111.7
68.1
SAMPLES
The optimum sampling sites for soil samples at Mineral Pigments
Corporation were predicted by the diffusion model. Ground level
concentration isophleths around the plant site were predicted
from seasonal and annual meteorological data for both the roofline
emission points and the kiln stack effluent. Areas of maximum
ground level concentration were predicted at 1° and 157° from
due north. Figure 7 presents the soil sample sites on the
topographical map and Figure 8 shows them on the plant diagram.
Sites #1 and #2 were located 120 m and 370 m respectively from
the plant on the 157° line. Sites #3 and #5 were located 490 m
and 120 m respectively from the plant on the 1° line. Site #4
was located 210 m from the plant on a 280° line and was taken
to serve as background. The soil sampling results are shown in
Table 5. All soil samples were taken to the same depth (7.6 cm).
A-13
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The soil type was similar in all areas sampled with a ground
cover of grass.
Table 5
Soil Sampling Results
Sample Total Pb (ug/g) Total Cr (_yg/g)
Site #1 26.15 22.77
Site #2 51.97 30.62
Site #3 220.3 28.95
Site #4 32.9 27.8
Site #5 301.6 41.32
When one compares these data with trends predicted by the dif-
fusion model, a discrepancy is apparent. The model would predict
higher soil concentrations of lead at Site #1 compared to
Site #2. This discrepancy is most probably due to historical
automobile traffic on Old Baltimore Pike where the #2 soil
sample was taken.
A-18
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APPENDIX B
SAMPLING AND ANALYSIS OF CHROMIUM AT
HERCULES, INCORPORATED,
GLENS FALLS, NEW YORK
Hercules, Incorporated
Lower Warren Street
Glens Falls, New York 12801
-------
1. PRESAMPLING SURVEY
1.1 Description of the Plant Site
Hercules, Inc., located on Lower Warren Street In Glens Falls, N.Y.
was chosen for a presampling survey as a typical chromium
pigment producer in accord with the criteria discussed in the
body of this report (2.2.1). A survey visit was conducted on
15 Septebmer 1976 by personnel of Monsanto Research Corpora-
tion (MRC). Contacts were made with Mr. Gary Dunn, Assistant
Plant Manager. The plant management chose not to cooperate with
the MRC personnel during the survey visit. As a consequence,
little information was obtained about plant processes and
operations.
The original facility was constructed in 1900, and the produc-
tion of chromium pigments was started in 1920. The plant
produces chromium oxide, lead chromate, molybdate orange, zinc
chromate and compounded chrome pigments. Normally, the plant
is in continuous operation (24 hours/day, 7 days/week).
Numerous buildings, some of which are interconnected, comprise
the plant facility. The buildings are located on a lot esti-
mated to be 150 m x 900 m. Approximately 2/3 of the northern
boundary is adjacent to the Glens Palls Feeder Canal, whereas
1/3 of the boundary is next to Route 254. Route 32 is
immediately north and adjacent to the Glens Falls Feeder Canal
and intersects Route 254 on the northern side of the canal and
immediately north of the major concentration of plant buildings.
The east section of the lot is a large automobile parking area
and is bounded partially by a gully (approximately 5 meter
depresssion) which can serve as a storm drain and by a driveway
B-l
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serving a single family dwelling. The southern border is the
Hudson River. On the west is a paved, two-lane road which
provides access to a portland cement plant and a quarry. Figure 1
shows the plant location (shaded) on a topographic map.
The plant is located on the flood plain of the Hudson River. A
railroad spur track is located on the south side of the plant
within the Hercules, Inc. property between the river and the
major grouping of buildings. The general area to the north of
the plant contains open fields bounded by trees, and small
businesses and some single family dwellings adjacent to Route 32.
To the east are located rows of houses paralleling Route 254.
Gravel pits and quarries are located to the east, west and
southwest. Located on the same floodplain and upstream of the
Hercules, Inc. plant to the west are a portland cement plant and
a sewage disposal facility.
Emissions from the cement plant and quarries can potentially
affect the soil and sediment characteristics of the area. The
effect of the sewage disposal facility on the water and sediment
are unknown and would depend on the types of waste processed at
the facility, the methods of disposal, and the efficiency of
its operation.
During the visit, intermittent (approximately every 20 min)
orange and yellow plumes (duration of approximately 4 min) were
observed as emissions from 2 stacks. Building roofs and
certain stacks were yellow and orange in color. Several steam
plumes and a plume from a large boiler plant stack were also
visible. One local resident located just north of the plant
complained that the black shingles on his roof are turning
green and that snow during the winter turns blue around the
plant.
B-2
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-------
Actual emission points are not known because of lack of coopera-
tion from the plant management. There are roof-type stacks with
a total height of approximately 15 m from the ground. The
boiler stack is approximately 45 m in height. No control devices
were visible; lack of cooperation from plant personnel precludes
knowledge of whether or not any exist.
The wastewater treatment facility was installed two years ago.
Process wastes are neutralized (pH ^7) by lime treatment;
Cr(VI) is reduced by using S02. Water effluent from the treatment
process is discharged continuously into the Hudson River at a
rate of approximately 13000 m3/day. Sludge generated in the
treatment plant is retained on-site in a land-fill.
Outfall is discharged from a concrete pipe having an internal
diameter of approximately 1 m. The water cascades down the
river bank (approximately 8 m drop) into the Hudson River. The
outfall flow is extremely rapid. At the point of plant dis-
charge, the river is divided by an island; the river branch
(approximately 15 m in width) passing the outfall moves slowly.
Other than a small amount of pink foam, no irregular characteris-
tics, e.g., color and turbidity, were noted at the outfall.
1.2 Description of Surrounding Area
The Hercules, Inc. plant is located in Glens Palls, N.Y. on
the Hudson River approximately 70 kilometers north of Albany, N.Y.
and 3-5 kilometers east of Interstate 8?. The general area is rural
and forested and the topography is hilly. Population is located
principally along the Hudson River in two cities, Glens Palls
(pop. 17,222) and Hudson Falls (pop. 7,997). A General Electric
plant is located in Hudson Falls and pulp and paper industry
exists throughout the area.
B-4
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2. SAMPLING AND ANALYSIS RESULTS
Sampling of the Hercules, Inc. site was conducted on October 5-6,
1976. The types, conditions, locations and results for the
samples collected during this time are contained in the
following subsections.
2.1 Air Samples
The location of the plant site and the surrounding topography
greatly limited the area in which the air sampling array
(Section 3.1 of main report) could be assembled. This meant
that only under very specific wind conditions could such an
array be used. Unfortunately, lack of wind or improper direc-
tion precluded the use of the sampling array during the dates
sampled. Due to the unfavorable conditions an alternative array
of samplers that roughly surrounded the plant site was decided
upon.
The locations of the high volume samplers are indicated on a
topographical map (Figure 2) and a site sketch (Figure 3). Sampler 1
was located to the south of the plant site near a quarry on the op-
posite side of the Hudson River. Sampler 2 was located on the west
perimeter of the site between the plant boundary and the portland
cement access road. Samplers 3 and 6 were located to the north
just across highway 32 from the plant and west of the intersection
of highways 32 and 254. Sampler 8 was located to the north across
highway 254 east of the intersection. Sampler 4 was located on the
east perimeter across the small gully (see site description
Section 1.1) on the north bank of the Hudson River. Samplers 5
and 7 were not used during the sampling period. Sampling times
B-5
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ranged from 25.50 hours (1733 m3) to 28.25 hours (1919 m3).
Wind data were obtained during the sampling period, and a
wind rose calculated from these data is included in
Figure 3.
The results from the analyses of the air samples are contained In
Table 1 and Figure 3. The highest total Cr concentration was
obtained at Sites #8 and #3 which are north of the main building
concentration. However, Site #6, also north, showed relatively
low total Cr concentration. There seems to be no general
correlation between the wind rose and the values obtained. The
values for Cr(vT) should be taken only as an indication of its
presence and not as true concentrations due to conversion of
Cr(VI) to Cr(III) in the preanalysis acid extraction procedure
(see Section 5.1 of main report).
Table 1
Air Sampling Results
Sample Total Cr (yg/m3) Cr(VI) (yg/m3)
Site #1 0.14 0.10
Site #2 0.12 0.085
Site #3 0-37 0.004
Site #4 0.045 <0.002
Site #6 0.072 <0.002
Site #8 0.56 0.018
B-7
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2.2 Water Samples
Water sampling sites were selected along the north side of the
Hudson River as indicated on the topographical map (Figure 4)
and the site sketch (Figure 5). Site #1 was located at the
plant outfall. Site #2 was located approximately three stream
widths (^45 m) downstream of the outfall at a point near the
intersection of the streams flowing around the small island
that is opposite the outfall. Site #3 was located approximately
six stream widths (^90 m) downstream at the east perimeter of
the plant site. Site #4 was located approximately 250 m upstream
at the west perimeter of the plant site (at this point the
Hudson River flows in a single channel).
Samples of approximately four liters were collected at each site
using 2 types of commercial water samplers (Manning and Isco).
Also employed was a water sampler designed by MRC which is dis-
cussed in Section 4.2 of the main body of the report.
Suspended particulate samples were obtained by filtering the
water samples through an 0.45 ym Millipore® filter as described
in Section 4.2 of the main report. Analyses were performed as
described in Section 5.3 of the main report.
The results for the water analyses (dissolved Cr) are shown
in Table 2 and Figure 5. In all instances both the total
chromium and Cr(VI) concentrations were below the detection
limits of 0.05 mg/1 and 0.0025 mg/1 respectively. The total
Cr results for suspended particulates are given in Table 3.
The results are erratic showing measurable values at the out-
fall (Site #1, 23.6 pg/l)and Site #3, (28.0 yg/1) but values
below detection limits at Sites #4 and #2. It is conceivable
that irregular flow patterns created by the several small
islands in the river could create the seemingly uncorrelatable
results.
B-9
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Table 2
Water Sampling Results
Sample Total Cr (mg/1) Cr(VI) (mg/1)
Site #1 <0.05 <0.0025
Site #2 <0.05 <0.0025
Site #3 <0.05 <0.0025
Site #4 <0.05 <0.0025
Table 3
Particulates in Water
Sample Total Cr (ug/1)
Site #1 23.6
Site #2 <10.0
Site #3 28.0
Site #4 <10.0
B-12
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2.3 Sediment Samples
Sediment samples (approximately 100 ml each) were collected at
the same locations as the water samples (Figures 4 and 5)
according to the procedure described in Section ^.3 of the main
report. Analyses were performed according to the procedure
described in Section 5.2 of the main report.
The results from the analyses of these samples are given in
Table 4. The upstream sampling site (Site #4) showed the lowest
total Cr value (0.019 mg/g) while sites #1, #2, and #3 showed
the opposite trend to that observed for the suspended particulate
results. A possible explanation that is consistent with both
the suspended particulate and sediment results is that Site #2 is
located at a point of relatively low turbulence resulting in
the settling out of particulate matter with attendant low sus-
pended particulate Cr values and high (relative to Sites #1 and
Table 4
Sediment Sampling Results
Sample Total Cr (mg/g)
Site #1 0.823
Site #2 3.59
Site #3 1.714
Site #4 0.019
B-13
-------
#3) sediment values, while Sites #1 and #3 are located at points
of higher turbulence resulting in larger amounts of suspended
particulates and relatively lower concentrations of Cr in the
sediment. Certainly this is the case at the outfall (Site #1)
due to the turbulence it creates. The other variations of tur-
bulence could be created by the flow around the several small
islands as cited earlier.
2.4 Soil Samples
The optimum soil sampling sites for the Hercules, Inc. plant
were predicted on the basis of the diffusion model (see
Section 3-3 of main report) which indicated a maximum concentra-
tion area at 23° (relative to due north) and a Secondary concentration
at l60°. The locations of the soil sampling sites are indicated
on the topographical map (Figure 6) and the site sketch (Figure v).
These sites were positioned relative to the main boiler stack
since it was a convenient visual point of reference. Site #1
was located at 180° at a distance of ^600 m in a forest near
the quarry on the opposite side of the Hudson River. Site #2
was located at 255° at a distance of ^550 m in a field between
Hercules and the portland cement plant. Sites #3 and #4 were
located at 23° to sample the predicted maximum concentration
area at various distances. Site #3 was at a distance of ^100 m
next to Route 254 opposite the plant, while Site #4 was at a
distance of ^400 m in the yard of an old house. Site #5
was located at 160° at a distance of ^45 m between the railroad
track and the river. This site was chosen to sample the predicted
secondary concentration. The samples were collected and analyzed
as described in Sections 4.3 and 5.2, respectively, of the main
report.
The results from the analyses of the soil samples are given in
Table 5 and Figure 7. As expected, Site #2, which lies the
furthest from any predicted concentration maximum, had the lowest
B-14
-------
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total Cr concentration in the soil. The other four sites seem
to follow a trend based on relative distance from the plant.
Site #5, which was located along the predicted line of secondary
concentration, had a higher total Cr concentration than Site #3
which was located along the predicted line of primary concentra-
tion. The explanation for this result probably lies in the
fact that Site #5 is closer than Site #3 to the plant (45 m com-
pared to 100 m). The fall off in concentration with distance
can be seen by comparing the results from Sites #3 and #4.
Table 5
Soil Sampling Results
Sample Total Cr (mg/g)
Site #1 0.329
Site #2 0.0473
Site #3 1.49
Site #4 0.428
Site #5 2.02
B-17
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APPENDIX C
SAMPLING AND ANALYSIS OP CHROMIUM AT
STOLLE CORPORATION
DAYTON, OHIO
Stolle Corporation
1525 West River Road
Dayton, Ohio
-------
1. PRESAMPLING SURVEY
1.1 Description of the Plant Site
The Stolle Corporation, 1525 West River Road, Dayton, Ohio was
chosen for a presampling survey as a typical chromium plating
facility in accord with the criteria presented in the body of
this report (2.2.2). Contacts were made with Mr. Al Lemon,
Plant Superintendant. The plant management decided not to co-
operate with MRC personnel during the study. Although no
information was directly available concerning the plant processes,
certain pertinent information was obtained from the NPDES permit.
According to the NPDES permit information (supplied in 197^0,
Stolle Corporation has 70 employees and operates on a 16 hour/
day, 5 day/week schedule. Their business consists of all types
of metal polishing, plating processes involving copper, nickel
and chrome and anodizing aluminum. An indication of the volume
of chrome plating done at the facility is given by the reported
amounts of chromic acid (4,160 kg) and potassium chromate (90 kg)
used during the period from January to June 197^. Their customers
include automobile and household appliance manufacturers and
various tool and die shops in the area.
The plant site is approximately 150 m x 180 m and consists of
one large building and three holding ponds. It is bounded on
the north by a construction equipment storage yard and a single
residence dwelling, on the east and south by West River Road
and the Great Miami River, on the southwest by a large open field
and on the west by a railroad track, Danner Road and Madden
Golf Course. Downstream at a distance of ^1000 m is the City
C-l
-------
of Dayton, Guthrie Road Wastewater Treatment Plant. The Dayton
Power and Light Company's Tate Station electrical generating
facility is located ^1 km upstream of the Stolle plant site.
The Tate Station Power Plant is a coal burning facility and
thus has potential for producing chromium emissions (Section 2.1.1
of main report) . It is not known what contribution these might
have on the samples taken in this study. The greatest likelihood
for contamination from this source is in the soil samples which
would reflect long-term contributions. However, since the Stolle
Corporation site is to the southwest of the power plant and the
prevailing winds are from the west and southwest, the likelihood
of significant Cr contamination from the power plant is minimal.
There is no other industry in the immediate area that would pre-
sent possible Cr contamination.
There are several visible rooftop vents (air emission points) on
the building, and white plumes (probably from heating) were ob-
served during the time that air samples were being collected on
February 10-11, 1977- No information was available concerning
the presence or types of control devices on air emission points.
All chrome rinses are reportedly treated with the "chromalator
process." The steps of the treatment include addition of sodium
hyposulfite, pH adjustment (to 6-9), and discharge into a
settling pond. The contents of the settling pond are released
over a period of ^8 hours. The treated wastewater is piped
^1200 m and discharged into the effluent stream from the Guthrie
Road Wastewater Treatment Plant at a point ^50 m from where
the treatment plant effluent enters the Great Miami River. The
wasfcewater had a green color at the point of discharge. The dis-
charge pipe and the wall of the treatment plant effluent channel
near the discharge pipe are a distinctive dark green color. The
total wastewater discharge from the Stolle plant is ^1200 m3/day
C-2
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which is diluted by the 210,000-230,000 m3/day outfall from the
Guthrie Road treatment plant before finally being discharged ini o
the Great Miami River.
1. 2 Description of Surrounding Area
The Stolle Corporation plant is located in the southwestern
metropolitan Dayton, Ohio area approximately 15 km south of
the intersection of Interstates 70 and 75. The immediate area
around the Stolle Corporation site has a relatively low
population concentration which increases as one moves toward the
Dayton population center. Dayton is located in a river valley
at the junction of the Miami, Mad, and Stillwater rivers. The
general topography is flat. The metropolitan area has a popu-
lation of ^865,000 and supports an impressive diversity of
industry. There are some 850 plants located in Montgomery County
producing over 1000 products with an estimated value of over
$1 billion. Major industries in the area include automotive
subassembly, appliance manufacturing and precision equipment.
C-3
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2. SAMPLING AND ANALYSIS RESULTS
Sampling of the Stolle Corporation site was conducted on
September 14-15, 1976 (water, sediment, and soil) and
February 10-11, 1977 (air). The types, conditions, locations
and results for the samples collected during these times are
contained in the following subsections.
2.1 Air Samples
Figure 1 is an aerial view of the site with the positions of the
air samplers indicated by the numbers in white. The air sampling
array described in Section 3-1 and Figure 3 of the main report
was used in sampling the Stolle Corporation site. The four-
sampler downwind array (samplers 3, 4, 5 and 6) was positioned
in the adjoining construction equipment lot with array dimensions
indicated in Figure 2. The downwind array samplers were operated
for periods ranging from 4.25 hours (288.7 m3) to 5.83 hours
x
(396 m3). Wind data collected at 5 minute intervals during the
sampling period showed an average wind velocity of 11.7 km/hr
(ranging from ^3 to 19 km/hr). Wind direction varied from
-20° to +30° of the center line described by sampler 1, the
source, and array samplers 3 and 5 (Figure 2). The barometric
pressure was 750.6 mm Hg and wet and dry bulb temperatures
were 4l°F and 45°F respectively.
In addition to the downwind samples, perimeter samples were
collected at sites 1, 2 and 3. The perimeter samples
were collected for 19.22 hours (1305.4 m3), 25.17 hours
C-4
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Figure 2. Ambient Air Sampling Arrangement Used
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C-6
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(1923.2 m3) and 19-55 hours (1327.8 m3) respectively.
The results from the analyses of the air samples are contained
in Table 1. As expected, the highest total Cr concentration
was obtained at Site 3, the nearest downwind centerline site
located ^90 m from the Stolle plant. The upwind sampling
Site 1 gave an indication of background values during the
sampling period.
Table 1
Air Sampling Results
Sample Site No. Total Cone. Cr (pg/m3)
1 Array 0.02
1 Perimeter 0.05
2 0.010
3 Array 1.0?
3 Perimeter 1.07
H 0.22
5 <0.01
6 <0.03
2.2 Water Samples
Water sampling sites were selected at the Stolle outfall and
three points along the Great Miami River. The upstream site was
^30 m from the point where the treatment plant effluent enters
the river, while the two downstream sites were located at
approximately 3 and 6 streamwidths (^100 m and ^200 m) from that
point. The numbers in black in Figure 1 represent the water
sampling sites.
C-7
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The water samples were collected on September 1.4-15, 1976. SampJ es
of approximately 4 liters were collected at the sites. Suspended
particulate samples were obtained by filtering the water samples
through 0.45 ym Millipore® filters as described in Section 4.2
of the main report. Analyses were performed as described in
Section 5.3 of the main report.
The results for the water analyses are shown in Table 2. As
expected, the highest Cr concentration was obtained at the
plant outfall (Site #2). However, in comparing; the upstream
(Site #1) with the downstream (Sites #3 and #4) river results
there seems to be no significant increase in dissolved chromium
concentrations in the river due to the Stolle outfall. The NPDEf
permit limits for chromium in the Stolle plant wastewater were:
Total Chromium - daily average 450 yg/1
- daily maximum 1050 yg/1
Chromium(VI) - daily average 355 yg/1
- daily maximum 940 yg/1
during the September 14-15, 1976 sampling period. The results
obtained are within these limits. However, more stringent
limitations were scheduled to go into effect on November 25, 1976
setting these new allowable levels:
Total Chromium - daily average 500 yg/1
- daily maximum 1000 yg/1
Chromium(VI) - daily average 50 yg/1
- daily maximum 100 yg/1
Had the new levels been in effect, the total chromium concentra-
tion of 580 yg/1 at the plant outfall (Site #2) would have exceeded
the allowable daily average. Stolle Corporation analysis reports
showed an average total chromium concentration of 117 yg/1 and
an average chromium(VI) concentration of 46 yg/1 during September
1976.
C-8
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Table 2
Water Sampling Results
Sample Total Cr (mg/1) Cr(VI)(ug/l)
Site #1 <0.02 <0.1
Site #2 0.58 0.56
Site #3 <0.02 0.1
Site #4 0.03 <0.1
The values for total chromium in the suspended particulates from
the water samples are given in Table 3. There is a definite
contribution to the chromium content in river water particulates
from the treatment plant effluent. This is shown by the higher
downstream values (Sites #3 and #4) compared to the upstream
value (Site #1). The higher value at Site #3 (0.14 mg/1) com-
pared to the outfall at Site #2 (0.07 mg/1) indicates that
either a significant portion of the chromium particulates are
coming from the Guthrie Road treatment plant effluent, or the
introduction of the outfall into the treatment plant effluent
is causing some of the dissolved chromium to come out of solution
producing higher particulate chromium values.
Table 3
Particulates in Water
Sample Total Cr
Site #1 5 Mg/1
Site #2 0.07 mg/1
Site #3 O-l11 mg/1
Site #4 0.02 mg/1
C-9
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2.3 Sediment Samples
Sediment samples were collected at the same sites as the water
samples with the exception of the outfall (Site #2). Approximately
100 ml of sediment was scooped from the bottom of the river at
Sites #1, #3, and #4 as described in Section 4.3 of the main
report and analyzed as described in Section 5-2
The results from these analyses are given in Table 4. The
results show no trend in the total chromium values.
Table 4
Sediment Sampling Results
Sample Total Cr (yig/g)
Site #1 1.03
Site #3 0.81
Site #4 1.18
2.4 Soil Samples
The optimum soil sampling sites for the Stolle Corporation plant
were chosen on the basis of the diffusion model described in
Section 3.3 of the main report. This model indicated a maximum
concentration area at 29° (relative to due north) and a secondary
concentration area at 180°. The locations of the soil sampling
sites are indicated by letters in Figure 1. These sites were
C-10
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positioned relative to the center of the building on the Stolle
Corporation site. Site A was located at 229° at a distance of
^ 100 m in a grassy field adjoining the Stolle site. This site
was selected to provide a background measurement since it was
not in an area of predicted high concentration. Sites B and C
were chosen to sample the predicted area of maximum concentration
and were located at 29° at distances of ^ 300 m and 100 m,
respectively. Site B was located at the fence line of the Monsanto
Research Corporation, Dayton Laboratory property along Nicholas
Road. Site C was located in a gravelly area along the Stolle
fence line. Sites D and E were chosen to sample the predicted
secondary area of maximum concentration and were located at
180° at distances of ^60 m and 200 m, respectively. Site D
was located in a grassy area at the south corner of the Stolle
fence line near West River Road. Site E was located on the flood
plain on the opposite side of the Great Miami River. The sampler-
were collected and analyzed as described in Sections 4.3 and 5.2
of the main report. Duplicate samples were obtained and analyzed
for selected sites.
The results from the analyses of the soil samples are given
in Table 5. No noticeable pattern can be seen in the data.
Table 5
Soil Sampling Results
Sample Total Chromium (yig/g)
Site A Sample 1 24.8
Sample 2 23.7
Site B Sample 1 16.0
Sample 2
Site C Sample 1 15.9
Sample 2
-Site D Sample 1 36.9
Sample 2 12.9
Site E Sample 1
Sample 2 19.8
C-ll
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APPENDIX D
SAMPLING AND ANALYSIS OF CHROMIUM AT
BREZNER TANNING COMPANY
PENACOOK, NEW HAMPSHIRE
Brezner Tanning Company
Penacook, New Hampshire 03301
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1. PRESAMPLING SURVEY
1.1 Description of the Plant Site
Brezner Tanning Company located in Penacook, New Hampshire, was
chosen as a typical tanning operation suitable for chromium
sampling. This particular tannery was chosen because its
wastewater effluent is treated at a municipal sewage treatment
plant that was included in a companion sampling study (Appendix E)
making possible the examination of tannery effluent before and
after treatment. No presampling survey visit was conducted.
During the sampling visit of November 17-18, 1976, contact was
made with Mr. Peter Fanny, Plant Manager and Mr. John Heffernan,
Lab Supervisor who were very helpful and willing to cooperate
with MRC personnel in the chromium sampling.
The tanning process uses a solution of chromium(III) sulfate,
Cr2(SOif)3, to cure the hides. Since this curing solution is
purchased directly in solution form and not prepared, no air
emissions (stack or fugitive) would be anticipated. Therefore,
no soil samples or air samples for inorganic chromium were
collected at the Brezner site.
The tannery occupies a site of approximately 75m x ^5m. Two
buildings are on the site - one contains offices and production
facilities and the second serves as a warehouse and loading
dock. The plant operates on a 5 day/week, 8 hour/day schedule.
Since the tanning process is a batch operation, there are peaks
in the plant wastewater effluent corresponding to the emptying of
vats which usually occurs around mid-week (Wednesday).
D-l
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The Brezner site is situated in the heart of the town of Penacook,
It is bounded on the north by a two-lane paved road, a city
operated wastewater neutralization facility, and a wooded area;
on the east by the intersection of three two-lane paved streets,
a parking lot, a church and numerous residences; on the south
by more residences and small businesses; and on the west by a
small river which empties into the Merrimack River, and U.S.
Highway 3. Although another tannery in the area discharges waste
to the same sewage treatment facility, it presented no potential
interferences to the samples collected.
The wastewater effluent from the Brezner plant goes into a
"super scooper" which is a crude on-site settling tank. From
here the tannery wastes are pumped across the street to a
city operated neutralization tank which uses a caustic neutrali-
zation process. After neutralization the wastewater is pumped
a distance of ^0.8 km to the Penacook Municipal Sewage Treatment
Plant. The sewage treatment plant wastewater is eventually dis-
charged into the Merrimack River (see Appendix E). The tannery
effluent amounts to ^35000 m3/day.
1.2 Description of the Surrounding Area
The Brezner Tanning Company is situated in the midst of the
population concentration of Penacook, New Hampshire. Penacook
is a town of ^3,000 people in a rural area approximately 9 km
northwest of Concord, the capital of New Hampshire. It is
situated on U.S. Highways 3 and 4 just west of Interstate 93-
The general terrain is hilly and wooded with little industrial
concentration.
D-2
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2. SAMPLING AND ANALYSIS RESULTS
Sampling of the Brezner Tanning Company site was conducted on
Wednesday and Thursday, November 17-18, 1976 to correspond to
the expected peak chromium discharge associated with vat dumping.
As stated earlier, no inorganic chromium air emissions were
anticipated. Therefore, neither inorganic air samples nor soil
samples were included in the study. However, one air sample
was collected for "organic" chromium species. A sample of the
plant wastewater effluent and a sample of sediment from a pre-
viously used outfall point on the Merrimack River were also
collected.
2.1 Air Samples for "Organic" Chromium Species
An air sample was collected at a downwind site (Site #2, Figure i)
just across the street to the east of the plant about 25 m from
the main building. This sample was taken to evaluate the possi-
bility of volatile organochromium species in the air around
the tannery site. The samples were collected by drawing air
through an XAD-2 resin tube as described in Section 4.1 of the
main report. Analysis was performed as described in Section 5.4.1
The results showed no detectable chromium (i.e., <0.2ug/m3) in
the air sample.
2.2 Water Sample
Since the tannery discharges its effluent directly into the
treatment facility, only a sample of the plant effluent was
collected. The sample was taken at the "super scooper" settling
D-3
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tank just before the wastewater is discharged across the street
to the city wastewater neutralization facility (Site #1, Figure 1.)
The sample was a muddy gray color with a heavy loading of sus-
pended solids and a pungent odor. The suspended particulates
were collected by filtration through an 0.45 ym Millipore®
filter. Analyses for dissolved and suspended chromium were per-
formed using the procedure described in Section 5-3 of the main
report. The results are given in Table 1. About 80$ of the
total chromium emissions in the plant effluent are particulate
in nature.
2.3 Sediment Samples
The Brezner plant has been discharging its effluent into the
municipal treatment plant for two years. Prior to this, the
tannery effluent was discharged directly into the Merrimack River
at a point not shown in Figure 1. Two sediment samples were
collected at the old outfall site and analyzed according to the
procedure described in Section 5-2 of the main report. The
results are given in Table 2. These results are similar to
those obtained for the downstream sediment samples in the
Penacook Sewage Treatment Plant studies (Appendix E).
Table 1
Effluent Sample Results
Type Total Gr (mg/l) Cr(VI) (mg/1)
Dissolved 2.3 °-°97
Suspended 10.8
D-5
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Table 2
Old Outfall Sediment Sample Results
Sample Total Cr (yg/g)
1 14.8
2 10.9
D-6
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APPENDIX E
SAMPLING AND ANALYSIS OP CHROMIUM AT
PENACOOK MUNICIPAL SEWAGE TREATMENT PLANT
PENACOOK, NEW HAMPSHIRE
Penacook Municipal Sewage Treatment Plant
Penacook, New Hampshire 03301
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1. PRESAMPLING SURVEY
Telephone contacts were made on September 3 and 7, 1976 with
Michael J. Obrlen of the Region I EPA office in Boston,
Massachusetts [(617)-233-5013] to determine a suitable municipal
sewage treatment plant that receives tannery wastewater for
evaluation in the sampling program. Through this process the
sewage treatment plant of Penacook, New Hampshire was chosen,
since it processed the effluent from the Brezner Tanning
Company (see Section 2.2.4 of the main report and Appendix D).
A presurvey visit was made to Concord, New Hampshire on
September 16, 1976 to consult with Mr. Ronald H. Ford,
Director of Public Works, Concord, N.H. and Mr. Walter E. Norris,
Wastewater Superintendant. The Penacook treatment plant is
under their supervision. Mr. Ford and Mr. Norris were very
cooperative in making arrangements for the sampling of the
Penacook plant.
1.1 Description of the Plant Site
The Penacook Municipal Sewage Treatment Plant is located on the
Merrimack River on the eastern edge of Penacook, New Hampshire.
The facility is two years old and processes the wastewater from
two tanneries in the area. The tannery effluents constitute
^80% of the total plant influent. The remaining 20% is muni-
cipal wastes. There is no other major industry in the area.
The treatment plant has a capacity of ^16,000 m3/day and was
operating at ^60% capacity (^9,500 m3/day) when sampling was
conducted on November 18-19, 1976. The Penacook plant is a
E-l
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secondary treatment facility with a wastewater retention time of
26 hours. Plant operation is continuous.
The overall plant site is large, occupying an area approximately
365 m x 180 m. The process area covers approximately 2 acres with
the remaining portion primarily occupied by an old landfill that
was formerly used for on-site sludge disposal. Currently the
sludge is trucked to a regional sanitary landfill. The plant
site is bounded on the north and east by the Merrimack River.
The opposite bank is wooded. To the south is the landfill area
and beyond that a wooded area. A railroad runs along the western
boundary of the plant beyond which are a few houses and a farm.
The population density increases to the west of the plant as
one approaches the center of Penacook.
The treated plant effluent enters the river through an ^1 m i.d.
concrete pipe. The actual outfall is subsurface at a point
^6 m from the river bank. At this point the river is large
(1/^5 rn wide) and the contribution of the effluent to the total
flow is small. There was no visible change of appearance in
the river water at the outfall. No difference was observed in
aquatic life and organic material above and below the outfall.
1.2 Description of the Surrounding Area
The Penacook Municipal Sewage Treatment Plant lies to the east
of the major population center of Penacook, New Hampshire in a
hilly and predominantly wooded area. Penacook is a town of
approximately 3000 people located approximately 9 km northwest
of Concord, the capital of New Hampshire. Two tanneries comprise
the major industries of the area.
E-2
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2. SAMPLING AND ANALYSIS RESULTS
The Penacook Municipal Sewage Treatment Plant site was sampled
on Thursday and Friday, November 18-19, 1976. These days were
chosen to evaluate the effectiveness of the treatment process
for the removal of the peak chromium concentrations corresponding
to the usual mid-week tannery vat dumping practices (see
Appendix D). Since the treatment plant has a residence time of
26 hours, Thursday and Friday were chosen as optimum days for
observing these effects.
No air samples for inorganic chromium were taken since no major
source of particulate inorganic chromium air emissions was
present. For this reason and also because the plant is relatively
new (2 years old), no soil samples were collected. There is,
however, a slight possibility for fugitive chromium emissions due
to aeration operations used in the treatment process. Two air
samples were taken to examine the possibility of volatile "organic
chromium species in the air around the treatment site. Water
samples for both inorganic and "organic" chromium, sediment samples
and sludge samples were collected. The details for the sampling
and analyses are contained in the following subsections.
2.1 Air Samples for "Organic" Chromium Species
Samples were collected at sites A and B of Figure 1 for
chromium species in air using XAD-2 resin tubes as described in
Section 4.1 and Figure 6 of the main report. Site A was located
over the treatment plant influent, and Site B was located over
one of the aeration tanks. The sample tubes were analyzed
according to the procedure described in Section 5.4.1 of the main
E-3
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report. The results of these analyses are given in Table 1.
Both values were below the detection limit of the method. The
difference in the detection limits for the two sites (i.e.,
0.2 yg/m3 for Site A and 0.4 yg/m3 for Site B) reflects the
different sample sizes collected at the two sites (6.06 m3
at Site A and 2.74 m3 at Site B).
Table 1
Organic Chromium in Air Results
Sample Total Cr (yg/m3)
Site A <0.2
Site B <0.i|
2.2 Water Samples
Water sampling sites were selected at three points along the
west bank of the Merrimack River. Site #1 (Figure 1) was
^30 m upstream of the treatment plant outfall,, while Sites
#3 and #4 were ^30 m and ^60 m, respectively, downstream of the
outfall. A sample of the plant effluent was taken at Site #2
at the point in the final settling tank where the effluent enters
the pipe that discharges it into the river since the actual out-
fall is subsurface.
Pour-liter samples were collected at each of the sites over a
24-hour period as described in Section 4.2 of the main report.
The suspended particulates were removed by filtration through
an 0.45 ym Millipore® filter to obtain a separate analysis of
particulate vs. dissolved chromium. Analyses were performed
as described in Section 5-3 of the main report.
E-4
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The results for the dissolved chromium analyses are shown in
Table 2. As expected, the highest concentrations of both total
chromium and chromium(VI) were obtained in the treatment plant
effluent. The total chromium levels in the river water (Sites #1,
#3, and #4) were below the detection limit of the technique
(0.02 mg/1). A surprising result is the higher upstream value
(Site #1) for chromium(VI) compared to those obtained at the
downstream sites (Sites #3 and #4).
Table 2
Water Sampling Results
Sample Total Gr (mg/1) Or(VI)(yg/1)
Site #1 <0.02 0.4
Site #2 0.05 1.3
Site #3 <0.02 0.1
Site #4 <0.02 <0.1
The results for the analyses of chromium in the suspended parti-
culates are given in Table 3. Although the total chromium con-
centration in the plant effluent (Site #2) was 0.16 mg/1, no
assessment could be made of its contribution to the total chrom-
ium in the particulate matter of the river water since the values
obtained for these samples were either at or below the detection
limit of the technique (0.5 yg/1).
Table 3
Particulates in Water
Sample Total Cr
Site #1 <0.5 yg/1
Site #2 0.16 mg/1
Site #3 0.5 yg/1
Site #4 <0.5 yg/1
E-6
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The total chromium (dissolved + particulate) in the plant
effluent was 0.21 mg/1. This is within the NPDES permit limit
for the Penacook facility which allows a monthly average of
0.269 mg/1 and a maximum day average of 0.537 mg/1.
Three 8-liter water samples were drawn through XAD-2 resin tubes
to sample for "organic" chromium species by the technique des-
cribed in Section 4.2 of the main report. One sample was taken
of plant effluent water and samples of river water were taken
upstream and downstream of the plant outfall by this method.
The ether extracts of these tubes were analyzed by flameless
atomic absorption as described in Section 5.4.1 of the main
report. In each case the value obtained for total "organic"
chromium was less than the detection limit of the technique
(0.15 yg/1).
2.3 Sediment Samples
Sediment samples were collected at the upstream water collection
site (Site #1) and the first downstream water collection site
(Site #3) by scooping ^100 ml of sediment from the river bottom.
No samples were taken at Site #2 (plant effluent) or Site #4
(the second downstream site). These samples were analyzed by the
technique described in Section 5.2 of the main report. The
results are given in Table 4. These results show a definite in-
crease in the chromium level in the river sediment as a result
of the discharge of the treatment plant effluent.
Table 4
Sediment Sampling Results
Sample Total Cr (yg/g)
Site #1 i|
Site #3 23.2
E-7
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2.4 Sludge Samples
A sample of sewage sludge was obtained from the digesters to
determine Its inorganic and "organic" chromium content. The
sample was processed according to the extraction scheme out-
lined in Figure 8 of the main report. The results from the
analyses of the inorganic fraction and the water soluble, base,
strong acid, neutral and weak acid organic fractions are given
in Table 5. Less than 1% of the total chromium in the sludge
was ether extractable "organic" chromium. It is interesting to
compare the results obtained for this sludge sample with those
obtained for the sludge sample from the Guthrie Road Treatment
Plant (Appendix F, Table 4). In both cases, the "organic"
chromium content is less than 1% of the total chromium. However,
the chromium concentration of the Penacook sludge is an order of
magnitude higher than that of the Guthrie Road sludge.
Table 5
Sludge Sample Results
Fraction Total Or (yg/g in dry sludge)
Inorganic 13,950
Organic
Water Solubles 0.63
Bases 5.85
Strong Acids 2.30
Neutrals 80.0
Weak Acids 12.1
Total Organics 100.9
E-8
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APPENDIX F
SAMPLING AND ANALYSIS OP CHROMIUM AT
GUTHRIE ROAD SEWAGE TREATMENT PLANT
DAYTON, OHIO
Guthrie Road Sewage Treatment Plant
Guthrie Road
Dayton, Ohio
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1. PRESAMPLING SURVEY
1.1 Description of the Plant Site
The City of Dayton Guthrie Road sewage treatment plant, Guthrie
Road, Dayton, Ohio 454l8 was chosen for sampling because
the City of Dayton Water Department personnel stated that the
bulk of chromium waste they receive is handled by this facility.
Contacts were made with Mr. Walton Farr, Director of the Depart-
ment of Water, Mr. DeFro Tossey, Superintendant of Wastewater
Treatment, and Mr. John Norton, Plant Engineer to obtain permis-
sion for sampling and aid in locating the sampling sites.
A preliminary survey visit was made to the Guthrie Road treatment
facility on December 17, 1976. The plant occupies a site of
approximately 640 m x 1280 m. There are two major buildings on
the site - one with offices and a laboratory and the second
houses the control room and maintenance facilities. Various other
small buildings, ^20 large trickle bed filters and several
large sludge pits are also located on the site.
The plant is bounded on the north by Guthrie Road, an open field
and Madden Golf Course, on the east by West River Road, an open
field and the Great Miami River and on the south and west by open
fields and wooded areas. The closest industry is on the opposite
bank of the Great Miami River and consists of light industry, an
asphalt batch plant, sand and gravel operations, and storage
warehouses. No significant interferences are expected in the
samples due to these operations in the area.
F-l
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Guthrie Road sewage treatment plant handles waste from the
City of Dayton and other sections of Montgomery County including
Englewood and Trotwood. The major contributors of chromium in
the wastewater processed by this facility are chrome platers
and large industry such as General Motors and Inland installa-
tions in the area serviced. It should be noted that the chromium
wastes processed by the Guthrie Road plant do not include any
contribution from the Stolle Corporation since its wastewater
is discharged into the processed effluent stream from the treat-
ment plant (see Appendix C).
The plant operates continuously and discharges 190,000-230,000
m3/day of treated wastewater through an open concrete ditch into
the Great Miami River. The average water retention time in the
plant is ^4.5 hours. The outfall is very turbulent and signi-
ficantly affects the flow of the river at the point of entry
and for some distance downstream as can be seen in the aerial
photo (Figure 1) which shows the effluent stream at Site #3-
A number of dead and incapacitated fish were observed below the
outfall. However, vegetation is plentiful and several people
were fishing in the area.
1.2 Description of Surrounding Area
The City of Dayton Guthrie Road Sewage Treatment Plant is located
in the southwestern metropolitan Dayton, Ohio area approximately
16 km south of the intersection of Interstates 70 and 75. The
immediate area around the plant site has a relatively low
population concentration which increases as one moves toward the
Dayton population center. The City of Dayton is located in a
river valley at the junction of the Miami, Mad, and Stillwater
Rivers. The general topography is flat. The metropolitan area
has a population of ^865,000 and supports an impressive diversity
of industry. There are some 850 plants located in Montgomery
County producing over 1000 products with an estimated value of ovei
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$1 billion. Major industries in the area include automotive
subassembly, appliance manufacturing and precision equipment
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2. SAMPLING AND ANALYSIS RESULTS
Due to the nature of the operation at the Guthrie Road plant,
no inorganic chromium emissions were anticipated. This
eliminated the necessity of collecting soil samples and air
samples for inorganic chromium. However, air samples for
"organic" chromium species, water and sludge samples were
collected at the site on January 5-6, 1977-
2.1 Air Samples for "Organic" Chromium Species
Air samples were collected at sites #4 and #5 of Figure 1 using
the technique for "organic" chromium species described in
Section 4.1 and Figure 6 of the main report. Site #4 was down-
wind of the trickle bed filters and Site #5 was over one of the
sludge ponds. These samples were analyzed by the procedure
described in Section 5-4.1 of the main report. The data obtained
from these analyses are contained in Table 1. Both samples
produced chromium concentrations less than the detection limit
of 0.2 yg/m3.
2.2 Water Samples
Samples of the plant influent (Site #1), the trickle bed
filter recycle water (Site #2), and the plant effluent (Site #3)
were collected using the metnods described in Section 4.2 of the
main report. The trickle bed filter recycle water is part of
the effluent (^63$) that is returned through the trickle bed
filters. The effluent sample was taken upstream of the point
where the Stolle outfall enters the effluent stream. Four-liter
samples were collected at each site over a twenty-four hour pericd,
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The influent and effluent waters were heavily loaded with sus-
pended particulates. The particulates were removed for analysis
by filtration through 0.45 ym Millipore® filters.
Table 1
Air Sample Results for "Organic" Chromium Species
Sample Total Cr(yg/m3)
Site #4, Trickle Bed Filters <0.2
Site #5, Sludge Pond <0.2
The filtered water samples were analyzed for dissolved chromium
according to the procedure described in Section 5-3 of the main
report. The results of these analyses (Table 2) indicate a
significant reduction in dissolved chromium during the treatment
plant processing. Of particular significance is the reduction
of the highly toxic chromium(VI) content from 0.8 yg/1 to below
the detection limit (<0.1yg/l) during passage through the treat-
ment plant.
Table 2
Water Sampling Results
Sample Location Total Cr (mg/1) Or(VI) (yg/1)
Site #1, Influent 0.04 0.8
Site #3, Effluent 0.02 <0.1
Site #2, Trickle Bed Recycle 0.04 <0.1
The results for the chromium analyses of the suspended particulate
samples are contained in Table 3. These indicate a reduction in
particulate chromium during passage through the treatment plant.
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There is some inconsistency in the results, however, due to the
lower chromium concentration (26.4 yg/1) in the trickle bed
filter recycle water compared with the effluent water (56.9 yg/1)
One might normally expect these results to be higher than or
equal to the effluent values. This would indicate that perhaps
the particulate chromium concentration is increased on recycling
through the trickle bed filters.
The results for total chromium (dissolved + particulate) in plant
influent and effluent obtained in this study (132.6 yg/1 and
76.9 yg/lj respectively)compare well with values of l8l yg/1 and
72 yg/1 reported by plant officials in July 1976. These were
described as "typical" values.
Table 3
Particulates in Water
Sample Location Total Cr (yg/1)
Site #1, Influent 92.6
Site #3, Effluent 56.9
Site #2, Trickle Bed Recycle 26.4
Sites along the Great Miami River below the treatment plant out-
fall were not sampled during this study because such results
would represent a composite for the treatment plant and Stolle
Corporation effluents since the Stolle outfall is introduced
into the treatment plant effluent water. Sampling of the river
was conducted during the Stolle site studies (Appendix C) and
these figures give some indication of the combined effect of the
treatment plant and Stolle effluents on the chromium content of
the river water, suspended particulates, and sediment.
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2.3 Sludge Samples
A sample of sewage sludge was obtained from the digesters and
processed according to the ether extraction scheme outlined
in Figure 8 of the main report. This scheme produces an in-
organic fraction, and an organic fraction that is further fraction-
ated into water soluble, base, strong acid, neutral, and weak
acid fractions. The results for the total chromium in each
of these fractions are given in Table 4. Slightly less than 1%
of the total chromium in the sludge sample was in the form of
ether soluble chromium species.
Table 4
Sludge Sample Results
Total Chromium
Fraction (yg/g in dry sludge)
Inorganic 911.0
Organic
Water Solubles 1.54
Bases 0.38
Strong Acids 1.02
Neutrals 3.84
Weak Acids 1.79
Total Organics 8.57
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-560/6-77-016
2.
3. RECIPIENT'S ACCESSION NO.
J4. TITLE AND SUBTITLE
Environmental Monitoring Near Industrial Sites:
Chromium
5. REPORT DATE
June 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S) Arthur D. Snyder, Daryl G. DeAngelis,
Edward C. Eimutis, David M. Haile, Joseph C. Ochsner,
Richard B. Reznik and Harlan D. Toy
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-661
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
P. 0. Box 8 (Station B)
Dayton, Ohio 45407
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-1980
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 5/76-6/77
14. SPONSORING AGENCY CODE
EPA - OTS
15. SUPPLEMENTARY NOTES
EPA project officer for this study is Dr. Vincent J. DeCarlo (WH 557)
401 M Street, S.W., Washington, D.C. 20460
16 ABSTRACT
A sampling and analysis program was conducted to determine concentrations of chromium
in the air, water and soil in the environs of industrial sites and sewage treatment
plants. Five industrial categories - chrome pigments producers, electroplating
plants, ferrochromium plants, leather tanneries, and sodium dichromate/chromic acid
producers - were presurveyed to select the final sampling sites.
Samples were gathered at two chrome pigment plants, an electroplating plant, a
leather tannery and two sewage treatment plants. The protocol for sampling air
utilized high-volume samplers in either a downwind array or in a plant perimeter
geometry. Composite 24-hour water samples were taken and soil core samples were
obtained.
The techniques employed for analysis of the environmental samples were intended to
differentiate between the two most common chromium valence states (III and VI). This
was accomplished for water samples but not for air, soil or sediment samples because
acid digestion converted chromium (VI) to chromium (III). All analyses were obtained
on a Varian AA-6 atomic absorption spectrometer.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
chromiumchrome pigment producers
water electroplating plants
sediment ferrochromium plants
soil leather tanneries
air sodium dichromate producers
sampling chromic acid producers
analysis sewage treatment plants
atomic absorption
b.IDENTIFIERS/OPEN ENDED TERMS
Environmental monitoring
Industrial plants
chromium
c. COSATI Field/Group
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (ThisReport)'
Unclassified
21. NO. OF PAGES
135
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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