RD-Ai33 714 CHARACTERIZATION OF SELECTED VOLATILE ORGANICS IN 1/2 RNASTEkIATER TREATMENT INFLUENTS(U) AIR FORCE INST OFTECH WRIGHT-PATTERSON AFB OH V S DUNOVANT SEP 83

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(CHARACTERIZATION OF SELECTED VOLATILE ORGANICS IN

WASTEWATER TREATMENT INFLUENTS

4A Thesis submitted to the

Division of Graduate Studiesof the University of Cincinnati

in partial fulfillment of therequirements for the degree of

MASTER OF SCIENCE

in the Department of Environmental Healthof the College of Medicine

1983 DTICS ELEC T E

by S OCT 181M

Victoria S. Dunovant D

B.A. Chemistry/Biology, West Virginia University, 1974

L&J

-4j

EUTRDMUON STATEMENT A

Appvod fo, public release;Distribution Unlimited

IINCI A'-;'SE-uRITY CL ASSIFICATI-)N 3,F THIS PAGE (When Dlts Im,.r-.

REPORT DOCUMENTATION PAGE R-A[ tI.C' [InN"

I REPORT NUMBER 12. GOVT ACCESSION NO I RErPiT . - r-0 'TLL N NjtjF.P

AFIT/CI/NR 83-50T /A / 2_______4 TITLE 'and Subtitle) 5 T I:PE OF REPORT & PERO CO./EREO

Characterization of Selected Volatile Organics THESIS/V J 7AIAP)4in Wastewater Treatment Influents

6 PERFORMING O1G. REPORT *.uMBER

7 AUTHOR(s) S. CONTRACT OR GRANT NUMBER()

Victoria S. Dunovant

9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT. PROJECT, TASKAREA 6 WORK UNIT NUMBERS

AFIT STUDENT AT: University of Cincinnati

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AFIT/NR Sept 1983

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UNCLASS

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IS. SUPPLEMENTARY NOTES

APPROVED FOR PUBLIC RELEASE: IAW AFR 190-17 WOLAVER

c 4 A / Dean for Research andProfessional Development

19. KEY WORDS (Continue on reverse side it necessary and identify by block number)

20. ABSTRACT (Continue on reverse side If necessary and identify by block number)

O O ,JAN", N s~ U N C LA S SDD 78M 1R3 MDjdON OF 1263 IS IS ? NCAS

SEC,.RITY CLASSIFICATION OF THIS PAGE . , e: Date rreJ

UNIVERSITY OF'r CICINNATI

SEPTEMBER 22, )83

I herey recommend that the tdaesi prepared ander myuuvpewis'in byVICTORIA S. DUNOVANT

eagd CHARACTERIZATION OF SELECTED VOLATILE

ORGANICS IN WASTEWATER TREATMENT INFLUENTS

be ecepte as ilin i pan of the reqwe fnr thedegre qfMASTER OF SCIENCE

Approved by.

Accession For

NTIS GRA&IDTIC TAB ElUnannounced

Justfictio

it A r- i. .__ _ __ _ _ __ _ __ _ __ _ __ _ __ _

;Dist

* - ' - -' -. - - |

ACKNOWLEDGMENT

I wish to express my appreciation to my Advisory Committee for their

guidance and encouragement: Dr. C. Scott Clark (my advisor) and Dr. Vicki

Hertzberg of Kettering Laboratory, Department of Environmental Health,

University of Cincinnati, and Mr. John Trapp of the Metropolitan Sewer

District of Greater Cincinnati. I extend my thanks to Dr. Shane Que Hee and

all of the faculty of the Department of Environmental Health.

I thank the Metropolitan Sewer District of Greater Cincinnati for

allowing me to conduct the studies at three of their wastewater treatment

plants and a special thanks to Mr. Ed Baker.

A special thank you to the United States Air Force, Air Force

Institute of Technology, Wright Patterson AFB, Ohio for the full-salary

stipend and tuition as well as their support and encouragement, especially

Captain Kenneth Kurowski and Captain Bob Perry, my program managers.

I would like to extend my appreciation to the Occupational and En- :N.-I

vironmental Health Lab (OEHL), Brooks AFB, TX for their analytical support 7.

and their encouragement. In particular, I would like to thank Col. William

Mabson, Chief of the OEHL, Lt. Col. Edward Lefebvre, Chief of the

Analytical Section and Mr. Leo Rodriguez, Head of the Trace Organics

Section for their guidance and encouragement.

I would like to thank Mrs. Jane Onslow and Mrs. Lois Carpenter for

their assistance in typing this thesis. I would also like to thank Mr.

Jozef Svetlik for his technical assistance and his encouragement.

Finally, I wish to thank my husband, Dan for his patience, support and

understanding, which significantly eased the completion of this thesis.

' -II-

•:

1.7; 1:; 1:I

TABLE OF CONTENTS

Page -

Acknowl edgments 1

List of Figures v

List of Tables vi

I INTRODUCTION........................................1

II BACKGROUND...................................

Plant Descriptions................................. 6

Mill Creek Plant................................. 6Muddy Creek Plant................................ 7Little Miami Plant............................ 8

III SAMPLING METHODS ............................. 9

Sampling and Analysis Plan .......................... 9Sampling .................................... 10

IV ANALYTICAL METHODS .............................. 13

Instruments ...................... . ... .. . . .. .. . 13-

Century Systems' Portable Organic VaporAnalyzer (OVA-FID)............................. 13

HNU Systems, Inc. (PID)....................... 14Bioinarine Combustible Gas Meter.................... 16

Laboratory Methods ................... ........... 17

Overview ........................... ........ 17Analysis of Charcoal Tube Samples .................. 17Purge and Trap Methods (EPA 601/602) for Analysis

of Water Samples............................... 18Calculation of Concentrations of Specific

Substances in Water .. . .. . ................ 19Calculation of Concentrations of Specific

Substances in Air.............................. 21

V STATISTICAL METHODS.............. ... ... ...... ........ 22

.. . - - ..

TABLE OF CONTENTS (continued) -1

Page

VI RESULTS ................................................ 24

Variability and Sampling Conditions Data ............. 24Charcoal Tube Sample Analyses ........................ 26Water Sample Analyses ................................ 27Comparison Studies of Water and Air Samples .......... 28

VII DISCUSSION ............................................. 31

VIII CONCLUSION ....................................... 35

IX FIGURES ..................................... 37

X TABLES ................................................. 46

XI APPENDICES ......................... 107

1.1 Computer Method Used for Charcoal TubeSample Analyses ........................... .... 108

1.2 Computer-Autosampler Sequence Used for CharcoalTube Sample Analyses ........................... 109

2.1 Computer Method Used for Water Analyses forPurgeable Halocarbons ....................... 112

2.2 Computer-Autosampler Sequence Used for WaterAnalyses for Purgeable Halocarbons ............. 113

3.1 Computer Method Used for Water Analyses forPurgeable Aromatics ......... ............ 115

3.2 Computer-Autosampler Sequence Used for WaterAnalyses for Purgeable Aromatics ....... 116

4.0 Computer Statistical Programs .................... 1174.1 SASRUN 1 ................. ....................... 1184.2 SASRUN 2 ................. ....................... 1194.3 SASRUN 3 ............................. 1204.4 SASRUN 4 ................. ....................... 1214.6 SASRUN 6 .......................... 1224.1 SASRUN 7 .............................. 1234.8 SASRUN 8 ....................... . ................ 1245.1 Determination of a Proper Statistical Method..... 125

XII REFERENCES......... ...... 128

References Cited in Text ............................. 128Additional References ................................ 131

-iv-

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LIST OF FIGURES

F IGURE PAGE

1 MSD Service Area ............................... 37

2 Diagram of Mill Creek Interceptors ................ 38

3 Schematic of an Automatic Bar Screen .............. 39_

4 A Comparison of the Century OVA (FID) andthe HNU (PID) ................................ 40

5 Century OVA Data ............................... 41

6 Century OVA Data ............................... 43

7 Century OVA Data ............................... 44

LIST OF TABLES

TABLE PAGE

1 Relative Sensitivities of the Century OVA ............ 46

2 Instrument Parameters for Gas ChromatographicAnalysis of Charcoal Tube-Air Samples.............. 47

3 Detection Limits for Compounds Determined by GCAnalysis of Charcoal Tube Samples ................. 48

4 Instrument Parameters for Analysis of PurgeableHalocarbons in Water Samples..................... 49

5 Instrument Parameters for Analysis of PurgeableAromatics in Water Samples....................... 50

6 Retention Times and Detection Limits for Halocarbonsin Water Samples................................ 51

7 Retention Times and Detection Limits for Aromatics inWater Samples .................................. 52

8 Summnary of Analytical Samples Collected.............. 53

8.1 Mill Creek Plant.................................. 548.2 Muddy Creek Plant................................. 558.3 Little Miami Plant ............................. 56

9 Sampling Condition Information and Century OVAAir Sampling Data..............................................57

9.0 Key for Tables 9.1-9.3 ............................ 589.1 Mil11 Creek Plant ................................. 599.2 Muddy Creek Plant............................ 639.3 Little Miami Plant ......... ................... 65

10 Pearson Correlations for Sampling Condition DataCompared to Century OVA Data (PPM)................. 68

11 Results of Analysis of Charcoal Tube Air SamplesCollected During Periods of Peak EpisodesObserved on CenturyOVA ...................... 69

11.0 Key for Tables 11.1-11.3, 12, 13 .................... 7011.1 Mill Creek Plant........... ......... .. ...... . 7111.2 Muddy Creek Plant............ .............. 7211.3 Little Miami Plant......... .. .. .. .......... .... 73

-vi -

LIST OF TABLES (continued)

TABLE PAGE

12 Results of Analysis of the 8 Hour TWA CharcoalTube Air Samples................................ 74

13 Results of Analysis of Charcoal Tube Air SamplesCollected at Other Sites......................... 75

14 Pearson Correlations Comparing Century OVA (PPM)Values with Results of the Charcoal TubeSample Analyses................................. 76

15 Three Different Types of Correlations ComparingCentury OVA Data (PPM) with Charcoal Tube SampleAnalyses at the Mill Creek Plant .................. 77

16 Results of Analysis of Chlorinated Organic Compounds(Halcocarbons) in Water Samples Collected DuringPeak Episodes Observed on the Century OVA.......... 78

16.0 Key for Tablesl6.1-16.3 .......................... 79

16.1 Mill Creek Plant ................................. 8016.2 Muddy Creek Plant ................................ 8116.3 Little Miami Plant................................ 82

17 Results of Analysis for Aromatic Compounds inWater Samples Collected During Peak EpisodesObserved on the Century OVA ................... 83

17.0 Key for Tables 17.1-17.3 ........................ 84

17.1 Mill Creek Plant ................................. 8517.2 Muddy Creek Plant ............................. 8617.3 Little Miami Plant ........................... 87

18 Pearson Correlations Comparing Century OVA (PPM)Data with the Results of Selected WaterSample Analyses............................ 88

19 Comparison of Air, Water and Century Results ......... 89

19.1 Mill Creek Plant........................... . .. 9019.2 Muddy Creek Plant ................................ 9119.3 Little Miami Plant ........................ 92

-vii -

LIST OF TABLES (continued)

TABLE PAGE

20 Statistical Information on Air and Water Data ........ 93

20.0 Key for Tables 2.1-20.3 .......................... 94

20.1 Mili Creek Plant ................................. 9520.2 Muddy Creek Plant................................. 9620.3 Little Miami Plant................................ 97

21 Comparison of Charcoal Tube Sample Results toCentury OVA Readings ............................ 98

21.1 Mill Creek Plant ................................. 9921.2 Muddy Creek Plant ................................ 10021.3 Muddy Creek Plant ................................ 101

22 TLV's ..................................... o..... 102

23 TLV's and S.J. Toogood, J. A. Hobson Values(British Paper).o.................... o........... 103

24 Summary Table of CTLV's and RAT's (14) .............. 104

25 A Summary of the Statistics Performed on theAnalytical Results .............. .... .......... 105

26 Summary of the Number and Magnitude of theHighest Readings on the Century OVA.... o..........106

-vj

INTRODUCTION

Municipal wastewater treatment facilities handle a variety of com-

binations of industrial, commnercial and residential wastes, all of which

contain complex mixtures of volatile organic compounds. Many of these

volatiles are known to pose a potential health risk to personnel working in

the sewers or in the wastewater treatment plant itself. Recent surveys by

the National Institute for Occupational Safety and Health (NIOSH) of a

wastewater collection system have detected dangerous concentrations of

vapors in some of the sewer airspaces (13,14). However, the complex

mixtures, the variable nature of the wastewater and the multiplicity of

confounding factors complicates the measurement and assessment of the

potential risks.

Various approaches have been proposed to assess the concentrations of

organic chemicals in sewer airspaces such as the measurement of individual

compounds in the air, the use of direct reading organic vapor detectors and

Lhe prediction of maximum possible air concentrations based on wastewater

data. Little information is available on the composition and variability

of the air concentrations in airspaces above wastewater.

An opportunity to address some of these issues was available by

conducting air and water quality monitoring where incoming wastewater

enters each of the three largest wastewater treatment plants of the

Metropolitan Sewer District of Greater Cincinnati, Ohio (MSD). These

influent areas are located in structures that extend below the surface of

the ground to coincide with the location of incoming wastewater, are

enclosed, and are locations frequented routinely by workers. Another

-2-

factor making these plants suitable for study was that each received a

different proportion of industrial waste and varied by more than an order

of magnitude with respect to their size.

The objectives of this study were as follows:

1) Characterize and compare the variability in air and water con-

centrat ions both wi th in and between each of the i nfl1uent areas of the three

different wastewater plants in Cincinnati, Ohio.

2) Compare analytical determinations for specific compounds to total

organic vapor concentrations determined by direct reading instruments.

3) Determine the correlation between vapor and water concentrations

of total organics and individual compounds.

4) Evaluate and compare four different schemes for assessing the risk

from exposure to vapor concentrations in wastewater facilities.

The individual compounds for which analyses were performed were the

U.S. Environmental Protection Agency (EPA) volatile organic priority

pollutants (15). Water concentrations for both halocarbons and aromatics

were determined by EPA methods 601 and 602 (40 CFR Part 136) (25,26).

-1 .-7 aA . . .- a - . --- . . .

-3-

BACKGROUND

Industries in the United States discharge over 1 trillion gallons of

wastewater, most of which is untreated, to public sewers each year. Other

chemical discharges occur from commercial and residential sewer users.

The content and concentrations of these discharges varies dramatically

from one plant to another and from one hour to the next.

Until the past four or five years, there was almost no existing

information regarding health hazards posed to personnel working in

wastewater treatment plants and sewer airspaces due to exposure to organic

chemicals. The primary reason for this lack of information resided in the

fact that identification and quantification of trace amounts of organic

chemicals was beyond the scope of existing analytical instrumentation and

techniques and because of the enormous number of possible sampling

locations. As analytical instrumentation and techniques became more

sophisticated and more available for practical use, interest increased

regarding wastewater contents and concentrations primarily from the

point-of-view of the plants' effluents into nearby bodies of water (rivers

and lakes). Initially wastewaters were analyzed for specific classes of

compounds such as polynuclear aromatic hydrocarbons (Reichert, et al.,

1971) (2) and polychlorinated biphenyls-PCB's (Schmidt, et al., 1971) (3)

and (Lawrence, et al., 1976) (4). In 1976, in response to complaints

concerning the enforcement of the Clean Water Act, the Environmental

Protection Agency issued a list of 127 priority pollutants (5). At about

the same time Glaze, et al., 1976 (6) and Chian and DeWalle, 1983 (7)

identified a wide range of compounds in wastewater effluents. Shortly

*1

-4-

thereafter, the U.S. EPA (and their contractors) also published several

studies of toxic chemicals present in wastewaters (Cohen, et al., 1981 (1),

Pelizzari, 1981 (8), Kyosai, et al., 1981 (10), Petrasek, et al., 1981

(11)).

However, the aforementioned studies concentrated on characterizing

the wastewaters without regard for the potential to adversely affect the

workers in these wastewater treatment plants. In 1980 and 1981 the

National Institute for Occupational Safety and Health (NIOSH) performed

two Health Hazard Evaluations (HHE), one in response to workers at a

collapsed sewer in Cincinnati (12) and the other a general survey of the

sewerage system in Cincinnati (13). In contrast to previous work, NIOSH's

study focused on worker exposures to chemicals present in the wastewater

and surrounding airspaces. NIOSH concluded that the potential for a health

hazard did exist and that appropriate corrective and protective measures

should be taken.

In this same time frame, Toogood and Hobson, 1980 (14) at the Water

Research Centre in Great Britain published a method for "Determination of

Safe Limits for the Discharge of Volatile Materials to Sewers." This study

proposed a method by which the maximum air concentrations could be

predicted from the wastewater concentrations by assuming equilibrium

concentrations in aqueous and vapor phases.

Lurker, 1982, 1983 (15,37) looked at the volatilization of organic

compounds from the activated sludge process within a sewage treatment

plant receiving pesticide wastes. Decker, 1980 (16) and Staley (17)

studied the fugitive emissions from a toxic waste incinerator; the former

. .

- -.. ,-.-- "o- . .- ~, -.- .- ~ -

-5-

was concerned with worker exposure and the latter with general en-

vironmental contamination.

However, until quite recently very little actual measurement of the

variability of air concentrations of airspaces in sewers and wastewatertreatment facilities had been undertaken. In 1983, Barsky (18) performed

a study comparing three direct reading instruments in the presence of high

humidity and then further tested these instruments in several sewer

locations and at the influent (wet well area) of a wastewater treatment

plant in Cincinnati. Barsky's study (18) coupled with NIOSH's studies

(12,13) and Toogood and Hobson's proposal (14) formed the basis for

formulating the objectives of this thesis. In addition, a study performed

by Black and Veatch (19) for the Metropolitan Sewer District (M"' of

Greater Cincinnati provided an indication of some of the compounds present

in the w:,stewater and their variability at two of the plants in this study.

The third plant had previously been monitored under an EPA-sponsored

effort (37).

-6-

PLANT DESCRIPTIONS

The three plants involved in this study are all located in the

Cincinnati area and are operated by the Metropolitan Sewer District of

Greater Cincinnati (MSD) for the Hamilton County Commissioners. A map of

the MSD service areas is presented in Figure 1 and shows the location of

each of the following wastewater treatment plants:

1) Mill Creek Plant

2) Muddy Creek Plant

3) Little Miami Plant

This study concentrates on the initial influent area of each plant

which is located immediately after the distribution chamber that receives

all incoming raw wastewater flow from the sewerage system. From the

distribution chamber, the wastewater enters the bar screen or bar rack. The

bar screen removes large foreign objects from the wastewater in order to

protect the pumps. From the bar screen, the wastewater flows into the wet

well where the wastewater is pumped from the wet well to an elevation that

will permit gravity flow throughout the rest of the treatment process. All

air and water sampling was conducted immediately adjacent to the bar screen

area, after the diversion chamber and before the wastewater enters the wet

well/pump area.

Mill Creek Treatment Plant

The Mill Creek Plant is one of the largest wastewater treatment plants

operated by MSD and it services the highly industrialized Mill Creek Valley

(Figure 1). It has a service area of approximately 133 square miles and

serves over a half million persons. The Mill Creek Plant is designed to

. . ..-

-7-

handle a dry weather flow of 120 million gallons per day (MGD) and has

facilities to handle a maximum of 360 MGD of combined wastewater and storm

flow.

Figure 2 shows the four Mill Creek interceptors that feed into and mix

in the diversion chamber which then forms the combined flows which enter

the bar screen and wet well. Figure 3 is a diagram of the screen building

which houses two parallel protective screening devices. The material

caught on the bars of the screening devices is removed by traveling rakes

and deposited in large containers for disposal.

The Mill Creek Plant bar screen area is ventilated using forced air

ventilation as opposed to exhaust ventilation in an attempt to shift the

liquid-air equilibrium backwards in favor of the liquid phase. Air ducts

about 12 inches in diameter bring air from the roof of the bar screen

building. The ducts extend down to about 2 meters above the working floor

just above the incoming wastewater. This ventilation provides between 5

and 10 room air changes per hour.

In addition to raw wastewater entering the plant, some return flow

from the plant was also being recycled into the interceptors from the

sludge digestor ("heavy" supernatant) and the thermally conditioned sludge

thickener (from the ZIMPRO process). The magnitude of these return flows

range between 0 and 10 MGD.

Muddy Creek Treatment Plant

The Muddy Creek Plant provides wastewater treatment from the largely

residential areas in western Hamilton County (Figure 1). This plant

services approximately 22 square miles and is designed to handle a dry

-8-

weather flow of 15 MGD.

The Muddy Creek Plant has two interceptors which feed into the

diversion chamber: the East Branch Muddy Creek Interceptor and the West

Branch Muddy Creek Interceptor. This plant has a stationary bar screen

which must be cleaned/raked by hand. The bar screen area is also totally

open to the upper floors of the pump building. The bar screen is ventilated

only by general building ventilation. However, due to the low capacity and

primarily residential wastewater the risk to employees is lower than at a

larger or more industrialized plant.

Little Miami Treatment Plant

The Little Miami Plant is the second largest wastewater treatment

plant operated by MSD and services approximately 86 square miles in eastern

Hamilton County (Figure 1). The Little Miami Plant is designed to handle

a dry weather flow of 38 MGD and has facilities for handling a maximum of

98 MG!) of combined wastewater and storm flow.

The Little Miami Plant has one primary interceptor which flows into

three interconnected collection and flood control chambers before entering

either of the two pump buildings. The newer pump building normally handles

the majority of the wastewater flow and is similar in design to that of the

Mill Creek Plant. It has automated bar screen rakes and is essentially

separated from the rest of the building. The Little Miami Plant also uses

forced air ventilation similar to that at the Mill Creek Plant.

-9-

SAMPLING METHODS

Sampling and Analysis Plan

This study involved two separate aspects: field surveys of the

I influent (wet well) area with direct reading instruments and simultanieous

collection of water and air samples for laboratory analysis. The field

studies were designed to evaluate the two different direct reading

instruments: the portable Century Organic Vapor Analyzer (OVA) equipped

with a flame ionization detector (FID) and the portable H-NU equipped with

L a photoionization detector (PID-11.7 eV). Both instruments measure totalhydrocarbons in parts per million (PPM), but are responsive to different

compounds with varying sensitivities. The water and air samples for

laboratory analysis were collected to determine actual concentrations of

individual compounds present in both the water and the air. These

concentrations were then correlated with total levels determined on the

direct reading instruments. The concentrations found in the water were

also correlated with the concentrations in the air. This study was also

designed to characterize both the influent quality and the resultant

atmospheric quality at three different waste treatment plants within the

MSD. The variability within each plant was monitored hourly and daily and

the three plants were compared to each other with respect to their

variability. Air and water data were also applied to four basic methods of

assessing personnel exposure to volatile organic chemicals: 1) pre-

dictions from water concentrations, 2) air sampling for specific comn-

pounds, 3) direct reading instruments to determine total volatiles, and 4)

r determination of vapor head space analysis.

*. . . . . .. . . L. . .. -_ - : ° . , . . , L . . - . ,. , .. . , .

-10-

Sampling

Samples were collected on seven consecutive days at three different

sewage treatment plants for 8-12 hours each day. The three plants studied

were all part of the MSD and were as follows:

1) Mill Creek Sewage Treatment Plant

2) Muddy Creek Sewage Treatment Plant

3) Little Miami Sewage Treatment Plant

The sampling was conducted in the wet well/bar screen area which is the

initial point where the combined industrial, domestic and commercial

wastewater flow enters the sewage treatment plants. The sampling was

conducted between 9 August 1982 and 6 September 1982.

Three direct reading instruments were used: 1) a Century Organic

Vapor Analyzer (OVA) with a flame ionization detector (FID), 2) a H-NU

photoionization detector (PID) equipped with an 11.7 eV lamp, and 3) a

Biomarine Combustible Gas Meter which determined percent oxygen, percent

LEL as hexane (lower explosive limit) and percent methane. These three

instruments were operated continuously and monitored visually. Readings

were recorded every 30 minutes and whenever there was a marked change in

readings.

Charcoal tube samples were collected according to three different

criteria. Eight hour time weighted average (TWA) samples were collected

for each sampling day at a flow rate between 0.014-0.018 liters per minute

(LPM). Charcoal tube samples were also collected each time there was a

marked increase ("peak") in either of the direct reading instruments (OVA

and/or H-NU). These "peak" samples were collected at a flow rate of 1.85

LPM for the duration of the peak unless the "peak" lasted longer than 30

.S' * "* *"' " " " " " " . . "" - " .' .. t. . - . " --

: -11-

minutes, in which case a second charcoal tube was utilized. At Mill Creek

(the largest plant), a peak was defined as a reading equal to or greater

than 100 PPM. At the other two plants a peak was defined as a reading equal

to or greater than 50 PPM. In addition, charcoal tubes were collected at

other points of interest such as the outside grate at Mill Creek and the

area behind the bar screen at Little Miami. These "special" samples were

collected at a flow rate of 0.92 LPM for approximately 60 minutes.

Water samples were also collected to correspond with the "peak"

readings. These water samples were instantaneous grab samples which were

collected in duplicate according to EPA guidelines (40CFR, Part 136,

December 1979, Methods 601, 602 and 624) (5,25,26).

Additional meteorologic, wastewater and plant operating condition

information was also collected to aid in the evaluation of the results: 1)

wet bulb temperature, 2) dry bulb temperature, 3) humidity, 4) water

temperature, 5) pH of water, 6) water flow into the plant in million

gallons per day (MGD), 7) direction and extent of ventilation, 8) outside

weather conditions (rain), temperature, and 9) characteristics of waste-

water such as color, smell and the presence of detergent. The above

mentioned data was collected every 30 minutes to coincide with the direct

reading instrument data. Hereafter, this information will be be referred

to as sampling condition data.

The samples (water and charcoal) were collected and kept on ice until

time of analysis. The samples were analyzed by standard methods using the

facilities at the Occupational Environmental Health Lab (OEHL), Brooks Air

Force Base, Texas. The analytical results of the analyses were evaluated

-12-

using the University of Cincinnati Statistical Analysis System (SAS-

796).

The results of this sampling strategy were examined with respect to

four different methods of assessing personnel exposure. The results were

first examined by individual compounds present. The total of these

individual compounds were then compared to the direct reading instrument

-. data. Next the results from the water analyses were examined in comparison

to Toogood and Hobson's (14) proposal that predicts the maximum allowable

water concentration which will allow the air concentrations to remain

below the TLV's. Finally, the water data was examined with respect to the

following proposal by MSD:

Gentlemen:

The MSD intends to make the following change in your Waste-water Discharge Permit effective May 15, 1982.

By no later than August 15, 1982, the total concen-tration of organic material in Permittee's waste-water shall not exceed that amount which causesa concentration of 300 parts per million (v/v) oforganic substance in the vapor space above a grabsample of Permittee's wastewater equilibrated at200C in a closed vessle whose volume is twice that

4 of the wastewater sample.

The MSD proposal which determines vapor headspace above the wastewater at

equilibrium was compared to the water analyses data that was analyzed by

the Purge and Trap method. This comparison is limited by the fact that the

MSD proposal represented equilibrium concentrations while the Purge and

Trap Method represented total concentrations forced out of the wastewater.

....

-13-

ANALYTICAL METHODS

Instruments

The two direct reading instruments were chosen to complement each other

* with respect to the compounds that they would detect and also because of

their portability and safety in potentially explosive atmospheres such as

* those likely to be encountered in sewage treatment plant influent areas.

V... Century Systems' Portable Organic Vapor Analyzer (OVA)

The Century Model OVA-128 is designed to measure trace quantities of

organic vapors and gases. It is incapable of causing ignition of hazardous

atmospheric mixtures and can measure concentrations ranging from 1 to

1,000 ppm. The OVA is a lightweight, portable unit which can be operated

on batteries or by alternating electrical current. This instrument

4 functions as a flame ionization detector (FID). Like conventional gas

chromatographs, the OVA must be calibrated with a known compound and

concentration. A continuous sample is drawn into the probe, metered,

filtered and transmitted to the FID. Inside the FID, a hydrogen flame

ionizes (burns) the organic vapors. The resultant positively charged ions

are collected at a negative collecting electrode with the aid of the

electric field between the conductors and the collecting electrode. As the

carbon-containing, positive ions are collected, a current is generated in

relation to the rate of collection. This current is amplified and

-. converted to an output signal which can be read on the meter or the recorder

in ppm's based on the calibration compound (20).

The OVA-FID is highly sensitive to hydrocarbons (saturated, un-

'. -- .. .•. .

-14-

saturated and aromatic) such as hexane, methane, benzene and toluene and

similarly sensitive to mono-substituted halogenated compounds. The FID is

less sensitive to polysubstituted halogenated compound and compounds with

a low ratio of carbon-oxygen, carbon-nitrogen or carbon- sulfur atoms. For

detection with the FID, a compound must have both carbon and hydrogen in

its' makeup. Therefore, it has only a negligible response to carbon

monoxide (CO), carbon dioxide (C02 ), ammonia (NH4), sulfur dioxide (S02),

hydrogen sulfide (H2S), carbon disulfide (CS2 ) and water (H20) (20).

For this study the OVA was calibrated based on toluene (10, 100, 500

PPM) in the presence of approximately 90% humidity using the same equipment

and method described by Barsky (18). Relative sensitivites of the OVA to

various compounds are listed in Table 1. These sensitivities are listed

using toluene (the calibration standard) as 100% and reflect sensitivities

in dry air (20) and experimental values in 90% humidity. The sensitivity

was not significantly altered due to the high humidity since the

calibration compound (toluene) was prepared in the presence of 90%

humidity.

H-NU Systems Photoionization Detector

The H-NU Model PI 101 is a photoionization detector designed to

measure trace concentrations of gases and vapors. The H-NU can be equipped

with several different lamps or sensors depending on the ionization

potentials of the compounds to be detected and the possible interferences.

The sensor is a sealed ultraviolet light source that emits photons

energetic enough to ionize many compounds. The ionized compound is driven

(by an electrical field) to the collector electrode where the resultant

........,' .. "- -. -:.. .-.- =.- _, ,_' " ... ..- .. ,.. .. • .-.

i • .. ... ,

-15-

current is measured.

The lamp used for this study is the 11.7 eV lamp. This lamp responds

to any gas or vapor with an ionization potential less than or equal to 11.7.

However it will not respond to compounds with ionization potentials

greater than 11.7 such as 02, N2 , CO, C02, H20, CH4, H2 or S02. Unlike the

OVA-FID the H-NU-PID will detect ammonia and hydrogen sulfide but not

methane.

In this study, the H-NU PID was also calibrated using toluene (10,100

and 500 PPM) in the presence of approximately 90% humidity. The H-NU

calibrated and functioned properly in the laboratory. However, in the

field the instrument's response deteriorated rapidly. After several

hours, the H-NU no longer responded to even the calibration gas. After

solvent cleaning of the lamp, the instrument would respond but with a

marked decrease in sensitivity. A new lamp was obtained from the manu-

facturer; however, the result was identical (See Figure 4). For this

reason further use of the H-NU was discontinued. The 11.7 lamp has a

decreased sensitivity in the presence of high humidity (18). This dis-

advantage in itself could be compensated. However, in the presence of a

mixture of water vapor and corrosive gases (S02, N02, H2S) the lamp did not

function properly. The 10.2 eV lamp may have operated properly, however,

it would not have detected ammonia or hydrogen sulfide and the 10.2 eV lamp

is also somewhat erratic in the presence of high humidity (18).

With the use of the H-NU coupled with the OVA, it may have been

possible to estimate the percent contribution of methane, hydrogen sulfide

and ammonia. However, because of the unreliability of the H-NU (11.7 lamp)

i o : . . . - - , .- , - . . , . b . . . . , , o . . . . .

-16-

in the presence of high humidity combined with a corrosive atmosphere, this

portion of the study was abandoned.

Biomarine Combustible Gas Meter

A Biomarine Combustible Gas Meter was also used in this study

primarily as a safety precaution. This direct reading instrument

determines % oxygen, % LEL hexane (lower explosive level), and % methane.

This instrument was also equipped bith an audible alarm. During the three

weeks of sampling the instrument conistently gave the following readings:

21% 02, <2% LEL hexane and -0.1% methane.

.."

'.:6 '*6 s- 7 - . -. * - --9: . % ' * * -

-17-

ANALYTICAL METHODS

Laboratory Analysis

Overview

All samples were maintained on ice following collection, during

shipment and upon receipt at the U.S. Air Force Occupational and En-

vironmental Health Lab (OEHL), Brooks AFB, Texas. The charcoal tubes were

analyzed using standard NIOSH methods which involved desorption in carbon

disulfide and subsequent analysis by gas chromatography using a flame

ionization detector (FID). The duplicate water samples were split into

two sets. The first set was analyzed for purgeable halocarbons using

standard EPA method 601 (40 CFR Part 136) (25,26). The purgable

halocarbon method employed a purge and trap gas chromatographic set up

equipped with a Hall Electrolytic Conductivity Detector (HECD). The

second set of water samples was analyzed for purgeable aromatics using

standard EPA method 602 (40 CFR Part 136) (25,26). This method also made

use of a purge and trap set up; however, the detector required was a

photoionization detector (PID). All of the samples were integrated into

the OEHL quality control program in order to verify the accuracy of the

analytical results.

Analysis of Charcoal Tube Samples

Analysis of the charcoal tubes was accomplished according to

standard NIOSH procedures. The front and back sections of the charcoal

tube were removed separately and desorbed in 1 milliliter of Baker

Analyzed Reagent Grade carbon disulfide, vortexed and allowed to desorb

for at least one hour. At this time the carbon disulfide mixtures

-18-

containing the desorbed compounds were transferred to two-milliliter auto

sampler vials. The samples were then analyzed automatically by flame

ionization (FID) gas chromatography (GC). Appropriate standards were

selected in response to the compounds found to be present in the water as

well as other compounds suspected to be present. Standards were run both

individually and as mixtures in order to determine retention times, con-

centrations and possible interferences. Each sample was run first on the

10 ft. 10% FFAP column as a screen and then rerun on one or more of the

three columns for verification and additional peak separation. The

chromatographic instrument parameters are listed on Table 2, detection

limits in Table 3 and the computer method and sequences employed in the

analytical procedure are presented in Appendix 1. In general, the com-

puter method automates the analysis, by controlling the run time, syringe

washes, sequence of injections, and the method of peak integration.

Purge and Trap Methods (EPA 601/602) for Analysis of Water Samples

In the Purge and Trap Methods, an inert gas is bubbled through a five

ml. water sample contained in a specially-designed purging chamber at

ambient temperature. The halocarbons/aromatics are efficiently purged

from the aqueous phase to the vapor phase. The vapor is passed through a

sorbent trap where the halocarbons/aromatics are trapped. After purging

is completed, the trap is heated and backflushed with the inert gas to

desorb the halocarbons/aromatics onto a gas chromatographic column. The

gas chromatograph is temperature programmed to separate the halo-

carbons/aromatics which are then detected with an electrolytic con-

ductivity detector/photoionization detector. The identification and

?. :.i<i < Z*, . ...: ¢ -< : . .. - .i ..

-19-

quantification of the individual compounds is confirmed using a second

dissimilar gas chromatographic column.

External standards were utilized both individually and as mixtures.

These standards were prepared according to standard EPA methods 601 and

602. Individual stock standards were prepared by weight in methanol

(mg/L) and then sequentially diluted to the low pg/L levels in methanol.

Mixtures were also prepared from the first stock standard and diluted as

above. Each standard sample (individual or mixture) for the GC was

prepared by taking one ml. of the desired stock concentration and adding

it to 99 mls. (in a volumetric flask) of organic free water. This flask

was capped and mixed and ten mls. were withdrawn for analysis.

The specific purge, trap, and GC parameters that were used are listed

in Table 4 for purgeable halocarbons and Table 5 for purgeable aromatics.

The compounds analyzed, their retention times and detection limits are

presented in Table 6 and 7, respectively for purgeable halocarbons and

aromatics. The computer methods and sequences employed in the analytical

procedures for halocarbons/aromatics are presented in Appendices 2 and 3,

respectively.

Calculation of Concentrations of Specific Substances of Water

The individual halocarbon/aromatic compound concentrations were

calculated as follows:

Sample area x Standard Concentration pg/l = pg/l (= PBB)Standard area

The individual concentrations were summed to achieve a total halocarbon

(WTCUGL), a total aromatic (WTAUGL) and a combined total (WTAC). For the

aromatics, the total area under all peaks was calculated as if they were

r1

7v K-. .47 -7 76 7.- - ~ ~

-20-

all toluene (WZAUGL) in order to relate the water concentrations to the

direct reading instruments (OVA) which were calibrated based on toluene.

In addition, calculations were made for total aromatics and total

aromatics expressed as toluene excluding 1,2,4-trichlorobenzene (WTABZ

and WZABZ, respectively). 1,2,4-Trichlorobenzene was determined in this

study because it was known to be present in high concentrations

particularly at the Mill Creek Sewage Treatment Plant. The suggested

methods of analysis for 1,2,4-trichlorobenzene are EPA method 612 or 625

which involve different collection and analysis methods from the ones

used in this study. These methods involve solvent extraction and

concentration of a one-liter sample, followed by florisil cleanup when

analyzing complex wastewaters. In contrast, this project only involved

collections of 20 ml. samples for purgeables. However, EPA has documented

1,2,4-trichlorobenzene using the aromatic EPA method 602 which was used

in this study. The standards for 1,2,4-trichlorobenzene were readily

identifiable, however the recoveries were only between 60-70%. This

compound eluted from the gas chromatograph at approximately 31.3 minutes

and in the wastewater samples appeared as a broad two-fold peak on both

columns which indicated an interference and made the quantitation

suspect. For this reason, the TCBZ results were only an indication of the

presence and general magnitude of TCBZ and not an analytically accurate

concentration. The raw analytical results are presented in the next

section.

do.

.- L : ; . - . - . -- - . . _ . . . . . .' .. , . . . . . -: . , . .. :.

-21-

Calculation of Concentrations of Specific

Substances in Air

The individual compounds identified from charcoal tube samples were

calculated as follows:

Sample area x Specific Gravity x 1000 1 x Vol (liters) = mg/m 3

Standard area m

These individual concentrations were also calculated in parts per million

(PPM).

The concentrations for individual substances in charcoal tube air

samples were summed to achieve totals (CTMGM and CTPPM) expressed in mg/m3

and PPM, respectively.

In addition the total chromatographic area was calculated based on

toluene (CZMGM and CZPPM) in order to compare the charcoal tube concen-

trations to those of the direct reading instruments. This calculation was

made both for the total identifiable compounds and for the entire

chromatographic area (which included unidentifiable peaks).

IN

-22-

STATISTICAL METHODS

Various statistical procedures were performed on the raw data at the

University of Cincinnati Computer Center using the Statistical Analysis

System (SAS-796) (31). The raw data was keyed into a WYLBUR (32) system

and then transferred to a University of Cincinnati data base (M80116) for

accessing by SAS-796. The SAS-796 statistical programs are briefly

described below and presented in detail in Appendix 4.

SASRUN 1 - This program transferred all raw data from WYLBUR to the

main data base in the proper format for SAS manipulations.

SASRUN2 - This program performed Pearson correlations between

Century (PPM) values and selected water and air values. Regression

analysis was also performed on the Century (PPM) values with respect to

the three different plants.

SASRUN 3 - This program performed Analysis of Variance (ANOVA) and

General Linear Model (GLM) on the PPM values with respect to the different

plants. This program also performed additional Pearson Correlations and

plotted the various variables with respect to PPM values.

SASRUN 4 - This program performed additional Regression Analyses

comparing total values for water and air as well as the Century PPM values

and plotted the respective variables.

SASRUN 6 - This program plotted an overlay of PPM values vs. flow by

plant and perfomed Pearson Correlations by individual plants on all other

variables (air and water).

SASRUN 7 - This program performed three types of correlations

(Pearson, Spearman and Kendall) by plant on all water and air variables,

'I

. , . , . .l.-, o * _. 'U . - : .. .- , -, , . : j . ,, _. . -. . ,

-23-

including the sampling condition information (see page 11).

SASRUN 8 - This program performed a one way nonparametric analysis by

plant on selected charcoal tube values. A GLM was also run comparing

different times of the day and different days for each plant. A second GLM

was run comparing weekday to weekend for each plant. Various values were

• also plotted to investigate additional relationships.

-24-

RESULTS

Variability and Sampling Conditions Data

Tables 8.1-8.3 suninarized the numbers and types of samples collected

at each of the three plants. The variation in sampling conditions and the

Century OVA data is presented in Tables 9.0-9.3. Table 9.1 presents the

data for the Mill Creek Wastewater Treatment Plant; Table 9.2 presents the

data for the Muddy Creek Plant; and Table 9.3 presents the data for the

Little Miami Plant. The key for the computer generated tables (9.1-9.3)

is presented in Table 9.0. Each of the parameters in these tables was

recorded every 30 minutes. The Century OVA data are presented in both PPM

and mg/in3. The data in Tables 9.0-9.3 are also graphicly displayed in

Figures 5-7, by plant. The above mentioned tables and figures represent

total hydrocarbon concentrations based on toluene as the calibration

standard for the Century OVA and demonstrate the wide fluctuation in

concentrations hourly within a single plant and between the three

different plants.

Hourly and daily variation in both total hydrocarbon (Century OVA)

values and the water and air concentrations was the most dramatic at the

Mill Creek Plant which was also the largest wastewater treatment plant in

this study. At the Mill Creek Plant the concentration of total hydro-

carbons was generally greater in the afternoon than in the morning (except

Monday) and was generally higher on weekends than during the week.

However, these data only represent one week's sampling and are not

necessarily representative of other weeks or other seasons. The values

were not statistically different from one hour to the next. However, if

-25-

the data were broken into only two time periods (0900-1400 and 1400-1900)

then there were a larger number of peaks during the afternoon hours at

each of the three plants (see Table 26 and Appendix 5).

At the Muddy Creek Plant the total hydrocarbon values were also

generally greater in the afternoon than in the morning. It was also

noticed that the concentrations increased in response to rainfall.

The Little Miami Plant also showed the same trend as the other two

plants in that the afternoon concentrations were greater than the

morning. However, at the Little Miami Plant the concentrations tended to

decrease with rainfall.

Table 10 shows the Pearson Correlations for sampling conditions data

correlated with the Century OVA data (PPM) for each of the three plants.

Several of these correlations were statistically significant at or below

the 0.001 level; however the correlation coefficients were relatively low

(between -0.30112 and +0.56456) which indicates that no single factor

could consistently be used to predict the presence of peaks on the Century

OVA.

At the Mill Creek Plant the Century readings were highest (according

to correlation coefficients) when the flow was low, late in the day, late

in the week (weekends) and when the air and water temperatures were high.

The Muddy Creek Plant readings were highest late in the day, when the

water was colored, when the water temperature was high, when the air

temperature was lower and when the humidity was high. In contrast, the

Little Miami Plant readings were highest when the flow was low, late in

the day, late in the week, in the absence of rainfall and when the water

-26-

and air temperatures were lower. All of these observations are based

on correlation coefficients with PcO.O1.

Charcoal Tube Sample Analyses

Tables 11.1-11.3 present the results of the analysis of charcoal tube

air samples collected during periods of peak episodes observed on the

Century OVA for the respective plants. At the Mill Creek Plant a peak was

defined as any Century OVA value greater than 100 PPM. Whereas, at the

other two plants a peak was defined as any value greater than 50 PPM since

the baseline values were much lower than the Mill Creek Plant. Table 12

shows the results of the analysis of the 8 hour TWA charcoal tube samples

for the respective plants and Table 13 presents the results of the

analysis of charcoal tube samples collected at other sites of interest.

The samples collected at these other sites include samples collected

above the airspace of the venting grate at the Mill Creek Plant where the

main sewer lines are combined prior to entering the wet well/bar screen

area. This venting grate was installed as an added safety precaution to

provide the volatile compounds being mixed an outlet prior to the

wastewaters' entry to the wet well. Other samples were taken only six

inches above water level rather than in the breathing zone area and

samples taken above pools of water in the wet well but behind the bar

screen at the Little Miami Plant where the building was open in the center

for three floors. Pearson Correlations are shown in Table 14 correlating

the Century OVA data (PPM) with results of the charcoal tube sample

analyses. Only three correlations were statistically significant at or

below the 0.001 level. These three correlations were all found at the

-27-

Mill Creek Plant and concerned the following compounds correlated with

the Century OVA (PPM) data: MIBK, chlorobenzene and toluene. MIBK and

chlorobenzene were only detected in about 10% of the samples, however when

they were present the Century values were high. Toluene on the other hand

was present in almost all of the samples and when the Century values

increased so did the toluene concentrations found in the charcoal tube

samples. Benzene also had a relatively high correlation coefficient at

the Mill Creek Plant. Table 15 presents three different types of

correlation coefficients (Pearson, Spearman and Kendall) comparing Cen-

tury OVA data (PPM) with the charcoal tube sample results for the Mill

Creek Plant. The Spearman and Kendall correlation coefficients are

nonparametric correlations; however they show the same trends as the

Pearson Correlations but with higher confidence levels (greater than

0.001).

Water Sample Analyses

The results of the water analysis are presented in Tables 16 and 17.

Table 16.1-16.3 gives the results of analyses for chlorinated organic

compounds (halocarbons) for the three respective plants with a key of

abbreviations in Table 16.0. The results of the analyses for aromatic

compounds are presented in Tables 17.1-17.3 with Table 17.0 as the key.

Table 18 presents Pearson Correlations comparing Century OVA data with

the results of selected water sample analyses. The results of the water

analyses did not correlate with the Century data. The confidence levels

were never below 0.1245 and many of the correlation coefficients were

slightly negative values.

-28-

Comparison Studies of Water and Air Samples

Tables 19.1-19.3 presents the Century OVA data (PPM) and the total

concentrations found on the charcoal tubes (in PPM and PPM based on

toluene) and also compares the water concentrations as total chlorinated,

total aromatic, sum of chlorinated and aromatic and a total aromatic based

on toluene (all expressed in pg/l - PBB).

Tables 20.1-20.3 presents statistical summaries of water and air

concentrations by compound: range, mean, median and frequency of de-

tection (%). Table 20.0 presents a key for Tables 20.1-20.3.

Table 21.1-21.3 compares selected charcoal tube samples to their

respective Century OVA values, both expressed in PPM. The first column

gives the total of the individual compounds found on the charcoal tubes.

The second column expresses this total as if all the compounds were

toluene. The third column expresses the total area of the chromatogram as

if it were toluene. This third column includes small unidentified peaks

in addition to the compounds identified. The fourth column represents the

Century OVA values recorded at the time the charcoal tube samples were

collected. The Centruy OVA values are expressed as PPM toluene since the

instrument was calibrated based on toluene. Even when the total con-

centrations on the charcoal tubes are expressed as toluene, the charcoal

tube samples represent less than 20% of the Century OVA readings.

Table 22 lists the ACGIH TLV's and STEL's for the compounds in this

study. These values are also listed in Table 23 along with pe- lent

values needed to calculate the CTLV's and RAT's presented in Toogood and

Hobson's paper (14). The CTLV represents the maximum allowable con-

.-

-29-

centration in water for a single compound so that the TLV in air will not

be exceeded. This value is calculated using the TLV, vapor pressure (VPo),

the limiting activity coefficient including sewage at the appropriate

temperature (Y,) and the molecular weight in the following formula:

TLV x MW x 760

CTLV= VPo 18 (MW H20)

Toogood and Hobson's (14) CTLV's are derived based on a static equilibrium

assuming no ventilation of the sewer airspaces. The RAT refers to the

relative atmospheric toxicity which is calculated by the following

formula:

K Ci

RAT = CTLV, i

Table 24 presents the CTLV's for the compounds detected at the three

plants as well as the maximum % of the CTLV detected and the range of the

concentrations found. Table 24 also shows that only at the Mill Creek

Plant did the concentrations exceed 5% (but less than 10%) of the RAT

proposed by Toogood and Hobson (14).

Table 25 presents a summary of the statistics that were performed

comparing air and water quality data in addition to the correlation

coefficients. In all of these tests the results were not statistically

significant.

Table 26 gives a summary of the number and magnitude of the peaks

observed on the Century OVA, which were compared statistically. Table 26

shows there is definitely a greater number of peaks in the afternoon as

opposed to the morning at each of the three plants. The statistics for

-30-

Table 26 are presented in Appendix 5 where a log linear model is developed

which is based on the data in Table 26. The best fitting model is as

follows:

log PPlant-time-peak = Uplant + UTime + UPeak + UPlant-Peak +

UTime-Peak

This model indicates that all interactions between plant, time and peak

must be considered except the interaction of plant with time.

.• .'

I ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ------- -.--.-.--------...------ -- - .- - ~ - -. . . .

-31-

DISCUSSION

Figures 5-7 graphically displayed the daily plant variation in total

hydrocarbon concentrations hourly and daily. The correlation co-

efficients in Table 10 showed that the hydrocarbon concentrations were

generally higher late in the afternoon and on weekends. The higher

concentrations were also correlated with lower flows which generally

occurred late in the day and on weekends. Table 26 compared the total

hydrocarbon concentrations in the morning (0900-1400) with those in the

afternoon and evening (1400-1900). The afternoon concentrations were

generally higher and much more variable at all three of the plants

confirming the results presented in Table 10. The two smaller plants

showed a more exaggerated difference between morning and afternoon

concentrations than the Mill Creek Plant which is probably more a

reflection of the lower flows at the two smaller plants.

The higher afternoon concentrations were probably due to the

startup of industrial activity in the mornings and the sewer transit

time (time it takes for the wastewater to travel from origin to plant)

as well as increased residential use in late morning. The changes noted

in association with rainfall could incorporate multiple occurrences.

The decreased concentrations at the Little Miami Plant may merely re-

flect dilution of the wastewater by strom runoff. The increased con-

centrations at the Muddy Creek Plant appear to represent a case where

the storm runoff washes the sewage through the system as a slug since

the Muddy Creek Plant is the smallest of the three plants with the least

amount of industrial contribution to the sewer system. The possibility

IZ 1

-32-

that this increase represents industrial fugitive dumping, though

unlikely, cannot be discharged. This increase during rainfall could

also represent soil leachate from some of the nearby tank farms.

In comparing the charcoal tube samples with the total hydrocarbon

values (Century OVA), it is noteworthy that in almost all cases the

charcoal tube sample represented less than 10% of the Century OVA

concentrations. Some of this difference may lie in the fact that the

Century OVA does detect methane and the very light hydrocarbons

(ethane, propane etc.), whereas the charcoal tubes will not collect the

permanent gases. It is also possible that the high humidity decreased

the adsorption capabilities of the charcoal, however no water was de-

tected condensed within the charcoal tubes. Many other factors (dis-

placement, ventilation, etc.) may have decreased the charcoal tubes ad-

sorption capabilities but none of these factors alone or combined

should have altered the results by more than 10-20%. If in fact the

Century is detecting primarily lighter molecular weight gases, then the

charcoal tube concentrations may actually be a better indication of

harmful compounds present: particularly since the charcoal tubes allow

identification of the compounds. The Century OVA merely gives an

indication of total hydrocarbons. In any case the Century OVA can

provide an immediate indication of the maximum possible concentrations

present from which immediate decisions can be made. The charcoal tube

samples can then be collected and the analysis can identify the specif ic

compounds and their respective concentrations.

The correlations coefficients (in Table 14) indicate a very good

-33-

correlation between the Century OVA (PPM) total hydrocarbon concen-

trations and the charcoal tube concentrations of toluene (correlation

coefficient: 0.82820 with P<O.O01) at the Mill Creek Plant. There were

also strong correlations between the Century OVA concentrations and

methylisobutyl-ketone, chlorobenzene and benzene. The latter compounds

were not routinely present, but were generally present when a peak

occurred. These correlations were present only at the Mill Creek Plant

and not at the two smaller plants. The total of the individual

compounds found on the charcoal tubes did not correlate well with the

Century OVA concentrations at any of the plants. At the Mill Creek

Plant it may be feasible to merely monitor for toluene as an indication

of routine peak concentrations, however, further documentation would be

needed before toluene could be used as a marker compound.

The added ventilation at the Mill Creek Plant and the Little Miami

Plant appeared to help decrease the total air concentrations by forcing

fresh air back into the sewers rather than drawing air out and thereby

shifting the equilibrium and encouraging volatilization. The venti-

lation grate at the Mill Creek Plant prior to entry of the wastewater

into the bar screen area also appeared to decrease the wet well

concentration as evidenced by the sampling conducted above this grate.

The water concentrations of individual compounds and total hydro-

carbons indicated very low PPM to sub-PPM concentrations which did not

allow adequate evaluation of Toogood and Hobson's (14) proposal. The

concentrations detected never exceeded 55% of the proposed CTLV and in

most cases were less than 10% of the CTLV. The RAT was never exceeded

-34-

since it is derived from the sum of the CTLV15. The total concentration

of the compounds detected in the water samples never exceeded 10% of the

proposed RAT and in most cases represented less than 5% of the RAT.

The water concentrations did not correlate well with the Century

OVA concentrations (P > 0.10) and in fact many of the correlation co-

efficients were slightly negative.

Both the Century OVA (and other direct reading instruments) and

the charcoal tube sampling are important in characterizing sewer and

wastewater atmospheres. The Century OVA can give an immiediate

indication of a potentially hazardous atmosphere. The use of this in-

strument can yield further information by placing a charcoal tube in

front of the probe. If there is little or no change in the Century OVA

reading, then the majority of the compounds are light molecular weight

hydrocarbons and permanent gases such as methane, ethane and propane,

which are relatively innocuous unless their concentrations are high

enough to affect the % of available oxygen. If there is a drastic drop

in the Century OVA reading, then further sampling should be done with

charcoal tube and water samples to determine the identities of the

compounds are present.

-35-

CON~CLUSIONS

The studies conducted with the Century OVA (a direct reading in-

strument) indicated dramatic changes in total hydrocarbon concen-

trations both hourly as well as daily. The Century OVA readings were

higher and more variable in the afternoon than in the morning at all

three plants. The readings were also higher on the weekend than during

the week at each plant. The readings were highest and the most variable

at the Mill Creek Plant (the largest plant).

Total hydrocarbon concentrations quite often reached or exceeded

100 PPM while the water and air concentrations remained in the low PPM

levels. This discrepancy indicates that a large percentage of the

Century OVA concentrations are probably due to low molecular weight

2 hydrocarbons and permanent gases such as methane, which are not col-

lected on charcoal tubes. Even though the charcoal tube concentrations

represented less than 10% of the Century OVA concentrations, there was

a good correlation between high Century OVA readings and high concen-

trations of toluene, methylisobutylketone, chlorobenzene and benzene.

These correlations were only found at the Mill Creek Plant and not at

the two smaller plants. During the four week course of this study no

TLV's, CTLV's or RAT's were exceeded.

rx The Century OVA can provide an immediate indication of the air

quality and by using a charcoal tube in front of the probe, an estimate

can be made of the degree of the hazard (i.e. % permanent gases).

A large hazardous slug was not detected at any time during this

study. However, the possibility of a hazardous slug is always present.

- 36-

* Proper coummunication between industries and wastewater treatment plants

should be paramount, particularly when a spill occurs. However,

frequently the first notification of a hazardous slug is received via

wastewater treatment workers. Perhaps, increased penalties to industry

(for spills) coupled with more complete and frequent wastewater

analysis of the influent (at least hourly) could prevent or at least

alert workers to potential problems. The analytical proposal for

headspace analysis of wastewater samples at the industries' effluent

made by the Metropolitan Sewer District of Greater Cincinnati (MSD)

would help industry "police itself." This proposal should also be

instituted with respect to hourly sampling of wastewater influents as a

form of "early warning device."

-37-

* a J ~ ' 4 .. 6.~.

owl

d e.

*~~~~ . . . . . .- .. - - -. ...

-38-

ji" I t =6 •

I, .-... . .-- -- -- 4----

r-- - * : . - .. . . . . . --- *.,II I,-- ; ,,: . . -_-_ _ . __

il ,'.~* , ', .

*g~ ~ s

W- II ",",'" O FA AL

.. ,./ U ,: / :1

143

h *--S ......-- .. W

t:9 , , i.a1 ;.I '-4

t. *,, : , ,. 6 o'l o *1 _,.J. . , 6 i* US, , 0

~~0 "It,' ..

0 44

:,' , .. . .: , ', ;.-;%tgas C4i

9 9999

. . 4

a. -39-

* I o

.4

r4JIjJ~Wa.C0

., , . . . .. , _ . . . .. : ;. . ' -- .-o _ .. .-. .. . ....S .- "- ... . -°

-40-

150 FID VS. PID (11.7eV)HNu PID

I. j(New Lamp)

Century FID0C100-

.0

0

12 13 14 15 16 17 18Time - 24 Hour Clock

Figure 4. A Comparison of the Century OVA

(FID) a-d the HNU (PID).

r-'a

*. . . . . . . -. . . . ... . . . . . .~

-41-

Century Data- Mill Crk PlantMon. (1) Tues.(2)

150 140 MOD 120 MOD

V 100-

0

-.,..-

1010- Wed (3 ISO Thur (4)1o 180 MOD 10 MOD

9 12 15 18 9 12 15 18

rm 24HorClc

ig Wed. (3) 150- Thur (4)IBO80MGD 140 MOD

*- , -100 l 100

S50 50

0'1 9 12 15'is 18s I . 12 15 18

:'-'Time - 24 Hour Clock

,..');';Figure 5. Century OVA Data.

-42-

Century Data - Mill Creek Plant (cont.)

150- Fri. (5) 150- WSa()140OMGD 110OMGD

100- 100-

50- 50-

IL

a 0* 1 1 1 1 1 1 U I I I 0: .. . . . . IC 0 9 12 15 18 9 12 15 18

* 300-j. Sun. (7)o 200~100 MVGD

150

o 100-

50-

01 .. .

9 12 15 1Time -24 Hour Clock

Figure 5 (continued). Century OVA Data.

L

-. , '- , . , , - -- . r ... -..- -.

r,

-43-

Century Data - Muddy Creek Plant

150- Tues.(2) 150- Wed.(3)12 MOD 10 MOD

100 100

IIL 9 2 1 18D 12p0

150, Thurs.(4) Fri. (5)

- 10 MOD 10-15 MOD

100- 100-

*01

9 12 15 1 B 12 15 18

Time - 24 Hour Clock&T Flow Throttled at Indicated Time period

Figure 6. Century OVA Data.

U..,..- 150 - 10 M. 0 -8 M . . .-GD..- * -. --

-44-

Century Data - Little Miami PlantMon. (1) 150- Tues. (2)

150: 28 MOD (TH) 28 MOD (TH)

100" 100"

50 50-

0 I. I I V , , ,

9 12 15 18 9 12 15 18

0

150 Wed. (3) 150 Thurs. (4)26 MOD 26 MOD (TH)

0loo: 100

50 so0

0 w * I * 0 II', VII

9 12 15 18 9 12 15 18Time - 24 Hour Clock

*(TH)-Flow Throttled throughout sampling period

Figure 7. Century OVA Data.

-45-li

Century Data - Little Miami Plant (cont)150- Fri. (5) 150 Sat. (6)

27 MGD 22 MGD

100 100

so-50 .a.. %.0 0 nA,, ,,

Co 0:11 11 11rrT, . .I . .I . .9 12 15 18 9 12 15 18.2 Time (x 100)

150- Sun. (7)119 MGD

100

50 -

4

9 12 15 18Time -24 Hour Clock

Figure 7 (continued). Century OVA Data.

5,I

"c -q' , .,,.' .". ." ." . , . ." • ' ' ." . ." ' . " " . , . - " ." " . . , , . . . -. • . . _ .. .

-46-

TABLE 1

RELATIVE SENSITIVITIES OF THE CENTURY OVA

Dry Air + 95% Humidity*

Toluene 100% 100%

Methane 83 80

Benzene 125 135

Trichloroethylene 58 65

Hexane 75 80

Methylene Chloride 85 100

Perchloroethylene 58 65

1,1,1-Trichloroethane 75 90

+Sensitivities published by manufacturer converted from methane to

* toluene basis.

*All standards were prepared in the presence of 90% humidity.

,.

*1 , . ., . ,, : '. _. , . .. ..- -. . . . . . . . . .. . . , . . . - .

-47-

TABLE 2

INSTRUMENT PARAMETERS FOR GAS CHROMATOGRAPHIC ANALYSIS

OF CHARCOAL TUBE-AIR SAMPLES

Instruments: Hewlett Packard (HP) 5710A Gas Chromatograph7672A Automatic Liquid Samplers (ALS-99

samples)HP 1000 Series E ComputerHP 3350 Lab Automation System

Detector: Flame Ionization Detector (FID)

Carrier Gas: Nitrogen

Attenuation: 10 x 2 =20

Injection Port Temp.: 2500C

Detector Temp.: 2500C

Run Time: 30 Min.

Column Temp.

Column 1: 10 ft. 10% FFAP 1000C

Column 2: 20 ft. 5% FFAP 1500C and2000C

Column 3: 6 ft. 5% Carbowax 20 M 1000C

Column 4: 10 ft. 5% SE-30 110CC

All columns 1/8 in. stainless steel coiled columns.

Computer Methods: ZR04, ZR05, ZR08, ZR09, ZR1O.

Computer/ALS Sequence: ALS9.

|-,.

-48-

TABLE 3

DETECTION LIMITS FOR COMPOUNDS DETERMINED BY GC ANALYSIS

OF CHARCOAL TUBE SAMPLES

Compound Screened Abbreviation* Detection Limits Mg

Freon 11 F-11 0.02Chloroform Chlor 0.02Methylene Chloride MeCi 0.02Bromodichloromethane BrCl2 0.03Dibromochloromethane Br2Cl 0.03cis-1,2-Dichloroethylene cDCE 0.011,2-Dichloroethane DCA 0.011,1,1-Trichloroethane Trich 0.01Carbon Tetrachloride CC14 0.10Trichloroethylene TCE 0.01Perchioroethylene PCE 0.01Methyl Ethyl Ketone MEK 0.01Methyl iso-butyl Ketone MIBK 0.01Benzene Bz 0.01Toluene Tol 0.01Ethyl Benzene E+Bz 0.01Chlorobenzene ClBz 0.01o-Xylene Xyl 0.01m-Xylene Xyl 0.01p-Xylene Xyl 0.01o-Dichlorobenzene Cl2Bz 0.10ni-Dichlorobenzene C12Bz 0.10p-Dichlorobenzene C12Bz 0.101,2,4-Trichlorobenzene TCBZ Not Detectable +

*As used in the data analysis.

+Not detectable using this method.

V4~

-49-

TABLE 4

INSTRUMENT PARAMETERS FOR ANALYSIS OF PURGEABLE HALOCARBONSIN WATER SAMPLES

Instrument: Tracor 560 GCLSC-2 Sample ConcentratorTekmar Auto Lab SamplerHewlett Packard (HP) 3352B Lab Data

Reduction System

GC Detector: Hall Electrolytic Conductivity Detector700A (HECD)

Purge Gas: 40 ml/min. (helium)

Inert Carrier Gas: Helium-40 ml/min.

Attenuation: 10 x 2 or 200

Solvent Flow: 4

Injcction Port Temp.: 110oC

Detector Temp.: 2500C

Trap Temp.: 1800C

Column 1 Column 2

Carbopack B 60/80 Mesh Porasil C-100/120 Mesh

Coated with 1% SP-100 Coated with n-octane

8 ft. x 0.1 in. ID stainless steel 6 ft. x 0.1 in. ID stainlesssteel

Initial Temp.: 440C 500C

Initial Hold: 3 min. 3 min.

Program Rate: 80/min. 60/min.

r Temp.: 2200C 1700C

Final Hold: 15 min. 4 mn.

Computer Method: PURG601:TOComputer/ALS Sequence: SEQ21B-SEQ21F

•.. . . . . . . . . . . . . . . . . . . . . .

-50-

TABLE 5

INSTRUMENT PARAMETERS FOR ANALYSIS OF PURGEABLE AROMATICS

IN WATER SAMPLES

Instrument: Tracor 560 GCLSC-2 Sample ConcentratorTekmar Auto Lab Sampler (ALS)Hewlett Packard (HP) 3352B Lab DataReduction System

GC Detector: Photoionization Detector (PID)-h-NU SystemsPID-52-02

Purge Gas: 40 ml/min. (helium)

Inert Carrier Gas: Helium 35 ml/min.

Attenuation: 10 x 6 or 160

Injection Port Temp.: 100C

Detector Temp.: 2500C

Trap Temp.: 1800C

Column 1 Column 2

Suppelcoport 100/120 mesh Chromosorb W-AW 60/80 meshcoated with 5% SP-1200 and coated with1.75% Bentone-34 1,2,3-Tris (2-cyanoethoxy)propane6 ft. x 0.085 in. ID stainless steel 6 ft. x 0.085 in. ID stainless

steel

Initial Temp.: 50oC 400C

Initial Hold: 2 min. 2 min.

Program Rate: 60C/min. 20C/min.

Final Temp.: 900C 1000C

Final Hold: 20 min. 20 min.

Computer Method: PUR6O2:TOComputer/ALS Sequence: SEQ22D-SEQ22H

• , ' ....'... .... (...... ... . . .............. .... . . . . .. . .

-51-

TABLE 6

RETENTION TIMES AND DETECTION LIMITS FOR HALOCARBONS

IN WATER SAMPLES

Compound Abbreviation* Retention Time"* Detection Limits ug/h

Methylene Chloride MeCi 7.34 0.25

cis-1,2-Dichloro-ethylene DCE 11.46 0.10

Chloroform Chior 12.02 0.05

1,2-Dichioroethane DCA 12.77 0.03

1,1,1-Trichioro-ethane Trich 14.08 0.03

Carbon Tetrachloride CC14 14.45 0.12

Bromodichloromethane BrCl2 14.89 0.10

Trichloroethylene TCE 17.15 0.12

Dibromochioromethane Br2Cl 17.70 0.09

Bromoform Brom 20.45 0.20

Perchioroethylene PCE 22.93 0.03

*As used in the data analysis.

"*Retention times for column #1 (Carbopack B, 1% SP-1000) 8 ft.

-52-

TABLE 7

RETENTION TIMES AND DETECTION LIMITS FOR AROMATICS IN WATER SAMPLES

Compound Abbreviation* Retention Time** Detection Limits ug/h

Methyl Ethyl Ketone MEK 3.00 0.20

Benzene Bz 3.44 0.20

Toluene Tol 6.U8 0.20

Ethylbenzene EtBz 8.77 0.20

p-Xylene Xyl 9.29 0.30

m-Xylene Xyl 9.54 0.30

o-Xylene Xyl 10.28 0.30

Chlorobenzene ClBz 11.39 0.40

mn-Dichlorobenzene Cl2Bz 17.61 0.30

o-Dichlorobenzene Cl2Bz 18.38 0.40

P-Dichlorobenzene Cl2Bz 24.33 0.40

1,2,4-Trichlorobenzene TCBz 31.30 0.40

*As used in the data analysis.

"*Retention times for column #1 (Suppelcoport 100/120 mesh coated with

5% SP-100 and 1.75% bentone-34, 6 ft.).

4 4 4 *4~ . - - - . Z- - . T

771

-53-

TABLE 8

SUMMARY OF ANALYTICAL SAMPLES COLLECTED

.

-54-

TABLE 8.1

SUMMARY OF ANALYTICAL SAMPLES COLLECTED

MILL CREEK

Number of Days Sampled 7

Number of Charcoal Tubes Sampled 28

*Number of Peak Charcoal Tubes 14

Nubro orTA hrolTbs7

Number of 8thorT Charcoal Tubes 7+

Number of Water Samples* 19

Century OVA Data Points Recorded** 128

+ Actually represents 14 charcoal tubes since they

were collected in series. Overnight samples were

also collected but in almost all cases the batteries

in the pumps died before morning so these sets of

* tubes in series were analyzed but not included in the

data.

*Water samples were collected in duplicate to allow

* analysis for both aromatic and halocarbon compounds

(i.e. 38 water samples were collected).

*Data Points recorded every 30 minutes for duration of

sampling.

-55-

TABLE 8.2

SUMMARY OF ANALYTICAL SAMPLES COLLECTED

MUDDY CREEK

Number of Days Sampled 4

Number of Charcoal Tubes Sampled 13

Number of Peak Charcoal Tubes 8

Number of 8 Hour TWA Charcoal Tubes 4+

Number of Other Charcoal Tlubes 1

Number of Water Samples* 9

Century OVA Data Points Recorded** 68

+ Actually represents 8 charcoal tubes since they were

collected in series. Overnight samples were also

collected but in almost all cases the batteries in

the pumps died before morning so these sets of tubes

in series were analyzed but not included in the data.

*Water samples were collected in duplicate to allow

analysis for both aromatic and halocarbon compounds

(i.e. 18 water samples were collected).

*Data Points recorded every 30 minutes for duration of

sampling.

-56-

TABLE 8.3

SUMMEARY OF ANALYTICAL SAMPLES COLLECTED

LITTLE MIAMI

Number of Days Sampled 7

Number of Charcoal Tubes Sampled 17

Number of Peak Charcoal Tubes 6Nubro orTA hrolTbs7

Number of 8thorT Charcoal Tubes 4+

Number of Water Samples* 9

Century OVA Data Points Recorded** 101

+ Actually represents twice amount of charcoal tubes

since they were collected in series. Overnight samples

were also collected but in almost all cases the batteries

in the pumps died before morning so these sets of tubesin series were analyzed but not included in the data.

*Water samples were collected in duplicate to allow

r. analysis for both aromatic and halocarbon compounds

(i.e. 18 water samples were collected).

*Data Points recorded every 30 minutes for duration of

sampling.

-57-

TABLE 9

SAMPLING CONDITION INFORMATION

-58-

TABLE 9.0

Key For Tables 9.1-9.3

Spl = Sample Number (consecutive)

P = Plant

1 = Mill Creek

2 = Muddy Creek

3 - Little Miami

D = Day (1 = Mon, 2 = Tues, etc.)

# = Number of sample for given day

Dt = Date in Month of August and September

Time = Time on 24 Hr. clock

PPM = Century Reading in PPM based on Toluene Std.

3MGM = Calculated mg/m from PPM (using Toluene)

FLO = Plant Flow in Millions of Gallons Per Day (MGD)

R = Ran, I = No Rain, 2 = Rain, 3 = Rain + Throttled Flow

S = Detergent, 1 - No Detergent, 2 = Detergent Present

C = Color, 1 = None, 2 = White, 3 = Red, 4 - Brown,

5 = Smell

pH = pH of Water using Indicator Paper (Scale 1-14)

AT - Air Temperature

WT - Water Temperature

H% - Relative Humidity %

.. °. .,- °. ....- . . . . . . . .

N7.71

-59-

TABLE 9.1

SAMPLING CONDITION INFORMATION AND

CENTURY OVA AIR SAMPLING DATA

. el':;...~ ~~ L -', ,, I... . rAv: FP£Z)" ." , .~ P, ', .R: A "....-.:Ji o

CCI "2 1 00L 121C 12/i 2 1 1 7.C 27: 7'C2 1 1 2 M" 1;j 150 ., 1:r I 1 1 7.022 7 1 74

02" 1 1 3 C- l1tf .OZ 3(2 1 1 ! 7.t 2 71 7'M'."0[ 1 2 t (" 12 c r:2C 7 5 2 -7.~ ' ' 95 7'

!L 12I5 ' 12 C, 3C2 I:; 1 i .C "2 71 C 7."0: 2 1 1230 C5' 22 i,'; 1 2 7.0 -2 7, "7/

2"7.1 ' 2 7. C :2 7C 7,'O[.: .'~ ~ ~ ~l- 1 -. .3 -. i 1 C, I 1 . . - 7,-0' 1 i; v,.C 152 i , 1 1 . 2 7

(7 2 1 1 22" !(*^2 I. 1 2 C' 22 Vc.2. I.. 2 ' 2., 2 1 2 7. 7 7. ECI 1 2 1 2 '2d'0% IC IC 12C 1 .. ( 7 ," 7

" 612I " IC -r .. ..."2121 10. [,C 22"1221 2 7 .0 727.2

0. 2 2 1L ILi. C4 251 12. 2 2 1 -.1' 7 40142 251 1100 5, 17: 1 7.A 'A 7i~C]2 1 2 5 .. .. 1. 2 ,.0 , 7L IC2

2' 1 " .'Z 2 2 7.C 2

0A12 F.u2 :~ 23; ( 7.C~7

CX L0 132 CC22'4:1 77:T22.-' 1 'lR. 1 CIC I I.: I 7.Ct 7~i7'.02212 C'.C 7c I-, I 121 7. r, 7 77

:. 0 : . 1 2 - , 4' T Cr. * ... 1. 1 1 2 7.5 .1.. . . ,. 2 1 7. , 7 7i "

0252 .2 1310 C., 02.3 E'.! 1.7707C2112 1130 C20 2 41 17'. I /'

2- 1 1, % C221C 127., 7' 74C''-~~~ 1 2 2C2,C 130 CC 225 1it'. 2 1 ' 7..71 :v =-030122"2. 12 - -4 2CC 142222 ".D 71 117-

,~~1 c,. 1 1i 1." Z- [ 2 : %"f.. . . ,[

P'7 1 2 22IO I52: 11: 14 01 1 1.-7'717C22 1 2 1'.27 15 " 17.' 72 7,.2S 1 2 2C10 17'5 . .. ; f1II7. 7 _

.. . .r.4

.. . " -7,I 5 ] .' . C' 1'1 7 f ", 7:3'

-4 A & . A '.

|C22 1 2 2.:1 f 19Ub C2G 075 W14 1 1 7. C 7: 71 72

K.

*4

- . -. . . . . .--°. -o **. -. ,-,,

-60-

TABLE 9.1 (continued)

M ILL CIXEt WATA7 TPZA&M-,r PLMrt (CO.rAlT,0JZ

ZP" 7 L M . c kLAI i, z C F A

1 2 11 C90r 025 C., 20 2 2 2 7. 72 59 !2o:'0 2 1i OS3C 015 05'. 20- 1 17.0 73 S,2

ZS 1-5 2 11 100C 03' 12', 203 2 1 7.0 72 59 C211 r-, o 1 1 1 7. 72 -c r-,2.7 1 3 r 2, 1 2 - - 1 1 7.1 7-

0? .: 11 i1 r 0L: I I 1 1 17.(- -2 ;2t"~~~C - 7 ii 12';' O 5 iMq 13[r 2 1 2 7.0 72 S '-'-11 1 2f.; 0 1:r 1217.t72 5'

C'.2 1 2 0 21 1. -, 2?2 , 2 1 7 -, , "-C42 1 2 112 12-. 5; 1 h 2 1 2 7.0 73 :C'2 112: iili 0? a1: 1 7.0 70 2

S2~.1 , ..( I" 13 1 1 7., 72 P 2C 4. 1 1 212 151 0t 24z C 22 1 7.0 2 ."0C 20 2 41 1 OW ?.2 1SC ill 7.273 1 SC

,047 1 . 1522 .,O: , 2Z' 1 .2 1 7.0 7 C 2C4: 2 r 1.1 . .113 1] 17.7 r n

-,_i 1:0 7 2 . 121 7.5 7 70 "' C5" ! 1 1 ..1 ,, %' 3=:., 11- 7.57'" 70 .2C,' ot51 1 - -57Z

- 1' ..,1 U %i Ic: 37 17' 1 1 1 7.57' 71 7.21.2 1 2C!! 12 1C I ,.2 7 Tc

C53 1 3 221" 9 7 .% 2 1 2 1 3 . 7f054 2 2211 1 30 C.30 22. 2 2 1 . 7.. 70 ,205- 1 2 231: 2 0 ,. 22 2'2,, 1 2 7.0 74 ": £2c 5 1, 12 COL'C"3 12, I 1 7.5 72-, -!"i~~~ ~ ,S r : " .

.572 %J ,3 LL . 1?, 22 7.5 72L1E 1 4 2 12 1".0 DOS 032' 1 '-% 21 7.5 72 ,

L5. 4 4 12 I,30 O02 00: 12 1 1 1 7.E 72 5, r20 1 4 5 12 1 n , 1 1 112- 117.5 72 11 £2"311 5, 12 113( 3, C2 120 1 7.572C:2 1 4 7 120. C:7 C. ,2 22 .C 1"

053 1 4 C 12 1230 00t 030 120 1 1 1 7. 72 GS 70 f' 1 4 S 12 13= 010 033 130 1 1 1 7.0 72 355

I -

-61-

TABLE 9.1 (continued)

KILL Mr-El' " rEATWr. Th .T PL-Ai (C0),%TIN:UL

SrL P 3 TI:-r PX MiC-- FLZ T, S C S7. AT I A %o2

C .2 I 12 3.2.., '0 C124, 1 ,. S'. ., 1 7.C 72 .C'! 1 4 1112 1400 C2^ r75 13' 111 7.r-72 5S 2C? I f 1212 143r 012 C2 033 1 1 7." 72 12 S2D', 321 42 1M0 0_2C 001402 17.0 72 o 'r0. 1 4 1412 153C 02, 075 140 1 1 1 7.0 72 5C C 27.1 4 1512 150C CIP 33 14C 12 1 7.C 72 Sr 82

07 1 4 r 112 1130 C 22 " -42 1 1] 7.C 75 9": 72C72 1 ' 1712 17,fiC C7L 221. 14C I 1 7.5 75 Sr 52,73 1 122 173K f05C 1 S 1'2 1 1 1.C "75'5 2C7." 2' 1S12 13-C "f", i . 7.. 75 . ,AC-5 2C32 12"3 010 032 V'O . 1 11 7.5 75 55 C'2r7" 1 2112 ILI 21 31 r.,10 1 1 1 7.5 75 r-

2 4 2212 1'5 fL" 22 12 • 1 1 1 7.5 75 62C_" 4 2.'" Z 1L' IM ., 113 .) 1 2 ".5 75 5E 12P" 15 1 13 110GIV 1 033 "14 7 1 7. rC.. 5 2 1- 1.- C" I r" -K 1 7.r 72 5 c.

-.. S 2 12 12v' '0272 i7T 1 11 7.C ? " r. e: r

22 5 13. 02 7 97C 26" 7 -2 -1 I . 7. r 7Z SS EC- 02 55 1 13[:O M15 121 1 1 7. 2 755C.'; 1 5 , I I32 02C 075 12 1 C 1 7.1 1 7 5 5C5 E A 7 I" 1422 C22 "L" 14, 11 1 7. 7: 50," 1 5 13 1" 10' 37 2.4 :1? 7.0' 7 2

' 5 5 S" E' I 1 2 1 7 . C 73 .

02 15 12.2 1 1,'C3 !r 112. S.L 75. rO?, 151112 1.3 C2.L 11.0 2 7. C 75 t2

.C 1 5 122.2 1 O--5 .1 14r : 2 2 7. C75 'C r-.,'S 1 5 1'13 1700 :3" 22 14 1 1 1 7.C 75 'S 22

C. 2 5 13 2)173 2 " 35 . 1 3 7.75 S '00,2 1 5 1513 15G, S 4'. 152 14 d 'A 1 2 5.5 75 55 5S,094 2 5 24" 1030 16 27- 24C 1 4 5 7: 5 S0,5 1 51"12 ICS0 C 2 0 -:, 12.1 5:75 -5 5

P3" 15 I1Z 1930 080 301 140 11 1 .5 7 !r 5:

. :a? :. ; %,% .. . ' " - . ". ". . -. ;7 " -. " - : .' . - : . , - .- . . .-. i,.. - .r . - . -- . . r . - .

-. '4

. -62-

TABLE 9.1 (continued)

KILL CP L- 'SATE$. T-EN'rL , PL\", (CCMMNI.ICD'

C.;: " i 14 11 IC .0 : IV..o 1 1 1 7.r 75 S,"z 0-2C9.I 1 5 2 14 1130 02C 075 ICC 1 1 1 7.07 S. ' 2MEV I 5 2 14 1200 040 151 110 1 1 1 7.C 75 52_CC 5 4 14 122 04) 251 11: 1 1 17.C 75 5 C21 2I I 5 1 300 12 37! 11 1 1 'A 7.C 75 F, S2"2 . 5 1. CCS 214' 11C I 7. 75 SS.2

1 1. 7 1: 1CE. OSC 3:I 1 1 2 17.075 5;4 1 1 . t. 143 1 C 37 10 I 11 7.1 , 75 .5-r 52_

105 1 . i 5 2 C J4 C 151 11 I I1 7.C: 7E 15 S2I. 'A . 153C, ,T2 11-- Alt I I I 7. 75 S 2

o.' 2 - 1.v. 1' ', o:15 r 11. 2 1 7.' 7 " .A-. 1 , 1214 172C C2C C7 12 2 l 7.270 51 ,

|4. V V- 1 I A 7. f, 7Ir 1 12514 173. 221 "' 1 1 1 .0 7^'2 . .S 1.... iZ C:C ? L I I; 17. 73 "1 5 A2132 1 C 1 C . 1L 3'. 12 27: 11C I I 1 7.C 7' SS. :211-1 1 1714 i0'' S." 151 11C 1 1 1 7.0 77 .-.*I . 1 7 1 15 13: CEL "' 1c; 1 1 .5 77 7 7115 1 7 2 15 1220 IC 37' 1C 1 1 1 5.5 77 7C 'I11 7 3 15 1400 12, .52 1C.,1 1 1 . 71217 7 4 15 1432 030 221 1 ''n 2 1 7.0 77 717

r 7 5 15 15,2 12; 1452 100 1 1 1 7.0 7 722'I 1 27 1 15 1520 12 4"2 1(0 CC . 7.0C 77 7C 71

12E i 7 - 15 IZ' 13" 4' I0C 1 1 7 C 77 -7 C121 7 2 15 i 3(;r.112c 1,.2 1 C 7.77 771222 . 7 9 15 17C) 3C0212w IC" 1 1 , . "7 73 71123 1 7 1C. 172 210 7'02 ,.2 I I2 7.1. 77 71 7124 17111C1f' 12" 452 11 0 2 : 7.C 77 71 '.

12E 7 121531 2"C " 301 1 7.077 71 7112,1 7 1315 19C 100 372 2.~ ; I 1 7.C 77 71 71127 2 7 1425 1 1:3f) 2 'C2 1 r 1 2 1 7. C 77 71 7.12Z. 17 1-15 200 0., 301 1022 1 1 7.r0 77 71 72

01*:i.

4-.° .. ° . % - % . .

-63-

TABLE 9.2

SAMPLING CONDITION INFORMATION ANDCENTURY OVA AIR SAMPLING DATA

MUDDY CMEK WASTATEr% TENE . ' PLA-'

SPL P D 01' TINE PP, P G FLD R !: C R! AT V"T t".

12E 2 2 1 17 100n 02C 075 C0 1 1 I 7.C 72 7. 9313C 2 2 2 17 1[3C 020 123 c10 i I 1 7.0 72 74 n1. 2 2? 17 31 100 020 07t 010 2 1 1 7.0 72 74 921 2 2 2 47 113C 04C, 151 C's I 1 1 7.0 72 74 V31 22 22 5 17 1200 022 120 '*3 11 1 7.C 72 74 93134 2 2 2 7 123C 052 1513 0 C2 1 1 7. C2 274 (D23'S 2 2 7 17 130C 05. 1 E; 01,1 1 1 1 7.0 72 74 9213522C1713030^ 113)0I 1 7.0 72 74 S3127 22 S 17 1350 0?, 03 0 1 1 7.0 72 74 91-- 2 2 1-27 1400 C7% 212 01: 11 2 7.C 72 74 S312 2 217 111- 3,£2 34" 1. ' 2 .2 7.(. 72740.

124 22 1217 100 09', 32 ,IC I I 1 7.C 72 74 S2141 2 2 1217 1523L 0 "r, :1 C1 C 1 2 7. C7 74 S-112 2 14 17 0 090 223 C21; 1 2 7., 72 74142 22 1517 1 30 CC' 224 CIC 1 ' I 7.C 72 74 9324 22 1517 17;0% d,07'" 2[25 C,2, 1 11 7.C 72 74 9114! 2 2 1717 1730o C5 211 CIC01 1. ' 7., 72 74 S.

11. 2 11? CS . "2C C 75 212.2 S. 5 !72 7C1- 2 3213 C 2 22 M. IC" 1 1 3.5 72 7 .14W 2 23 1 lOX. 1 2. "7! 010 1 1 1 7.C 73 7C S714,c 2 24 1^ 1"3G 024 C6 V' 231 1 1 7.C 72 7C Z150 2 5 h11C 3d 020 704 -IO 1 1 1 7.c 72 70 "1512? 18 113C 02" 075 L1 I I 1 7.0 7.0 V71,2 2 3 1? 12Cr C15 C5 OX, 3I I .. 73 7r "'15 2 3 2 1 1230 C2 075 ClI(' I I I .0 72 7 8154 2 3 9 1C 13Cr 022 0. ! I 1 1 7.C 77 70 .155 2 2 1102[1 31 Z030 113 r3, 11 1 7.C 73 7( t'S15 23 i21^ 140C 025 094 lt ' 1 1 17. 72 7 S157 2 3 1 13 143 " 032 12C 01; I1 1 7.C 72 72C 22 5. 2 3 V1.f IS:C 023 075 011 1 1 7.C 72 70 £"15S 2 3 513 153C C22 C3 CI,- 1 3 1 7.C 73 7, C1 2 1 18 160, 0 ." 002 01. ' 1 1 7. rf 73 7iol 2 3 171C 130 024 0s; 01C 1 1 1 7.0 7.3 70 S12 2 3 11C1 170' 030 113 0 1 1 1 7.C 73 70-C'1.73 2 3 ISIS 1730 C24 090 01 1 . 7 7 9d

-64-

TABLE 9.2 (continued).%, ~~~~IU.DY C.NMA .Tg' Tjqi M', -Y PL%': ' (". ,ITIPUZ. )

IPL P Z, I DT' TI-:l PP. FG. FLL R S C F. i AT W :

2" 23 2C2 1'If,2 5 r,'01 r I I .I 72 70 SE- 2 4 1 2 V ICOO 025 05-^ 02'02 i 7.( 72 7 C -F

.- :2 .2 29 .L;3( nK30 l ^1c i i I 7.n 3 2 . c1",2 4 ? le 1160 03, 11:- OIC I 1 1 7.0 73 7L'1ZC 2 4 4 IS' 113C C:2 #0W. O(. 1 1 1 7.0 73 7C r,13! 2 4 5 It 120C G24 09t; 01' 2 1 1 C 7 3 71 F2T; 2' 1! 12:, (.2C C75 C2!N I 17. 73 7(. F21 2 4 7 2!, 12C" C271 !.20 1 1 1 7.0 72 7"17: 2. 19 1.3C C., II3 1 21 7.,. "7,, 717' 2401 14 0.2 12r C20 11 7. 72 7C174 24 ICI':. .2= c". 1. r I I 7.C 77 7C FYS2 4 1115 15o0 "C? 12u 011 2 2 7.0 72 70

! 2412";~ 15-," U" 1=1 C.. a 1 1 -7.07'271-1-7 2 f( 1.1 !.'' '.. .. '' *7, **a.? ~ ~ie . a.-2. 1 .: 1 7. 7. ".. .J-"" q" ( , l, . l''t . " 1 " , : .,2 1 7. C 72. 7[ t

17" . i ] 7C., G4." 152 lC . I I 7.C 7." 70 ZI ,. 2 4 1,1 . 7 1 I.0 [l (.,1 1 a 1 7.C -3 7C 3I 'I 2 4 171w I ,L'' ;3! 135 01£ 1 1 2 7.r7' 73 rM 2 1 2L 120 0.20 075 CIO I 1 .5 72 3 r.

1 ]-3 22 5 2 20 1 1 1 0 n'. 11 1 . 77 7 731I. 2 S 2": 13VO 022 r. "'' 1 5..72 7

:,,1%!' 2 5 e2L 123' C20 P7[- Or. I 1 1 A,.5 -2 73 r5 X 5' 2 4 '' 1%1 0: 5 or 1 1 .5 72 73 "

SF7 2 5 % 2(' 14 .0 C1" 02 15 2 1 2 7.0 72 72 .lIO 2 5 7 20 150C : CD C, 1 1 1 1 7. 72 7"?? 2 5 2C I5C CO P"L rO 1,1 1 1 7.C "2 7. -19025 .2C COD 0 37'. ,NC I 1 5 5.5 '723 5-"1Si 2 5 .' !CS ID 4V. 010. 1 1 5 S. c 72 -Or

12 2 5 112c 1i2(' 05 257 C,! 1 1 1 S.5 72 7v c'1S: 2 ! 122C 17C.100. I .,I 1 1 -. 5 725.1V 2 5 1220 1730 C' Z 345 CI0 I 1 1 6.5 72 73 £31-5 25 142C 1000 100 376 01C 1 1 I5.! 72 73 93191 25 1520 10,0 020 075 01D 11 '5 72 73 93

.... .................. .

-65-

TABLE 9.3

SAMPLING CONDITION INFORMATION AND

CENTURY OVA AIR SAMPLING DATALIMTTL ! Vwl 'ASTCMATER T.ILq' PLANT

SPL P V ,' DT TIKX' MP, Ma.: FL: R S C R, K KAT 'IT h

197 2 1 1 20 11CC 02', 03E C2 C. 2 1 1 7.C 74 75 51312 30 113K 012 04 C2 2 11 7.0 7. 75 c 529£ 3 1 3 3L 12CC CIO 03" C2K 3 1 1 7.0 74 75 952C.C 3 1 4 30 123( L4- 151 C2' ; 1 1 7.0 7Z. 75 952( 31 53 130( 01C 633 2 1 I 7.C 74 75 952,. 3 1 3 3C 1335 02; 075 C2: 2 I 1 7.C 74 75 9.52C- 2 1 7 3R 1400 C12 C45 C 2,- 1 1 7.0 74 75 SF-20,.. 1 Z' 3 0 143V1 030 C2 L, I 7.C 7 4 75 orF2F5 31 £ "15C oCI C2Z 3 1 7.C 74 75 ''-" ,CZ ,3( .01 C 2 -12 7.1 7.' 75 520 :1 " I 'I'V 1U0 0 ' cS 02 31 ] 7.0 74 75 .E2r.. 2 1 1230 1 0 C1I3 03E 02Z 3 2 1 7.C 7. 75 V!.200 3 1 17.?-C 17-0 012 C'5 C2' 3 1 1 7.0 74 75 £5210 3 2 1 31 lO2. C03C 23 020 1 1 7.0 7" 0 t"21 -- 2 2 31 1130 04' i25n 02,3 I 7.0 74 2

21- 32.2: -.. .. 113 C2Z 7 7.0 7 7 t ,.C21.32 f 31 123C 020 075 C-7 3 2 7., -- 7' 4.2:-, 32522 1 C3, L3Z 11: 2 7721E 3 2 5 3 1330 025 04 C2' I I 7.C 75 749,2 2 7 2 14V 03 11 . -2t 11 7.0 7! 74 S'122722 31 , 0t25 C4 02^ 2 1 1 7,C 7 "70;, -21t .293 4' 15C o 113 C2 21 1 7.C 7' 7. S.219 3 2 I0l 152.r 041. 151 ' 2.;' 7,. 7 7 r220 3 2 1131 1500 C2Z 105 C2 31 1 7.C 7c 74, ')r221 3 2 122 1 2'"C 0.2, 075 CXZ 3 1 27.C 7-, 74 to"222 3 2 1331 1700 "15 055 C2'. 1 .1 7.; 76 7223 3 2 1431 1730 P22 0f'd C2: ? 17.0 71 74

*2243 10?i 1 122 '.r. 14.302S1 22 5 .E 7. 7', 55225 2 C 12"' 040 151 '2, 1w-,0 .- 10.,2 1 1 1 S.e- 75 7,- 1-5

22S 2 3 3 01 1300 032 12C 025 1 1 2 5.5 75 74 "52273401 130 2W I M ,7 02n 1 1 1 C.5 75 74 S 522E 3 3 5 01 1400 03S 125 C25 1 1 n.5 75 7'. S5229 3 3 k C] 143' m15 245 C2 S 1 1 6.5 75 7. 5230 3 3 7 01 150C 0S0 3Cl 02 1 1 6.5 75 74 S5

-66-

TABLE 9.3 (continued)

-' LlI T' F -LMwI V.A&-TaokTi T TMET PLZwr (CMTINUED)

• SPL P D P DI T,1A ,PP, FLC2R S C PA AT %"J!' i

21 ? S C1 1-Z30 04C 151 (2' 1 3 1 5.5 75 74 ,3t232 3 9 01 103 010 03- b2i 1 1 1 5.5 75 74 95233 3 1001 1030 07C 211 02' 111S.57574 VS5234 3 1101 170(; 020 075 C2' 1 1 1 6 0.5 75 7A. 9-1235 3 12'% 1730 C32 12C 027 1 1 5.5 75 7. 52 1 3 3 13-1 1 C20 C?5 C2Z I 1 1 5.5 75 74 9S2' 2-7 3 ,:I(.2 MC[o C25 05 02 1 .1 1 6.5 715 74 52. .202 IC3C C20 C75 25 11 Z.5757' £523. ( ' M2 11O5 02C 10O5r C2. 111 Z.! 75 74, VS2(3p02 13, C?.0 123 02 1 1 S.5 75 74 .:

-2.'2 ( 5 L2 125 02 : 1 1 1 :.5 75 74 9:2 6 C2 I23k, C22 5'3 C2 'A 1 1 .5 75 74 v4- 2 7 C2 130(, 032 12,'n 02r 1 F.5 75 74 c,

2',4 3 £ C2 1215 02t !CS 02 1 1 1 (.5 75 74 9245 3 r2 133n 024 C [0 2 1I 1 .5 75.7...4241 - 4 1C"2 140C C24 0a02- J 1 1 1o 75 7.0 nr24'7 4 3 102 14' 3 040 12 G2' 1 .5 7S 7t .

.- 3 4 122 I .. I.. 1 1 7S 74 S2'.B:n13 1! 2V L3 125 C2 1 C.E 75 74 %,525C ? V.2 1500 C2C 075025 1 1 26.5 75 74 912_A' 3 4 1502 IS13 C24 09 C211 1 1 5.5 75 74 C.0

4 25234 1302 17V: 022 023 C2 2 1 1 7.07 7. V52 3 5 C 092C CiC r,,' 2 1 1 7.0 7f 55 C-2254 5 2 C3 1 (I! lu 03 C27 1 1 7.0 7 7 .. S2! -- 2 5 3 55C27 1 I 1 7.0 75 74 £i25' 3 54 (3 110C 025 0"f 0271 1 1 7. C 7E 74 S527 5 5 V3 113C 3G 113 020' 1 1 7.C 7 cr25: 3 5 1 G3 120 024 12 : 027 1 1 7.0 75 74 !25r.' _35 7 03 1220 C5w 1" c27 1 1 1 7.C 75 7 C£

U2 3S : 1300 03C 113 C27 1 1 1 70 75 74, 52 1 3 5 0 03 1330 04C 151 02; 1 1 7. 75 74 'VD26 2 3 5 1003 14Oh 050 1,C 025 1 1 1 7.C 75 7.5252 3 5 11 3 1425 020 075 C25 1 1 7.C 75 74 55

- - - - - -

-67-

TABLE 9.3 (continued)

LITTrLE Nuob I rsTE. ATIrt TR-a'T.I;l, PLI,Ti (C',.".'JE)

S P D ' I 'a. ":. X T.: %*C FLZ. r S C l " T ? .'T V-

-3 5 1203 15GO r.25 MZ C25 ! I 1 7.0 75 7 49 r.2S 5 13L3 1530 022 0 Z3 C2 1 1 1 7.0 75 74 9-

I,1,1 030 113 02' 1 1 1 7.0 75 74 rr2'7 153 12o C2 075 c51 I 1 17.c 75 745

51 .0 .2 12C02 ' ,.C 75 7 SE2 3 17"3 "5'. 11: 025 1 1 7.C 75 74527L 2 f 1 C4 12(, .'12 C,& 022 1 115.571G327 20a 123 f1 C.. 02- 1 1 1 .5 71 53 21.2: -, 2. C U -O' . ! s

27 : 7 24 04 123 2FU C0 0221 2 1 .5 71 53

274 - 5 0! 1" 4 C 1 2 211 . -, 1 ci27C4 .- C. 1ML Z C-5 C22 1 1 .571 53277 3 G. 1!0,.,0 04'a A5 C22 1 2 .5 71 Cl2, 2-. 2 . 04 15-O 042 12 I 1 1 1 ;. 71 1 4a"T- 1 1 . -S 7 , Gr 71z,21"04 1:. "C- ,_r .' 1 1 71 '.

7 "2 _,, . C2 11 .7! . 3,1104 17, 2 - . , .

S2tI 17 .' .- O, 1o1 '22 1 n.5 71262 3 3 1 'A 1 52 0772C 11 6.!71 12^0 3 7 1 C5 1206 C2e 075 C1' Z I 7. 71 f:7 rr2i- 4 3 i 2 CS 1220 0,3,4 121 015 1 1 1 7.C 71 "7 52L" E 3 7 " C5 I.. V "3F 14 C.' - 12 7. C 71 "72., 3 7 4 05 1330 02 15 011 1 1 1 7.'1 71 "7 :2:7 27 5 05 14 U, 4 7 1 Z r I 17.0 71' "72 4'1, 3 75 05 14 2L : 52 1 '. 2 i I 171.t 7 11 57 <2 P 3 7 7 05 1500 05 211 M1 I I I 7.C 727 -r

2 2 7 e 05 15 t 10C4 241 C.' I 1 1 7.0 71 7 !:2-'1 2 7 0 CS 1'JC 040 151 01 1 1 7.C 71 07 .5S223 7 ICO5 153b 043 172 n1I 1 I 7.7 7 57 or.22 .3 7,11 /C5 17CC C.-'a2 1 Bur CIE 1 1 I CI. 71 , -it214 3 7 1205 1730 C(4 151' C.. I 1 1 7.C 71 7 C52S5 3 7 13C5 1,..6 050 i: 011. I I I 7.C 71 "7 5S2 S. 3 7 1405 1.3V 052 lf OloI 1 1 17.0 71 . 7 .257 3 535 1900 0 l8S 010 1 1 1 7.0 71 37 55

3. ,7 ',50 19-.

pp e

*, -68-

TABLE 10

PEARSON CORRELATIONS FOR SAMPLING CONDITION

• DATA COMPARED TO CENTURY OVA DATA (ppm)

Mill Creek Muddy Creek Little Miami

Flow -0.30112 -.09656 -0.47012

Time 0.28294 0.42529 0.26308

Day 0.28558 -0.03210 0.43885

" Rain -0.06056 0.08456 -0.87108* * **

DET -0.03344 --

Color 0.04488 0.38817 --

pH -0.17020 -0.26487 -0.16762•** ** **

* Air Temperature 0.35366 -0.51863 -0.27862

Water Temperature 0.23388 0.51987 -0.34161•, ** **** **

Humidity -0.12786 0.56456 -0.21257'0 * **** **

P<1.0** P<0.10

*** P<0.01

"4 **** P<0.001

- .* 4 _- .4 - .'5, -.. 4 .*.** ,..* .4.. .... : , _ ,- . ,. ,: : ,,, , : - - * . . . ." _ ° . - . -

-69-

TABLE 11

RESULTS OF ANALYSIS OF CHARCOAL TUBE AIR SAMPLES

COLLECTED DURING PERIODS OF PEAK EPISODES

OBSERVED ON CENTURY OVA

rnnf 7 . r .-. - .- .-

-70-

TABLE 11.0

Key For Tables 11.1-11.3, 12, 13

Spi - Sample Number (coincides with Century Spl 's)

ID - Internal ID Number

P Phase, 1 - Air, 2 - Water

CTRIC - 1,1,1-Trichloroethane

CBENZ - Benzene

CTCE - Trichloroethylene

CPCE - Perchloroethylene/1,1,2,2-Tetrachloroethylene

CTOL - Toluene

CXYL - Xylene

CCLBZ - Chlorobenzene

CHEK - Methyl Ethyl Ketone/2-Butanane

CMIBK - Methyl Iso Butylketone

CTPPM - Total PPM of Individual Compounds

CTMGM - Total mg/m 3

CZPPM - Total peak area expressed as Toluene in PPM

CZMGM - Total peak area expressed as Toluene in mg/m 3

NOTE - 1 - Peak - No Water Sample Collected

2 a Tube placed in front of Century Inlet

S-3 Outside Grill

4 - Inside Grill

5 - One Floor Above Bar Screen

*Concentrations reflect total of front plus back of charcoal

tube; at no time did the concentration in the back section

exceed 25% of the concentration in the front section

9-.

S. .o

0 fl

*6~~~ 00 6 0 000

C0 w U" 0 00000 U)0coo aco. 0

a0 0 66 roe e 0 00

ow 00.0 C fl H b

0~Cw00000Nm 0Z

o.00 0 02 V 0 0060

C~0.119 S LA ZM 6 t00 w 19

t

%I Q a tj s

* -72-

ts Ig Y

0 0000 o 0 4

ro 0 0 0 0 0 ~ I 0 0

S0 '3 00a '. jP z t1. % 00 0 a 0 wa a4 w

0 Z X, p H >

e% 0 3 CD 0 0 0) 0 Iz02888888 '>

~ R .

0 j 0

ZWJ Lab8

N N.

* 0 0 0 op 000 z

* z E 000n

*b 0 0 *

U, 4a 0z

-73-

ocoa8co

En0O 0 OC0 0 0

_ 0Z000 00 n "a

0 0

~h0

W 0 0 C -l

*l 0 0 10 0 0 0o t b

03 V'

Do~ w IM 0

C* 0coom 0 '

<0

CON,

Help

-74-

TABLE 12

'- * RESULTS OF ANALYSIS OF THF 8 HOUR TWA

CHARCOAL TUBE AIR SAMPLES

OCOCQMW 'D SAI4PLC ANUMYSS

EIGHT HWJf" T# SWA.ES

P.ILL a= ST TR TRE IT uT

SPL IW P ciau c z CrCC cc CTOL crp. C%4 cZP4 czmGM

258 ol 1 2.1C C. 00 0.00 0.00 0.00 2.1C 11.34 00C2.5; OCCO.W5.2c.9 03 1 0.00 0,00 0.00 0.CO 0.00 C.00 0.00 0004.85 0001.293C. 05 1 3.44 0.20 0.20 0.15 0.1. 4.10 31.26 0003.32 00P0,E3;1 11 1 0.00 0,00 0.00 0.00 C.00 OO0 0.0c 0.00 0.00302 21 1 0.0 0.08 C.00 0.00 0.00 ',0 C0.26 0002.98 OCO.79XC.3 27 1 0.00 0CA 0.00 0.00 0.00 0.00 0.00 0.00 0.0.304 34 1 0.00 0.00 (.00 0.00 0.00 DOc 0.0 0.00 0.00

VMli2 cpJzK UST.MamE Ta~r.M " P!~nI

SZI. =,; p Cm z r. C=Z CTC. CnCE C7OL CrTP Cmomv. CZPp ..

X-5. 41 1 0. . .GCA .0O0 r 0.00 0. 00 0.00 0.00- 1 0.03 0.(i O.CC 0.00 0. " 0.M 0.00 0.OC 0.00

307 49 1 0.00 5.45 C.00 C.2S 0.00 5.73 1Sf.27 412&.20 1093. 43C: 52 1 0.00 0.o0 0.00 0.00 0.00 C.OC 0.00 =M4..5 0O13,.1

LITTLE VIAMI thEMAATE '1TREKZ- IATt

SPL ID P CBRI CSZ CAVE CPO CTOL CT. C'' CZPP CL

309 2 G 00 0.0C 0.00 0.00 0.00 C.00 0.00 0C28.71 C',07.62310 S2 1 0.00 0.00 0.00 0.00 O.0C 0.00 0.00 0018.70 0(U04.5311 65 1 0.00 C.40 0.00 3.76 0.00 4.1.) 26.50 0031.09 0000.25317 39 1 0.00 0.CC 0.C 0.33 0.00 0.38 02.55 0022.19 0005.CM3 4 73 1 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0002.02 O00.53

-'. 325 77 1 0.o 0.00 0.00 0.00 .0 O.OC 0.00 0001.80 00.s31r 02 1 0.00 C.0 0.00 0.00 0.0 0.00 0.00 00C7.94 0002.1

m "~~~ . . . . -- , . to . ...- ; , ---. ,,,t ,- ,--,, ,,

. .-

-75-

*c. 0 c,

S0 0 ho C

. . . H

€~~~ B3FP.PPPPPBrt

is. • • •• • • . . . 0

-t 8BBB 0 -

i''

0ftJ

. .° .. 0 .k ;0 -i V

0 000888*DI0 0

a~" SOW

W to

"OI

w-=- .. * ... : * *, - - - - - - - - - -. o . , .-" - - .. ' -.- " -- .' -'-.- -. ' " '* ' ' L

P7 1 -

-76-

TABLE 14

PEARSON CORRELATIONS COMPARING CENTURY OVA (ppm)

VALUES WITH RESULTS OF THE

CHARCOAL TUBE SAMPLE ANALYSES

Mill Creek Muddy Creek Little Miami

CTPPM -0.01332 0.51508 0.43555

CZPPM -0.06622 0.55275 0.71340

CMIBK 0.72766 0.48269 --

CMEK -0.15495 0.25675 0.47584

CCIBZ 0.69740

CXYL 0.04805 -- --

CTOL 0.82820 0.15315 0.46201

CPCE -0.17561 0.51317 0.55370

CTCE 0.04685 0.45159 0.72932

CBENZ 0.65416 0.34900 0.70012

CTRIC -0.14456 -- -0.17869

* P<1.04, ** P<0.10

S** P<0.01*** P<0.001

"p

o. ~ .....

-. -77-°.,

TABLE 15

THREE DIFFERENT TYPES OF CORRELATIONS COMPARING

CENTURY OVA DATA (ppm) WITH CHARCOAL TUBE SAMPLE

ANALYSES AT THE MILL CREEK PLANT

Pearson Spearman Kendall

CTPPM -0.01332 0.30326

CZPPM -0.06622 0.43050

CMIBK 0.72766 0.60235 0.52138

CMEK -0.15495 -0.1949 -0.15401

CCIBZ 0.69740 0.61197 0.52430

CXYL 0.04805 -0.12022 -0.11698

CTOL 0.82820 0.65145 0.52074

CPCE -0.7561 -0.29630 -0.22167* * *

CTCE 0.04685 0.03763 0.03650

CBENZ 0.65416 0.60785 0.50017

CTRIC -0.14456 -0.07903 -0.06267* * *

* P<1.0• * P<0.10S** P<0.01

S*** P<0.001

'4

-78-

TABLE 16

RESULTS OF ANALYSIS OF CHLORINATED ORGANIC

COMPOUNDS (HALOCARBONS) IN WATER SAMPLES

COLLECTED DURING PEAK EPISODES

OBSERVED ON THE CENTURY OVA

-79-

TABLE 16. 0

Key For Tables 16.1-16.3

Spi = Sample Number

ID = Internal ID Number

P = Phase, 1 = Air, 2 =Water

WMeCL = Methylene Chloride

WChloR = Chloroform

WTric = 1,1,1-Trichlcroethane

WB2C =Dibromochloromethane

WTCE = Trichloroethylene

WBC2 = Bromodichloromethane

WPCE = Perchloroethylene

WTCUGL = Total Chlorinated Compounds in UG/L

WTA+C = Total Chlorinated + Aromatic Compounds -UG/L

WTAC-Bz= Total Chlorinated + Aromatic Minus 1,2,4-Tni-

chlorobenzene

e- -7

ixai

E-4 'N CZ P. m 0%r% C k vcCZ. ' CM ar i2 6 ~ 0 0 S 0 0 a 0 0 a 0 0 a 0 6 0

t o 0 6n IS N 0 m Oft L.0 2 cce 0- 0 0

0* a

0 &c~0 0 N rrCO OU l

eg p )p

egg 0 0 0 gec e.O

0 ~ vcooxc~msQ 4 eqe. q

4 4 * .j g -0Ca C2 Q

ggegego0 0 a0 0 00 00 0 0 00 0

Ix inn eR SSif e CJNMh

oo 'o 0 U 8Cw ot %7 N *Q enP"V1C le4 -1% -1Ci.

14~~~~~~~ Q N N N N N~4 Ntdr

rAF j o -- 0 a o t0446 C~ e-OU PO

-4- pisw.*>0 43 0 .0 f 0 0 0.* ~ l'~r VW

2; C ;0g00 ;0 0.040c 04 0

z 1 0enL-d

ft P C

0 0E-4 %C . - 10 &A Vq~N -4 %

I ly r r-0 0n000m

e.o rA- v- kn O -

*w 6w C1 m 0 0 0 0

(0 0 in ooo oj

lz- C. 0000

m W0 £i 8 Ci 0 %Ed 0 &4 C% v Ca 8 -

C4j 0 H

P.4 ~~o~occ

SH 9 .

24 04CQ

Im 0 00 Q ..a %"0 88c 0 1O8

(0

0 W0 0 4: 0 u.4800000-4 0

S0 U 9* § C

rao cn r4

00 N'-.-- 0ue

(n .4

4..4

* ~ - - -

C.)C

* 0

In,

el M Si 0 0 S0 0 0

04

N~~C (4 C; -.461 1

0

rz3 i

V_ W N 04 0-

00

H- IU- CCCC

c nn* 'O

04c4 0 ins4e %

in cm 0~NU 0 qr N '. 0 %

4 C.n N r4 .4 4 C

-83-

TABLE 17

RESLTSOF ANALYSIS FOR AROMATIC COMPOUNDS

IN WATER SAMPLES COLLECTED DURING PEAK

EPISODES OBSERVED ON THE CENTURY OVA

-84-

TABLE 17.0

Key For Tables 17.1-17.3

Spl = Sample Number

ID = Internal ID Number

P = Phase, 1 = Air, 2 = Water

WMEK = Methylethylketone

WBENZ = Benzene

WTOL = Toluene

WETBz = Ethylbenzene

Wxyl = Xylene

WC12Bz = Dichlorobenzene

WTCBz = 1,2,4-Trichlorobenzene

WTAUGL = Total Aromatic Compounds in UG/L

WZAUGL = Total Aromatics Expressed as Toluene (UG/L)

WTA-Bz = Total Aromatics Minus 1,2,4-Trichlorobenzene (UG/L)

-, . -.,, . . .' ' . . , " . " . . , . - . . ,, . " ' .4 ..> " . ' . i "

T qw a. 0, 0%0 -ek wf

-. M.. m~ to 0w -C lCl% 0qcm Lo P- C4 N e. n N qw C4C r " %, WI~ 8 rn -41-

N~. -4 I3n l0.4 *k 40 N c 0 %

A0 =amCovXY~~"wr

E4

W~ 0 0 IV o 0 6. Sq w I" *

E-4 U 1- C-100 0i C. q%. U -4 r: -0!1%r- C oCci g W. r0. V. 0 or , ^

z E4 -4 -4 0 Q 0 0~ 0 - . 04 0) P4-4 -G0! 0 FC "-

z N -rn '- a N- V

60 0 0 0 0 % I C' I'-

ce 0. ca 8 II-I' n1 0 00 ne alir ~0 C4 (4 * 0 M 0 01 @0 Vo n S - %

rP4 0 r.! r!.Qr!-rO

in "3 0 * 0 & 0 0 0 0 S 6OS O O 0 a00S

cn ~~ 000 000 CV40n 40 Ccl C

o r. 0i n oa00 -P4

CO'X *- 004il *t ON *'0aC C."r- *n3l h

~r in~iM 4v M --4 0 0 C4 0 0 0 0-0000 v0Q0a r16-1-4 -

0 . z Q0 0 V0-4 M t.-44 QC

co 00 0 0 C or o nr

al8 1P

0 ^I - Z c - ; r zc-oQv98- N- qw 4-S- C C , O I c)-

c-p0 mM0N

CO M CO N

0" -4 W.P" .-

In~An

E-4

0n tU)0 l4 C; O ".

cn NNz 0 U = _ t

E4 ' 13:c0oo4

U) 0 C'C; " 8

Ef 41 N

W IN,U) ,, 9

0-98!

.A~P at c c.~ ~

r-A133 714 CHARACTERIZATION OF SELECTED VOLATILE ORGANICS IN 212W1ASTEWARTER TREATMENT INFLUENTS(U) AIR FORCE INST OFTECH kRIGHT-PATTERSON AFB OH V S DUNOVANT SEP 83

NCASIFIED AFIT/CI/NR-83- OT F/G 13/2 NENLS OE 5EEEEmhhmiEsmhEEEEmhohhh

LLa

1IL25 11111'-___4 .6----

MICROCOPY RESOLUTION TEST CHARTNATIONAL BUREAU OF STANDARDS-]963-A

'N ' °

. o = . . , . . .. ..

-Nw • . % , . , .• = =. . . . . • - . o.q

9 f" ' alv %P 02 N rn

a% m enviA * q # c~~V- 0 e n en- N -.

C4~~h qq. G

.4 E4 OX88

2~ .* .* . *l0 -- - n9 w cN000 s. cm

Q *- 0 Q 0Q 0

gZ 0 v r

0 co co

E- 8 2 %MNNP4O

0i ,, I cc 0

004

P44

N4 N in %r NNIpq z n w

ro1 4 0CP"a

W a COCCOL8c

-88-

TABLE 18

PEARSON CORRELATIONS COMPARING CENTURY OVA (ppm)

DATA WITH THE RESULTS OF

SELECTED WATER SAMPLE ANALYSES

Mill Creek Muddy Creek Little Miami

WTAUGL 0.30380 -0.19401 -0.362172. * * *

WTABZ -0.19008 0.20491 -0.35578

WTCUGL -0.06432 -0.39438 0.19329

WTAC -0.12706 0.38305 0.06388* . ,

WTACBZ -0.20787 0.17289 -0.28234

WTOL -0.20331 -0.08843 -0.31353

WTCE -0.11786 -0.55055 -0.37511

SP<I.0

•* P<0.10S** P<0.01

S*** P<0.001

ca . . . .

-89-

TABLE 19

COMPARISON OF AIR, WATER AND

CENTURY RESULTS

-iI • ,, ' --. ., . , ...... .. ......... .. .. . .. . .

-_1 77 - 77-.77

00

1. v in 4 1 A 0 P.A 0 IZ.4 0

P .V4 4P.. P4 P.4f P. O

.4 w CO P. 914 C t O P04 t-a

a 1 0mo m ee f f

IA ISO V,1I C.m 61 @Uf" r-W1 @I 4ma11 ft 4 Z .C ft P. ;t0 m

ats

48. .4 f OC. ft.f.

@ Ci to P w a e

A 0

b% 1 P4 f @ O ft M V4 VO

00 CtOP. VU 06tf

29 so*p

MI 'n %0 an C4 0 1N I - in -. e a 4

C%%D W "a4 6 a t, I

wIU (. lE 61 . 4

C, "

th x a M h "

a. Pm 14 in

= C4 C4 I C4 % V4 N

Lina'S 4 US % 1 9

w 1q an 6'W S I

ON' r.* a "a

4Jfl5 ~ ~ C (. * M;

A..

el el al inn -

S~~0 Ic "M .. . . ..

in r

- r .. . S

*% Ch S M 0

0% 0% 40 1 fV4 44I v

pq Ipal 0 %0 M Id

4. m P's 0 0

0

LPI

-Z6

2A -93-

TALE2

SUMR.F I N WTRDT

-94-

TABLE 20.0

* Key For Tables 20.1-20.3

cis 12 Dichloroethylene

CCl4 ND in water

ClBz

*124 TCBz values are not quantitative due to improper methodthus interference from phthalates and other base/neutralcompounds

-These compounds not found in air (charcoal samples) due tohigh chlorination and low affinity for charcoal

Xylenes - Total of ortho, meta and para isomers

Cl2Bz - Total of ortho, meta and para isomers

Waters

JCarbon Tetrachloride and cis-l,2-Dichloroethylene werenot detected in any apls (ND<0.l)

Charcoal tubes were also ND<.01 for Freons (113, 13, 112,-: 12, 21)

C-i 2-Dichloroethylene1,2-Dichloroethane1,l-Dichloroethane

Ethyl BenzeneND None Detected (below detection limits)

a. , .* ,- -. . :. ".-.'".. . . ...'- ., . .. " . --.. ...- . . .. .,.. . . .. ", • S

1% 0 U t C t 0

Iii ft a V v4 i t f

"I1 . . .

U~ a in0i~m

ft .4 '! 1U @4

in v W- a %0 NtU 0

In .4 n .4 U P

rn at #A .4 4

FA. a.4i 0

14 14 -

V4 P

IM u

.44 4.4 j 04 Av i . .4

RI4 v v . E 0 m

m MD - 0

II - .4 v v .

, * 9pv v

.4 94 1

I .4

oil a- 0 10 00 1 NAaf" %D

Nw to ft 0 EmND 1

0~6 id4

N &. K gj~~ N * 0 -6 -IN 1 ~ '

0

'I~~4 r. - -

-C, 4 I-

5~ sc

t .4 44n V0 ~W 40 InC

0.10

on 4 k

f04I. ~p. 0 ' 40 N 00 4

ow

0"~- N UN I .4 % 0 - 4-

0 1 4 Ai .3

d6a

3..L6-

-98-

TABLE 21

COMPARISON OF CHARCOAL TUBE SAMPLE

RESULTS TO CENTURY OVA READINGS

... ~ ~ ~ ~ ~ ~ ~ : -'- -- J. . . .--.. . - I

-m• -99-

2TABLE 21.0

COMPARISON OF CHARCOAL TUBE SAMPLE RESULTSTO CENTURY OVA READINGS

MILL CREEK

PPMTot. Indiv. Tot. Indiv. Century

Spl # Compounds Compounds* Tot-Area* Value*

5 7.806 11.68 12.15 100

9 8.099 4.04 4.39 50

10 5.979 3.41 3.66 100

13 0.016 0.015 0.015 6

14 0.819 0.20 0.20 30

15 1.331 1.01 1.01 60

17 4.841 10.79 10.79 50

21 1.533 0.66 0.66 100

22 1.871 0.74 0.78 50

. 23 5.089 2.17 2.28 100+

24 7.446 4.66 4.76 100+

30 6.026 4.96 4.99 100+

31 1.344 0.70 0.71 100+

37 7.390 12.07 18.02 300

38 2.652 4.46 6.08 200

*Expressed as Toluene

~-I00-

TABLE 21.1

COMPARISON OF CHARCOAL TUBE SAMPLE RESULTS

TO CENTURY OVA READINGS

MUDDY CREEK

PPM

Tot. Indiv. Tot. Indiv. Century

Spl # Compounds Compounds* Tot. Area* Value*

43 0.097 0.09 0.09 70

44 2.429 2.43 2.56 80

45 0.947 0.94 0.97 80

48 0.103 0.07 0.07 35

51 2.281 1.45 2.02 40

54 30.072 10.03 11.57 100

55 1.911 1.53 1.70 100

56 23.645 7.01 9.43 100

57 17.433 6.90 7.45 60-100

*Expressed as Toluene

-.

;- w N-101-

TABLE 21.2

COMPARISON OF CHARCOAL TUBE SAMPLE RESULTSTO CENTURY OVA READ~INGS

LITTLE MIAMI

PPMTot. Indiv. Tot. Indiv. Century

Spi # Compounds Compounds* Tot. Area* Value*

64 0.692 0.24 0.49 20

67 65.931 31.95 61.89 s0

68 110.858 41.66 43.17 80

71 0.299 1.05 1.16 30

80-- - 0.12 80

e81- 0.58 100

*Expressed as Toluene

-102-

TABLE 22

TLV'S

Compound TLV** STEL***

MEK 200 300

Benzene* 10 25

Toluene 100 150

Ethyl Bz 100 125

Xylenes (omp) 100 150

Chloro Bz 75

Dichloro Bz (omp) 75 110

1,2,4-C13Bz (TCBZ) 5 -

Methylene Chloride 100 500

Freon 1000 -

1,1-Dichloroethane 200 250

1,2-Dichloroethane 10 15

1,1,1-Trichloroethane 350 450

1,1#2-Trichloroethane 10 20

Carbon Tetrachloride* 5 20

Trichloroethylene* 50 150

Perchloroethylene 50 -

1,1,2,2 Tetrachloroethane 1 5

BrCICH2 200 250

Br2ClCH - -

BrC12CH -

Bromoform 0.5 -

Chloroform* 10 50

Range 0.5 -1000 5 - 500

*Suspect Carcinogens**TLV - Treshold Limit Value* American Conference of Govern-

ment Industrial Hygienists (ACGIH)***STEL- Short Term Exposure Levels (ACGIH)

,. : . ,_ . . .. . -. . .. . . -. -. ... - : .- .. ... - . . . . . ... -. .. ,

-7~- 7, -7 7, 7

-103-

Vapor ft*urrnty TV

walumm. 32 IW am0 39.46 33.13 6.7 U193 6.3 x13 ago 3.6 #3.95

aft A". too 125 .51 a1.9 3.5 8164 3.3 X104 a" 1.3 A3.62

Zyl .. P a". too ISO 8.73 13304 3.3 uRile 3.5 Big' A 1 .1 /0.91

CUB. A12. is -- Sam~ 2G.a 1.981ae a..81 is 2S.e /1.3cost 40e8p) 147 7 5 vI .8 33 . 4443U9 o 44/.

*3.3.-in all 5owmml 06.9 In $g0 417 733 273 ag0 m60 6.3 /2.5

trm. 12 Sal 1333 -

* .1-CI 2cs, 9.3 33 264 330.7 366.7 786 1.5 /10.31

1.2-C12camd 33 is 1 316.1 u61.7 060 - so 0.76 MAN4

III ,Inch 133 25 430 12a.1 232.52 6.4 ae36.7 31 2 a"0 2.5 /1.3

Ila "Ask 133 to 33 34.SI 3.17 1.4%u103 1.3481466 to 1.4 /6.72

as.1 s2 iS 3014.2 313.7 1.1 U14 - I6 0.0316.0)

SCR 11.4 so 1S0 7.39 133.73 6.6 al3~ - tW 3 A909)

we3! 163.9 so - 13.20 39.11 6.1 Ku14 - Roo 3.63 /48.231

1132 Cl4 Casa 163 1 S I

No a129 00 330 nIsrcMS20 - -

24m 34 - -

25afm 3 3.6 - 3.5

Chlereferm, 116.4 so so 134.33O 360.4 71 163 10 6.33 /6.18

"a. 3.0-1000 1-500

e3uapect cari~nspas

09ime"wue prembibtei by 141V 4petre2.m "twit-leu flash Vt.)

-104-

TABLE 24

* CSUMMARY TABLE OF TLV'S AND RAT'S

C TLV CTLV Range

Mccl < 7% 6.3 mg/L ND-0.488 mg/L

Chloroform < 3% 0.33 ND-0.011

1,2 DCE < 0.4% 0.76 ND-0.003

111 Trich <17% 2.50 ND-0.429

CC14 --- 0.052 ND

BrC12CH --- ND-0.025

TCE < 0.9% 1.20 ND-0.011

BR2CICH --- ND-0.001

PCE <23% 0.63 ND-0.148

MEK < 0.5% 2.25 ND-1.270

Bz < 2% 0.15 ND-0.004

Tol < 4% 2.00 ND-0.083

EtBz <24% 1.30 ND-0.312

Xyl (o,m,p) <55% 1.70 ND-0.947

ClBz 2.00 ---

C12Bz (orm,p) <20% 4.40 ND-0.904

1,2,3 TCBz --- ND-1.829

*ND-None Detected (below detection limits)

>RAT 25-100% 10-25% 5-10% 0-5%

Mill Creek 5 8

Muddy Creek --- ......--- 2

Little Miami --- --- --- 3

mg/L >26.22 13.1-26.2 2.6-1.31 1.31-2.62 .26-13

RAT - Relative Atmospheric Toxicity*ci

RAT- Z C - 2.622 mg/LBaV (excludes ToK)

*Based on Toogood and Hobson (14)

-105-

TABLE 25

A SUMMARY OF THE STATISTICS PERFORMED COMPARING

ANALYTICAL RESULTS FROM AIR AND WATER SAMPLES

Variables

Procedure Dependent Independent pi Results

REGRESSION PPM PLANT PLT NS

ANOVA PPM PLANT PLT NS

GLM PPM PLANT PLT NS

GLM PPM PLT PLT NS

GLM FLO PLT NS

GLM PLT-FLO PLT NS

- REG PPM PLT PLT NS

* REG CZPPM PPM PLT NS

REG WTAC PPM PLT NS

REG WTAUGL PPM PLT NS

REG WZAUGL PPM PLT NS

REG WTABZ PPM PLT NS

REG WTCUBL PPM PLT NS

REG WTACBZ PPM PLT NS

REG WTACBZ CTPPM PLT NSNPARlWAY CTPPM PLT NS

NPARIWAY CTPPM PLT NS

NPAR1WAY CTOL PLT NS

NPARIWAY CTCE PLT NSNPARIWAY CMIBK PLT NS

NPARlWAY CBENZ PLT NS

GLM PPM AMPM NS

GLM PPM PLT NS

GLK PPM DAY NS

GLM PPM WEEKDAY/WEEKEND NS

GLM PLT NS

GLIN DAY NS

, . .. - . - ... . - .- - .. .. . .. . . . .. ~... -. A-

I.7

14 m

A. 4Ja.

04 -a tf

-. * W A M "f%d.,4

0 Bf C c

0, A 0 0

04 0, 0 C

091

:3 ° ." -- -. - , - ' . -.. -, - l - - - .. - , , r .

-107-

an

a.o

a.:

APPENDIX 1

.5 COMPUTER METHODS AND SEQUENCES FOR

CHARCOAL TUBE SAMPLE ANALYSIS

4

a.I

,S

.J..

* *.a* * * - .- _ . ,_-.. " " .

-108-

APPENDIX 1.1

COMPUTER METHOD USED FOR CHARCOAL

TUBE SAMPLE ANALYSES

SEP IS, L982 910METHODS ZR09CHANNEL 9

1. DATA INPUT

RUNTh *PKS1s.60, 3S

f tV/tIN DELAY KIN-AR BUNCH.300, 6I.0, 10, AUTO

]INTEGRATOR EVENTSTIME EVENT/E

CONTROL EVENTSTIME EVENT ECM PLYif:!! t /E

2. DATA ANALYSIS.PROC RPRT UP-UNK

ZERO.. LO, NO

UNITS TITLE

3. USER PROGRAMS

POST-ANAL DIALG-PRG PARAM-FILE

j" /N

4. REPORTS

1 1 tDVC ORPTS

•2"/E

'p

'"

S*.

N %<.L,'.9L. .-

.-

0. _

-109-

APPENDIX 1.2

A COMPUTER -AUTOSAMPLER SEQUENCE USED FOR

CHARCOAL TUBE SAMPLE ANALYSES*s IS 1919 "i 100 3 7a

6ZaU~jo: aits'

3a~e~. 3.9

'Us

.a 3.0 6 ,pse 191 ss.109,$es3S 5102137 93, 983-606 9908 .449 .68

-' ST0. 1. p 1 9 oM .6 .

SM1.LUUI S. 303's2. 6M 29:816 Seem 1.-90 6.-~ SnPae6 L . V9966 0 96S66 ses60. 8.0666. 1.0666

7 SI, v P.99663 0 963 M-s6.6, A.6606. 1.6666a 51L3 , 3 996S Pole 396653 * 6.6, 11409.6 .ISSI

9 W. 9966 39666 166.66. Se-o .6666, 9.666if OWLS , Po. s R964 ollie M 6.33. &.066, b.99::is 59.3 *I0. 993666 96366 * 166. sees. s.eems9 000 1 sell9 969 6.0, 606, 6.0666

66 39o *It. 0 11612 894112 see6.@$. 1.' 6 109136 517 3 99661 MIS 699612 16.66. 8.6666, 9.6613 591. $41, 996613 1 98663 S66.6. 1.6606, a .6Is:is VLSI is6. 99614 evll 09614 6.. 1.6666, &.66S V~IS * 1.6, s vm 09061; U 66-.68. i-sss, 1.86610 7 6 si a10S. P91117 sol? SGO.06, 1.6666. 4.6666to VSIl so6. 99617 evl* 69661?, 1 6.6 .6666. 6.066to 69163 to 1,9916 mo 6961 ee16.66$ .0@ . 6.0666t9 39.13 so6, F99619 8 9669 *136.6. 1.6660, 1.68633 PL14, at3. 996636 * 90636 se666.6. 1.6666. 6.6666at IWeso 228. 996633 *99622 MA16.6. 1.6666e. 1.666633 691.1 n 33 099623 * 90623 9916.6. 1.6666. 1.6066S4 6916 to 34.99814 *9024 too6.$$, 1.6666. 1.66as "Li.6 *IS. 996631 @tst 6961 6.66. 1.9666 1.666630 P1.36 * 6. 966 *966 *AC 16.6 .6666. 1.0601 7 S150 7, 096637 *99627 Mm66 .66 1.6666,. 6.666620613 963 VZ p96626 stlt 66.60, 6.6066. 6.6060

39 9122 * 9,99339 mm 39639 16.6. 6.6663, 6.60636 P133 *31, 996838 69631 See66.6. 1.6066. 1.666631 391.4 *31, 90631 2,03901 as666.6. 6.6663. 1.666032 691.3 W 3, 996632P 9932 40666.66 6.6066. 1.666033 39&3o 33 . P96333 2 96633 106, 6.6466. 1.660034 691.7 *3,964 391634 * 166. 6.6636. 1.66663% SPIN1 31S. 996621 M IS 39631 66.3. 8.6666, 1.636b34691.39 36, P9936 09936 see6.m6 6.6666. 6.666637 691.30 a? 39, e 9967 191037 MM360. 4.00. $.Sol0so 017: P,990338 96636 666. 6.0886. 6.6639 VLIl at3, 96639 * 66639 .666.66. 6.66669. 6.60666 W3 48, 993.6 096646 SO166.6. 6.63, 6.6666

41 691.33 46. 993461 1196641 so133.6. 6.66. 6.666343 39134 * 0, 99063 11966431 *166.06 6.6066. 1.663643 69131s 43. 99143 * 93641 &s666.6. 6.6603. 6.96644 691.34 , , 996644 * 909" M-66.6. 6.6666, 6.66641 9i3 * 41'. 96641 0906411 * 166.63.06.6 . 6.663646 39133 4, 996640 sto 3934 I,::: 666.66 , 06. 6.6647 391.39 *49: 9090647 a 39364? se6006ll066 6.366340 391.46 43. 9411 *906841 s166.36 6.6666. 6.636649 333 9: P9949 * 96649 *666.06, 6.06. 6.3666so A3 6, evec0 owe 63s6co16.0, 1.0606, 1.6606

APPENDIX 1.2 (continued)

* COMPUTER - AUTOSAMPLER SEQUENCE USED FOR

CHARCOAL TUBE SAMPLE ANALYSES

3, 3. 1

910. so, I

0*N9Lt-AE SILS PROC-MCL RAII-FILE XIL-T 03-ANT 39-40412 8799 St 10 9010 fo* 0950 mi , 6.690. moos0e3 01391 S21. rp90s * 90011 iw£6.0. 3.0060, .000

4 09*42 , 3, P90013 RV09003 6 I6.48. 1.0000. 1.0000S GPL43 S 4. p9014v 014 w 6910.00. 1.0800, 1.080f 091.44 5s 11, es PVMS1 se s90ome1000 . , 1.6007 mft4s S61, M9001 NI 096010 6 0.0 1.0669, &.000

S 946 OM 17,M P901. 0017 * 0.0. lO . 1009 09*47 so1, P9000 6901 so 100.0, 1.600, 1.000

10 39*418 * 1, P90019 ,vos M909M e~ , m.esa. m.osso11 39L49 1 0 91600 2 98060 6150.8. 1.4101*. &0.00112 09*10 6 1. 096661 * 09001 * Ase., m.uss. &.Sto£3 BIDS0$ 62, P99662 1 961162 *10.0, 6.00, 1.1000

14 09*11 6 3. P9803 4 90662 100 . 1.0000. 0.0010is 19*12 * 4, P96664 2 90664 M-0000 1.00, 1.0001* B9*13 6%4, P90011 0901 se100.e, 1.0800. 1.0017 SP*IS' ,", 098666 1 900*4 Af100.0. 11.406.0 6.06010 98 PLS 67. p951EY ' 090007 m m000. 1.0000, S.4660t9 09*10 be*, 1981.6b , OU64bw M-10.0, S1000. 9.00LBe 09*67 * 9, P91W* * 0909 2610.00, 1.600. S.l26.as 09*10 70, 9075 *8070 *10600. 6.600u. 9.00410

*22 0919 U. 01,98071 * 90071 M-s0.0. 6.1.00 I.0cr23 M.600 1 2, 990072 119172 to10.0. 6.0000. &mgo824 51ips 73, 91673 R 90073 oc£0.00 1.0000. $-so::IS S9*01 *74. P96874 *09006741 *10000, S.6804. 6.9002* 0902 *71, V90071 09007S 100. 1.0008, 1.00027 011043 *74, 109887* 09974 *500.00, 1.0000, 0.000*b

29~~ ~ 0L4",V9T 9007 a100.0. 1.0000, 1.000so19s o 96678 09977 mm000. 1.0000, 1.000

30 095."00V967 096079 , 10. 1.0000, 6.000031 PL:~7 * 0, P90005 090000 &ws0.0. 6.000. 6.00032 09*40 Cs, 991 1 96001 * 10000. 1.0000. 1.00033 09*09 8 2. v9sec. 090002 100. 1.0000, 1.000034 09*70 *03, F911413 *090003 stem.5, 3.00sO, 6.0831 01112 4, "9604 8 90004 100. 1.0000. 1.00034 09Ls I 61, p9sses "Se 09031 0000. 1.9000 &Moo037 0002 86 0,P9501d, §9900 * 1000. 1.0000. 1.68&030 0L73 0791107 Olon 0900 mo0.0. 00, 2.180139 041 go0, V9sges mse 0900110.0 6.900. &.soot

*40 09*7 "1 9.00049 ste 09009e10 . 1.6060, 1.900041 0976 90, P90090 Itm t9090-to0.00 0.0100, 1.899a42 07 6 1 901 009 0.0 .00 .80043 091L70 *a9, rp9909. 090092 %s1o-.o, 1.0000. 6.000044 W09 93. P99993 *090092 Se1e.m, 0.0000, 1.0041 09100 94 P99994 1 90694 se100.0. .00. 1.00044 07013 9s, V90q91v aset m9m1 0 . 1.0100 1.00047 O9*0* * 6 9 09996 098694 soso 0.0.0 .00 .00040 09*02 91:, 097 909097 Nv06.0, 0.0000, 0.000040# v 1 11 "9. 990590 .d009 As£00. 1.9000 0.0000

10 ~ ~ ~ ~ b o 666.669,9099 *0909 0 . 6.0000, 1.0000

APPENDIX 2

COMPUTER PROCEDURES FOR WATER

ANALYSES FOR PURGEABLE HALOCARBONS

..................... ,. . . . . . . . . . . . . . . . . . . . .

9 . .

9~ 7

APPENDIX 2.1

COMPUTER METHOD USED FOR-WATER ANALYSES

- FOR PURGEABLE HALOCARBONSit 29 190'. 23:45

I;EImov: PUR6011 70CHANUEL 22

1. DATA INPL'7

30.0- 75

MV. "3N DEL01Y "IN-AF RUNCH.1669 '.30 5000. ONCE

INTEGPAT0W. EVENTS'TIME EVE141

I /E

C Otll'L EVENTS.TIMlE EVENT ECM RL-,'

fFC'C RPFPT SUF-UNI:CS7I,- E,,;. NC

K* L ' GEAELE HALOCAF.LC-t4"

PEF-Fil. %.PTa PP-UNIt 111-01L I)VT.1 .S 1.0 088E* 0. 4 950 - (s 00

TIME AIIc'.'j4T FAVTOP NAMIE?4 - J.9000E- ze2.9fiqSE- 7, t"PETNLENE Ct4.OIIE

09 . .0000E.0 1. 0GO8E4 6. *0R0IiNC.LsCt4ZA

11-1.1'. :.60N.E- 19 1.906E# Sot LI-DI CKOLPOCEIHF.IE5 11.4i- I.00E- (4s 4.001lE- f. &CIS-12-DICLEThYLENEt lt02% 1.9060E- So 1.668DE. 99 S.CHLOROFPMf3 2.70. 1.9000E. So 5.77SOE- 5. &212FRE014

' ZfA 3 .9C00E- is 3.S06M# So &EP ICHLOPO.THIN:0 14.PI- 1SO0E* 0. 5.SE70E- 6. 1111-TFIc'4L0PETP0IE

31 14.45. 1.0006E# So 4.lSESE- 69 &CAPSON TETRAtI4LORP EI- 149 1.6e09E* 0. 2.2S!:E 6. &BRON0DICHLPRWtElmA4E

14 17-159 I.G060E# G 2.69e2E- 5o &TRICHLOEIYLENE1! 7.091.00E#go1.634CE- S &ISPOOMM4OrsIETtIANE

17, 19 .439 1.SOOE. So 3.00beE- s tC IE- 13-111CLOPPfROPE4jIt 19.75p 1.0000E* 99 2.92*:)E- 4, 1 *CNLOP02f.*UOiCPtOFAllE1' 20.45o. 1.0000E. S. 2.74'SE- G. 0ERONDFOP

*20 22.939 1.91180E# So 6.76'3E- 6. II1122ETRCNL.PDET4YLE21 23.90. 1.0090E# So 1.S0DOEo 0. 43322ETRACHLCWEIWANE

S23.8M Z.6609E. Go a.SSOOSE* Go I14D ICKOE*L'TANEVI 25.76. 6.,5.I .9C6E- 69 &CLOftDEN:ENE24 -4

4 3. UsEr P#OGRAMS

POST-AtIAL DIALG-PRG PMAM-'I-LEiNF02 ILP

APPENDIX 2.2

COMPUTER -AUTOSAMPLER SEQUENCE USED FOR

WATER ANALYSES FOR PURGEABLE UALOCAPBONS

LEV acl. PSC 9: 4:-. .ECI.,J4. E: ;EC!2- f.

* tUE:$OUENCE 1

PLIP EC,:: C'

:7..:1L# F0O-WSH:

KWK -r-rf E-'TL* PPC'C-FILE PAW-FILE 5IL-P STI-AlT SNP-rq-Z. . 'pAtoC: ,RAM'4O 2, 10'. (1."# 1.0000. 1.0vc-

N T 4- 2. ~PA0c0cC RA(4DO02 jag.;;, N.ooc. .4. PAQOC: , RA0004 0. 3.tX - 3.0000- V.'

4.P0Oi RADOC05 IC 10.(.Y000 1. .CIZI

E 9 * . PA M0C * R IME 9 10X .0 .eoec; . 00eOt N0 9- FRPAOC. F A0iO0i I 30.t .000C. 1.00c,

C, 9 Ie. PIAO0C * 10G 1 ie.. .000 9..VeCC1 -E t 9.P71' ,POO ,;~,0,1S~.ISCC

APPENDIX 3

COMPUTER PROCEDURES FOR WATER

ANALYSES FOR PURGEABLE AROMATICS

S..... ......-

APPENDIX 3.1

* COMPUTER METHOD USED FOR WATER ANALYSES

FOR PURGEABLE AROMATICS

S. 9sU' OE; IS240Mr1N(,!:: P&162'TOCNNEL 21

I. wi'FT INPUIT

,k~ItI . sF1. S^;~e' 150

.sec'. .. 309 19ou. ONCE

INtTEGFATOP EVENTS.TIME EVENT

CONrTROIL EVE141TIME EvEt4T Ecm PL'

* ~Z. I)PTF' ANALYSIS

L1141I. TITLE*1%9 L. - PUCEAELE FiIF-011AI

T!61 AfCOLiI,7 FACTOP NAMIE3. 4c, 1.0000'E# to . .3SE- 4. SPIEl2.449 5. 800ft- -. E929CE- 69 9E1t4:01tC. OS. 1.BOCOE* 09 . I .($E- 59 IIDLUE14E

4 6.79 I.90CCE* 09 9.4973E- 6, 9ETHTLEEt4LNE

5,.21 - i.OvOE* 0.- 1..12C'IE- 5: IF-XYLENE-t* . i-.S .0000E- 0. 6.10e E- fs IPI-XYLENE7 10. 2 . 1.0000cE# 01 9 50E&iE- 69 &'-XYLE14E

~ :.:~' IOOOE 0 E.470ef 5v &CHLOP~kut4:F14r37I.fls 1.0000cE+ Do 1.900E# 0- tMiI'ICLOFE4:t14

C, J .^4e - J.Oc'cOE* 09 1.9000OE# 0- OF=IIC#4LOEEt:E

I /E

VS'-EF PRCIGPIMS

FF, T*A4AL lDIALG-Pf&G PAPAM-FILE

4. PEFORTS

RIPVC #RPITSI Lis IZ 'E

APPENDIX 3.2

COMPUTER -AUTOSAMPLER SEQUENCE USED FOR

WATER ANALYSES FOR PURGEABLE AROMATICS

SEDLIE04CE: SEC'Z:CHANN4EL 2~1

$LTESE0.. EtIC I

ItIALC-F*r.P' Arli-FILE

~-IP.E-~AE ETL# PPOCC-FIhE ij- F ILE ~.'L~STI'-AM1 SMF-~AT'

* .PAW'C, R AM.,~' , I C.~. o.C . OCOC -. .oc'cu

4-~ PA0004K - PA00 1 eCiCA . .~C (4 1 - I

5 . FRM - RAOOc04 - 1ezi.o". 1.90K0. j*.3R'i . PFwOCI"C- R PC'OU 106. C, 0. 1. 100c, 1. OOC'

F~io. R AC0'0E 10 lo. C,-1.00MC, IC, OPA00 RE.O. It' *c l . eco ~oPA00(s . PAi0 *RC00C. I etc. 1 1. 00c,C' .00c1

I C, PAOC!- I e.0O p*c I tc... I etooc* iill c

* ~ - ~ -. S ~ -

.4'.

44'

J -117--C

~4

APPENDIX 4

COMPUTER STATISTICAL PROGRAMS

4.4.

4.

.4'

.4

-. 4

.4.

77 .77 !

-118-

* APPENDIX 4.1

SASRUN 1

/f'ENIOIA JOB (0.134801) ,DWOVAf? SASRLI%// TZPZ- (0 v30) .RE010N-260KOMSLVEL(I1p1)/ROMEP MRINT k4T3// iEXiX SAS796,RMIN2O'O(

% //)M IC DSNAL'flI 0. D2i'?EC, DISPNOL.D, LtT.6YSrA, V3LmER*aRX51//VDCL D DSBNII C. DCL. DSP=OLD, IT-SYS~ ,VOLaS~.'K

//l'ZIP1 MO D6NuAIO~I. ~T FacDISOOW LIT4SYSDA 9 VOLSER"'RI151

//ZACTSP DO DSN*JA4I 01. C1SLPeMDSP-OLD 9 UITSS,VLSERRC1l//D'.T1Yy DM ESN44I 01. YCTAY, DS P-OLD9 VIT.VSSERVD=MTJ15I/A4RITE MO UNI1T-338OISN*',DHI1.SASRU \11,// DISP-(NE&,CNTLG) .SPACE-(TRK, (5.5) .RISE) .VOL4ERw480116//sASC.SySii mD*MfTA ONE;INrILE ECENT=;INPUT SPL 2-4 PLT. 6 DANY e SO 10-11 DTE 12-13 TIME 15-10PWV 20-22 Mm 24-26 FIO 28-30 MIN 32 DET 34 COL 35Ri 38-40 AT 42-43 WC 4-4& Hlm, 48-49 SS 51-53 Ml 55-57CW, 59-5'1 P04 63-65 P 67;flNTA 7hO;INFILZ CWAM,;LJPUT SPL 2-4 ID 6-7 P 9 KWEK 11-16 WBENZ 18-23 W'TOL 25-3U'AVI6Z 32-37 M~L 39-44 WCL2BZ 52-53 WTALCL 60-G6 IZAUGL 70-76.%MBZ 7.33-64;M17I. THRflL;iNrILE DCL;INPUT SPL 2-4 ID S-7 P 9 KC1ECL 11-16 VCLR 18-22 W'flUC 24-29WB2C 31-35 WZCL 37-41 %SC2 43-46 WPCE 48-53 W7CLGL 55-Cl

?263-69 WT&ACSIZ 71-77;-DA FOUR;INFILE &=TFr.;INPUTT SPL 2-4 ID 5-7 P 9 C~rrIC 11-15 MENZ 17-21 CTCE 23-27CPCL 29.-33 CTOL35-39 CXYL 41-45 CCLBZ 47-51 CMEK 65-90

K Oh1IBJK 92-96 CTPP.4 53-Sc'C cnaM 6D-65 CZM.I~ 70-75 CZ%M 7--2;ERTA FIVEuINFILE DACISP;ISMU SPL 2-4 ID, 5-7 P 9 CTRIC 11-15 CBENZ 17-21 CTCE 23-27%CE 29-33 CT1OL 35-39 CCLBZ 41-45 OIEK 47-51 0sIIBlI. 53-57

0XY 59-3 CTPv 65-59 Cfl. 7U-75 CZFPfW 77-82 CZM4.'4M 84-90NMJT 92;

V ITA SIX; INFILE DACiAY;* INPU SFL 2-4 ID 5-7 P 9 CTRIC 11-14 CBENZ 16-19 CTCE 21-24

CPCE 26-29 CMO 31-34 CrPP. 36-39 C1.4G~i 41-45 CZPPM 47-53CZMMM 55-61;PROC SOr DTAmNE; BY SPL;M1c ScrT DTAwzwo;By sPL;

PROC SOR; VATAUIMiIEE;BY SPL;IN=lO SORT DATA-F=;RBY SPL;PROFC SORT VATAEIVEIBY SPL;Ie-C SORT DKTASIX;BY SUL;EATA WRXTC.ALL;MUEGE WE 7WO THRE FOUR FIV SIX; BY SPL;FrC PHINT DATA4'UTE.ALLJ

1 7

-119-

APPENDIX 4.2

SASRUN 2

//WMlIOll -(OoK348Cli) oDW~OVAW1 Si6SRL22',// TIME= (0, 30) tMGION-256K/OR3Lr&E MRINT WT3

/EXE= SAM7S5/ARITE MO UNIT-3380rVOL-ERME01161/DS4*i *Cl. SASRIl t MSP.0w, SPACE= (TK, (5,5) ,RLSE)

//SPS.SYsit4 DO *MC~AA *C4;SET& WRITE .ALL;F=O S=R;BY PiT;

* PJ= CORR DTAptVITEALL; VAR PPM; WITH DAY;PRJC CORR DATAMRTL.ALL; VMR PPM; WITH Tfr.E;PRJC CMH DTAuRXTEALL; VAR PPM; WrI IFLC);PR3C CORR DTAmRITE.ALL; VAR PPM4; WnIT RAINJ;PROC CM~R M~APUtRITE.ALL; VAR PEW.; WI&' liLW~;PROC CORR O~rAm~rITL.ALL; VAR PPM;- WITH DEl;PROC COWR ]DTA44MTE.ALL; VAR PPMi; WITH COL;

*PROC CORR rATAWKIT.ALL; VAR PPM;1 Wrfli Pu;PROC CORR DTIAMRMEALL; VAR PEW.; WITH 147AtL;PtIM CORR 13TAskITE.ALL; VAR PIM; WITH iFLA=XZL;PR3C CORR DTAWMRTC.ALL; VAR PPM; WITH WMEBZ;PROC COHR DkMoRTALL; VAR PM; WI'lh W72VLGL;PrOC COM W.AuWRITE.ALL; VAR PPM WITH h7AC;PROC CORR DATAAMIUTE.ALL; VAR PM; 1I17% WTAC&Z;

*PROC CORE D',"A4RITE.ALL; VAR PM; WITH CTPPM;-PROC CORR lDTAa~UTE.ALL; VAR PPM; WITH CZPP.4;

* ROC REG; 140DL PFMsPLT;

-120-

APPENDIX 4.3

SASRUN 3

/fITilIO12 JOB (0tK348H)tDWVM4T ShSRLI'3',// TINE- (0,30) #RMONu2SSKP'ROMJT MINT RM7V3// E=E SKS796.//6%1RITE M U'NT33SQVLER1M80116,

* // w .4WMHI .SSRLrn1 tDSP-LSPACE- (TKU (5,5) ,PISE)//SAS.SYSIN DD*MTA ONE.-SET WITE.ALL;PROC WMV7 DTA*'ITE.ALL; CLASS PLT;- MOCEL PP4'PLT;PROC GLM D'NTARITE.ALL; CLASS PLTMM&L PPMU'PLT;

LSMEANS PLT/E STDER PDIE'k;PRO)C SORT DMAm*RTE.ALL; BY PLT;PkX CORR DkTAUVTE.ALL;BY PLT;VAR WMI; WIrh DAY--HUm;P=O PLOT WL~ARXTE.ALL;BY PLT;PLOr PP14*(D1AY-HUM)

PROC' COMfl CTAWRA'F1kALL NOMISS;SY PLT5VAi PM;WITH. *WE..CZiQ%I;PROC PLOT DTAK*~lRTE.ALL;DY PLT;PWFT PP4*(W.EK--CZ-IG);KOC GA, lTAvTJTE.ALL;CUZ1 S PLT;

MhODEL PPMi-PLT PLO PLT*FlO;PROC GLM 0RTA4,@TE.ALL;CLASS PLT;

MMML PPM -PLT FlIO;

*~~ 7 -*

-121-

APPENDIX 4.4

SASRUN 4

~4f//viEilCl4 JOB (o,K348CH),DUNlOVAHrr SASRLU40o// TIME- (O,30) *.RGID1241.,/*PturE M1INT iT3

//EXI SAS7935MA~I UNITw3380 .VZL=SER44C011 (1

//&&S.SYSI4 WEXCA ONE;E WRITE.ALL;PROC S=~R DTAK%7ITELLLg8Y PLT;PX= W);hi CLASS PLT;P'aXZL PWasPLT 110 PLTFEW;PRXC QJ.I;CLAS5 PLTfl.a=EL PPMwPLT TWI;PAOC CMRSgBY PLT; VAR PPM4WIrh *E--CZmm;PROC REG;BY PLI';M=L PPMumT;OUPJ? OWjrBsaHI PPRPPN;FRJC PLOT DATA4O6k1; PLC? P~PLTI PRPPM*PLT * '/VERIAY;TITLE MiDICTED VS. ACTUAL PPM;gIN-= REG;ZY PLT;F'ODL crP'MftPPA4:oIYPUT )JrBOi12 P=*RC-?wh:;PkOC PL." W.TAmBns l21PLOT CllPPf *PPm~ Pi=CPPM*PPMS=l' Rlt.YTITLE PREDICTED VS. ACTLLN. CTPFi';PRC PXG;Y PLT; MODEL CZFMi=PWt; OLRPTT WIUmBXfl3 PaPiCZPMr;PROC PLOT DrATA.3On13; PLOT CZPM1*PWi PRCZPMrjPPM-"'/VERLAY;.TITLE PREDICTED VS. ACTW4L CZP~ihI;AIXC RELp;BY P'L.?5 MODEL l%?ACu'PAlOUTPFT EOUTTH4 P*PM7AC;PROC PIM DkAmEW1WP; PLOT %'PAC*PPfM P A.PPIW'*'/JVERLAY;TITLE PIk.DICTED, VS. ACTUAL WTAC;PROC REG; BY PLT;VKOEL rA.ULP FM;OLUrFUT 017F4OTH5 PRw"YALJL;PROC PLCI' fATA4mJfli5; PLOT WTALGL*PP1 PR'AUL*LPP V.-9*f/OVERLfY;TITLE PMWDICTED VS. ACTUIL WZALWL;PROC REG;BY PLT;4M.L 1%ZALPPP1JOUffPl7 OU?4GOUd PuPR%'ZP.UGL;PR3C PLX DANM07116; PLOT WZAUGL*PPMl P~iU2AL*PPIV''* /OVERLAY~;TITL.E PREDICTED VS. ACTUAL WZAUGL;FlRGU;BY PLTWMEL %h'ThBZmPPmOULftr OUT-BOTH"7 P-P~ABZ;-PROC PLOT DATAuBEfl7; PLOT WABZ*PP.%a M.ITABZ*PP4' *$/OVERLAY;TITLE PREDICTED VS. ACTUAL WrAILzPPsOC REGBY PLT;ih;ODEL wIUL-PiNOUPUT OLJTmBaTIIC PwPR-.'2CUL;PROC PUJT WrAmBOHE; gPLOT WICUL*ML'P P'IVIIZ'PPM'-* @/OVERLAY;TV'L& PREDICTED VS. ACTUKL h CUGL;PAXC REG5BY PLT;MOIXL %%Au~PPM;OUrjur OIrooTniw0 PPR'2CBZ;PFUC PIMW AA4SISOLOPT WTACBZ*PW.R~CZW''OELYTITLE PREDICTED VS. ACTiAL'WTACBZgPROC REG;BY PLT1140ML %7ACSZmCTPPFg wrTP'r OJTUSOIV P.PRA"T=CZ;PROC PLO DATAWYMOLOT P KrW'AZ*CFPP rvTAC2Z*CTFPPI-' * /WELAY:TITLE PRED1CTZED VS. WRTUAL WVJMZ;

-122-

APPENDIX 4.6

SASRUN 6

/brMD4HI016 JOB (0vK34CH),pDUN0OAII &%MMMN',// TI-1E- (0.30) ,MIO-124K/ROM11E PRINT MT3// EXEC SPhS795i//WRITE MO UK! m33S0rV0LwSERW.80116,// ~1D*1l401D.SSRLN,DISPOLDSFCE-(7RK,(5,5) ,RLSE)//SAS.SYS1N DODTA C;CSEr WRITE.ALL;IF PLTl THEN1 DO;FW1.'FWDPP41PP'1;E:4D;11 PLT&2 UMEN DO;FD2FW;PPf42.;ED;IF P"T*3 T&IE94 DO;FWZ3=FW;PWA3*PPM; DO;PROC PLO'1;PLO PPMI'kL~lw'A' PP42FW2-'B' PP43FW3a'C'/OVERLAY; %F=~ CQRR;BY P LT;VAR DY-CM7I;

-123-

APPENDIX 4.7

SASRUN 7

//WM431017 JOB (0,K348CH),DtWIVANT ShSRLV-7'./1TIMEZ-(O,30) ,RCrnUNulO24I(

/RO~fE PRINM RT3// EXEC ShS796

* I/WRITE DO UNI?. 338O.VDL4SERuf42C016,// G* 1ENHl 01.* SASrUtNl,DISP.OLD, SPACE- (TK, (5,5) ,RLSE)

* //SAS..SrSIN DO *DATA 04E;SET WRITE.ALL;PROC COniR FEAMC1a SPEARMAN jcFMAML;BY PLT;W&J DIY-NJMI;PROC CORR PEAM0IN SPE.Ri4z KLVQLL;BY PLT;

- VA1k DAY TIME PW WMD(K--CZMGhA;

ZI.

-124-

APPENDIX 4.8SASRUN 8

'/WV-1ID1S JOBS (0,10481) ,'DWOVAtRr SASRUNI*4I TIME.(0,3O) ,RF~IO4.1024K

d 'R*POI7T mo PRW KWTf4'E)= ShS796

* '/tARITE M LUNIT.33C0 ,VOL.SERW*801 16,,/ WDwSN~D jl 010 SASR1,DISpmOLD* SPACE- (TRK,(585) .RIE)

PkTA 04E;SET WRITE.AL;31=C NMPAY;CIASS IPLT5-VAR CrPP14 CZFPr4 CrOL CTCE QbIBK CBW;)ATA TWO; SET WRITE.ML:F OSOC LE TIM L.E 1200 THEN~ AMPM-1;:F 2201 L.E TIPE L.E 1500 711EN AMPMa2;7 1501 LE TIME LE 1800 THEN AMP43;:F IC0l LE TIME LE 2100 THEN AMPM4;4M GLM;CIASS PLOT AMPMI MRY;IODEL PR4kWIM FLT DAY;YCA THREIg SET WRITE.ALL;:F 2 I.E MY L.E 4 THEN W-1;:F rAY-i 71EN M02;:F DkY=5 THEN DD02;.1 6 L.E DAY LE 7 TIM D0u3;MXO GLMo;CLASS M PLT MAY;iODEL PIPM=D PLOT MAY;W'rA FOJR; SET WRITEALL;4=X FWI;BY PLOT;LDTr PlMCPOL;

n=O PIZ; BY PLT;4=.O PP4CIP14;*XO PLOT; BY PLT;'1.0 PMCFf1;4=O PF;T BY PLT;'WE PPMQ4IBK;4WO PLG'; BY PLT;

* 4=O PP14*CLBZ;4MO PLOT; BY PLT;4LM PPM*CPCE;'RX) PLOT; BY PLT;WLT CTOLWIU.;

46X PLOT; BY PLT;

4MO PLr; BY PLT;

PLOT CBD429%4;JPOC PLOT; BY PLTs

-125-

°°

APPENDIX 5

DETERMINATION OF A STATISTICAL MODEL

FOR THE CENTURY OVA DATA

5%*

U ,.°

5',! °.

| %.

45"

1,1

0 Q 0 q0 U) m

0 0 0 000 0 0v

AtO 0 4 0 0 0 0 00cr- r-0 D 0, Ln - i I

0

-n cc n 4% q 0 r~N~

0 04er- 1) Ln %o 0n v- v04 r o 4 o c o' %o %o coH w (D 04 r-4 "I r 4% O1 4 I -I 1- r- -I

14E-4

1E-

a'..4 IN. E

-4 -4 -4 -0 -44 -4 -4 -4 -4 -4

4 4

P4 .Eu . . . . .C4 m qw i %0 r- w 0% 0 F4 m 4 0 0 r

4 r4 P-4 4 P4 r4 P

610

|71

-127-

APPENDIX 5.2

The goal of this statistical program is to find a model

that fits well (i.e., small Chi Square), with as few terms

as possible. The best fitting model is as follows:

log PPlant-Time-Peak n UPlant * UTime + Upeak

+ UPlant Time + Uplant Peak

+ UTime Peak

This model has a Chi Square (X2) of 3.46 with 4 degrees offreedom which yields a P <0.005.

If the plant-peak term is eliminated, there are only 4

degrees of freedom with a X2 diff - 54.18 as follows:

(17)-(161 - X2 diff - 57.64 - 3.46 - 54.18; df - 4

Therefore, the plant-peak term must be retained since

P <0.005.

If the plant-time term is eliminated the result is as

follows:

(17)-(15) - X2 diff - 4.32 - 3.46 - 0.86; df - 2

This X2 diff is not significant and the plant-time peak can

be eliminated. This yields the following model:

log Plant-Time-Pak Plant UTime Upeak

+ UPlant-Peak + UTime Peak

The X2 for this model alone is also very small which indicates

a good fitting model.

This simplified model indicates that all first order in-

terections between plant, time and peak must be considered

except the interaction of plant with time.

,"% w -,.' \.., - .% , ,-,.'. .-.-. , .. .. -..- ° ...... ".- ... ." . - .. .

-128-

REFERENCES CITED IN TEXT

1. Guidelines for Establishing List Procedures for the Analysis ofPollutants, 40 CFR, Part 136, 44, 69464.

2. Reichart, J., et al., "Carcinogenic Substances Occurring in Water. and Soil," Arch. Hyg. Bakt., Vol. 155, 1971.

3. Schmidt, T. T., et al., "Input of PCB's Into California CoastalWaters from Urban Sewage Outfalls," Bulletin of EnvironmentalContamination and Toxicology, Vol. 6, No. 3, 1971.

4. Lawrence, J., et al., "Adsorption of PCB's from Aqueous Solutionsand Sewage," Env. Sci. and Tech., Vol. 10, 1976.

5. Federal Register, 44, 15926, March 15, 1979.44, 43660, July 25, 1979.44, 56628, October 1, 1979.

6. Glaze, W. H., et al., "Analysis of New Chlorinated Organic Compoundsin Municipal Wastewaters After Terminal Chlorination," In:Identification and Analysis of Organic Pollutants in Water, Ed.Keith, L. H, Ann Arbor Science, Ann Arbor, Michigan, 1976.

7. DeWalle, F. B., et al., "Presence of Priority Pollutants and TheirRemoval in Sewage Treatment Plants," U.S. EPA, Grant R 806102,July 1981.

8. Pellizzari, E. D., et al., "Collection and Analysis of PurgeableOrganics Emitted from Treatment Plants, U.S. EPA-600/2-80-017,

* March 1980.

9. Cohen, J. M., et al., "National Survey of Municipal Wastewatersfor Toxic Chemicals," U.S. EPA, October 1981.

10. Kyosai, S., et al., "Desorption of Volatile Priority Pollutants inSewers," U.S. EPA Report, September 1981.

11. Petrasek, A. C., "Removal and Partitioning of the Volatile PriorityPollutants in Conventional Wastewater Treatment Plants, U.S. EPA,October 1981.

12. NIOSH Health Hazard Evaluation Report (HETA 81-207-945), Metro-politan Sewer District, Cincinnati, Ohio, August 1981.

13. NIOSH HEalth Hazard Evaluation Report (HETA 81-134-1079), Metro-politan Sewer District, Cincinnati, Ohio, March 1982.

€k-..-...,- 2:... ... .. .....,....-.2.,: - ,i-i.., -;-*&.:., i. -. -..-:... .. ,. . , . .. .

-129-

14. Toogood, S. J., Hobson, J. A., "The Determination of Safe Limits

for the Discharge of Volatile Materials to Sewers," Water ResearchCentre Technical Report TR-142 and Supplement, June 1980.

15. Lurker, P. A., et al., "Worker Exposure to Chlorinated Organic Com-pounds from the Activated-Sludge Wastewater Treatment Process,"Am. Ind. Hyg. Assoc. J., Vol. 44, No. 2, 109, 1983.

16. Decker, D. W., "Worker Exposure to Organic Vapors at a LiquidChemical Waste Incinerator," Am. ind. Hyg. Assoc. J., Vol. 44,296, 1983.

17. Staley, L. J., et al., "An Assessment of Emissions from a HazardousWaste Incineration Facility," Proceedings of the Eighth AnnualResearch Symposium, U.S. EPA 600/9-83-003, April 1983.

18. Barsky, J., et al., "Simultaneous Multiinstrumental Monitoring ofSewer Headspaces by Several Direct-Reading Instruments," submittedto Am. Ind. Hyg. Assoc. J., 1983.

19. Black and Vetch/consulting engineers, "Report on Priority PollutantSampling and Analysis for the Metropolitan Sewer District of Greater

* Cincinnati, Kansas City, Missouri, 1982.

20. Operating and Service Manual for Century Systems Portable OrganicVapor Analyses, Model OVA-128, Century Systems Corp., Arkansas City,Kansas.

21. H-NU Systems, Inc., HNU PI 101 Owners Manual, Newton Upper Falls,Mass., 1980.

22. Elia, V. J., et al., "Hazardous Chemical Exposure at a Municipal

Wastewater Treatment Plant," Environ. Research (In Press), 1983.

23. Clean Water Act of 1971 (PL 95-217) Section 307 (a).

24. National Resources Defense Council (NRDC) et al.,8 ERC 2120 (DDC 1976) modified 12 ERC 1883 (DDC 1979).

25. Selected Analytical Methods Approved and Cited by the U.S. EPA,S6pplemental to the Fifteenth Edition of Standard Methods for theExamination of Water and Wastewater, 1981.

26. Methods for Organic Chemical Analyses of Municipal and IndustrialWastewater, U.S. EPA, July 1982 (#601, 602).

27. Dietz, E. A. J. and Singley, K. F., "Determination of ChlorinatedHydrocarbons in Waters by Headspace Gas Chromatography," AnalyticalChemistry, Vol. 15, No. 11, September 1979.

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28. Driscoll, J. N., Becker, J. H., "Industrial Hygiene Monitoring witha Variable Selectivity Photoionization Analyzer," American Lab-oratory, November 1979.

29. Barsky, J. B., et al., "An Evaluation of 10.2 eV and 11.8 eV Photo-ionization Detectors, an H2S Ecolyzer and the Century OVA forMonitoring Organic Vapors in High Humidity Atmospheres," Am. Ind.Hyg. Assoc., (submitted June 1983).

30. Feiler, H., "Fate of Priority Pollutants in Publicly Owner Treat-ment Works, Interim Report," U.S. EPA, No. 440/1-80/301, 1980.

31. SAS Users' Guide: Basics and Statistics,' Statistical AnalysisSystem (SAS), SAS Institute, Cory, North Carolina, 1982.

32. University of Cincinnati Computer Center (UCCC) WYLUR ProcessingSystem.

33. Daniel, W. W., Biostatistics: A Foundation for Analysis in theHealth Sciences, John Wiley and Sons, Second Edition, 1978.

34. Threshold Limit Values for Chemical Substances and Physical Agentsin the Work Environment with Intended Changes for 1982, AmericanConference of Governmental Industrial Hygienists (ACGIH), Cincinnati,Ohio.

35. NIOSH/OSHA Pocket Guide to Chemical Hazards, DHEW (NIOSH) Publi-cation No. 78-210, August 1980.

36. Thibodeaux, L. J., et al., "Quantity and Relative Desorption Ratesof Air Strippable Organics in Industrial Wastewater," Env. Sci.and Tech., Vol. 11, No. 9, 879, September 1977.

37. "Sources of Toxic Pollutants Found in Influents to Sewage Treat-ment Plants," II. Muddy Creek Drainage Basin, Cincinnati, Ohio,EPA, MDSD, Final Report on Task Order No. 6, Contract No.68-01-3857, Report No. ADL 81099-51, June 1979.

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ADDITIONAL REFERENCES USED BUT NOT CITED IN TEXT

1. Roberts, P. V., "Removal of Priority Pollutants by VolatilizationDuring Wastewater Treatment," U.S. EPA Report, Project EPAR-806631.

2. Pellizzari, E. D., "Volatile Organics in Aeration Gases at MunicipalTreatment Plants," U.S. EPA Contract No. 68-03-2780, June 1981.

3. Petrasek, A. C. et al., "Fate of Toxic Organic Compounds in Waste-water Treatment Plants," U.S. EPA, December 1981.

4. Callahan, M. A., "Water-Related Environmental Fate of 129 PriorityPollutants," EPA-440/4-79-029a.

5. Convery, J. J., et al., "Occurrence and Removal of Toxics inMunicipal Wastewater Treatment Facilities," U.S. EPA, Paper forpresentation at the Seventh Joint U.S./Japan Conference in Tokyo,1980.

6. Westick, J. J., and Cummins, M.D., "Collection of Automatic Com-posite Samples Without Atmospheric Exposure, JWPCF, 51, 2948,December 1979.

7. Warner, H. P., "Determination of Henry's Law Constants of SelectedPriority Pollutants," U.S. EPA, April 1980.

8. Thistlehwayte, D. K. B., "Control of Sulphides in Sewage Systems,"Ann Arbor Science Publishers, Inc., Ann Arbor, Michigan, 1972.

9. Kingsley, B. A., Selaver, S. J., "Sampling and Analysis ofPurgeable Organic Compounds in Water Using Solids and Thermal De-sorption," Abstract from Amer. Chem. Society Meeting, Seattle,Washington, March 1983, p. 194.

10. West, D. S., et al., "Portable Minature Sampler for PotentialAirborne Carcinogens in Microenvironments: Phase 2 Evaluation,"U.S. EPA-600/S2-81-165, March 1982.

11. Weber, W. J., et al., "Effectiveness of Activated Carbon for Re-moval of Toxic and/or Carcinogenic Compounds from Water Supplies,"U.S. EPA-600/S2-81-057, June 1981.

12. Burch, D., "Ambient Air Non-Methane Hydrocarbon Monitor," U.S.EPA-600/S2-80-201, May 1981.

13. Weber, R. C., et al., "Vapor Pressure Distribution of SelectedOrganic Chemicals," U.S. EPA-600/S2-81-021, May 1981.

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14. Jayanty, R. K. M., et al., "Laboratory Evaluation of Non-MethaneOrganic Carbon Determination in Ambient Air by Cryogenic Pre-concentration and Flame Ionization Detection," U.S. EPA-600/S4-82-019, July 1982.

15. Brown, G. E., et al., "Response Factors of VOC Analyzers Calibratedwith Methane for Selected Organic Chemicals," U.S. EPA-600/S2-81-002, May 1981.

16. DuBose, D. A., et al., "Response of Portable VOC Analyzers toChemical Mixtures," U.S. EPA-600/S2-81-110, September 1981.

17. Karaffa, M. A., "Industrial Hygiene Evaluation and Recommendationsfor a Comprehensive Health and Safety Program for Sewer MaintenanceWorkers," Prepared for the Metropolitan Sewer District of GreaterCincinnati by PEDCO Environmental Inc., March 1982.

18. Thomas, Q. V., et al., "The Chromatographic and GC/MS Analysis ofOrganic Priority Pollutants in Water," Journal of ChromatographicScience, Vol. 18, November 1980.

19. Bellar, T. A., Lichtenberg, J. J., "Determining Volatile Organicsat Microgram per Liter Levels by Gas Chromatography." J. Am. WaterWorks Assoc., 66, 1974.

20. Angell, J. B., et al., "A Prototype Gas Analysis System Using aMiniature Gas Chromatograph," U.S. EPA-700/7-80-184, December1980.

21. Wilson, J. L., "Determination of Volatile Organics in Industrialand Municipal Wastewaters," U.S. EPA-600/S4-81-071, December 1981.

22. Singh, H. B., et al., "Atmospheric Measurements of SelectedHazardous Organic Chemicals," U.S. EPA-600/S3-81-032, July 1981.