United States
             Environmental Protection
             Agency
              Environmental Sciences Research
              Laboratory
              Research Triangle Park NC 27711
EPA-600 2 80-109
May 1980
             Research and Development
&EPA
Impact of a  Primary
Sulfate  Emission
Source on Air Quality

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                  RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional  grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

    1. Environmental Health Effects Research

    2. Environmental Protection Technology

    3. Ecological Research

    4. Environmental Monitoring

    5. Socioeconomic Environmental Studies

    6. Scientific and Technical Assessment Reports  (STAR)

    7. Interagency Energy-Environment Research and Development

    8. "Special" Reports

    9. Miscellaneous Reports

This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to  repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                               EPA-600/2-80-109
                                               May 1980
                     IMPACT OF A

          PRIMARY  SULFATE EMISSION SOURCE

                    ON  AIR QUALITY

                          by
              K.R.  BOLDT,  C.P.  CHANG,
     E.J. KAPLIN, J.M.  STANSFIELD, B.R. WUEBBER
             YORK  RESEARCH CORPORATION
            STAMFORD,  CONNECTICUT  06906
              CONTRACT NO.  68-02-2965
                   PROJECT OFFICER

                   JAMES  B.  HOMOLYA
EMISSION MEASUREMENTS  AND CHARACTERIZATION  DIVISION
     ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
   RESEARCH TRIANGLE PARK,  NORTH CAROLINA   27711
     ENVIRONMENTAL  SCIENCES RESEARCH LABORATORY
         OFFICE  OF  RESEARCH AND DEVELOPMENT
        U.S.  ENVIRONMENTAL PROTECTION AGENCY
   RESEARCH TRIANGLE  PARK, NORTH CAROLINA   27711

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                           DISCLAIMER
This report has been reviewed by  the Environmental  Sciences
Research Laboratory, U.S. Environmental Protection  Agency,  and
approved for publication.  Approval does  not  signify  that  the
contents necessarily reflect the  views and  policies of  the
U.S. Environmental Protection Agency, nor does mention  of  trade
names or commercial products constitute endorsement or -recom-
mendation for use.
                              11

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                             PREFACE
As concern  for  the  human  health  effects of pollution has grown,
so also has  the  response  to  that concern.   Today, one of the
primary goals of  environmentally related research is to further
quantify  the relationship between pollution and human health
effects.  As a  result,  Federal,  State and  Local agencies,  as
well as the  private  sector,  are  directing  resources into
studies that further  clarify the nature of this relationship.

Research  into the causes  and effects  of sulfate emissions  is a
prime example of  this  effort.  Sulfate has been linked in  epi-
demiological and  laboratory  studies with adverse effects on hu-
man health.  Such studies have,  in fact, indicated that sulfate
may be more  hazardous  than sulfur dioxide  or total suspended
particulates.   Studies  in Europe and  the United States have
shown sulfates  to be  major contributors to reductions in visual
range caused by  atmospheric  aerosols.  Studies of acid precipi-
tation in Scandinavia  have implicated sulfuric acid in a vari-
ety of adverse  ecological effects.

Several major studies  are ongoing in  the United States to  as-
sess the  atmospheric  sulfate situation. Among these studies
are EPA's Project MISTT and  Project MESO,  which involve the
transformation  and  transport of  sulfates in the atmosphere.
Project SURE, managed  by  the Electric Power Research Institute,
focuses effort  on the  distribution of Sulfates in the North-
east.  MAP  S is  a study initiated by  the Department of Energy
to evaluate  present  and future effects of  energy production on
pollutant levels.   EPA  has initiated  Project ACES to evaluate
presence  and formation  of sulfate and other aerosols in the at-
mosphere .

The formation of  sulfates, the effect of an oil-fired utility
on ambient  sulfate  levels, and the relationships between sul-
fates contributed by  a  point source and background levels  in
the vicinity of  that  point source are the  subject of this
study.  The  effects  of  meteorology and source emission vari-
ables are also  addressed  in  detail.

The data  generated  by  this study adds significantly to the body
of knowledge being  accumulated on sulfates, their origin and
their impact on  the  environment.

We at York  Research  Corporation  are particularly pleased to
have the  opportunity  to carry out this program for the United
States Environmental  Protection  Agency.

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                            ABSTRACT
A specific point source of sulfate emissions was  chosen  in  the
Northeastern United States to assess  the  impact of  sulfate
emissions on air quality.  A comprehensive  particulate  and
sulfur emission characterization was  performed  at the Albany
Steam Station, owned and operated by  the  Niagara  Mohawk  Power
Corporation in Glenmont, New York.  The plant has four  operat-
ing 100 MW boilers, installed in the  early  1950's and origi-
nally designed to burn coal and oil.  During the  assessment the
plant fired Venezuelan fuel oil containing  1.9% sulfur,  200 ppm
vanadium, and a fuel additive to inhibit  corrosion.

Emissions of total sulfate varied from 22 ppm to  55  ppm  (22
kg/hr. to 82 kg/hr. per boiler, using modified Method 6  tests);
sulfuric acid concentration averaged  74%  of the total sulfate.
Particulate concentration ranged from 60  mg/Nm  to  170 mg/Nm^
(12 kg/hr. to 70 kg/hr. per boiler; 32%-67% of  the  particulate
emissions were soluble sulfates.  Mass median particle diameter
was 1.8 urn to 4.0 urn, as determined by in-stack cascade  impac-
tors.  Vanadium was implicated as the driving force  in  the  mag-
nitude of the primary sulfate emissions.

Historical meteorological and air quality data  for  the  local
area was examined.  Meteorological and air  quality  parameters
were measured concurrently with emission  measurements.   The
presence of local sulfate sources was detectable  by  the  moni-
toring network; however, the plume from the plant tended to
pass over or between the monitoring stations during  most of the
sampling period.  On the few days when the  impact was observed,
5 km downstream from the plant, the sulfate impact was  34%  to
60% of the total sulfate concentration.   Daily  ambient sulfate
concentrations were from 3 ug/m  to greater than  40  ug/m ;  long
term geometric mean concentration for the area was  10.4  ug/m .

The measurements discussed in this report were  acquired  during
the period September 18, 1978 to October  15, 1978.

This report was submitted in fulfillment  of Contract Number
68-02-2965 by York Research Corporation under the sponsorship
of the U.S. Environmental Protection  Agency.  This  report
covers a period from September 18, 1978 to October  15, 1978,
and work was completed as of September 10,  1979.
                               IV

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                       TABLE OF CONTENTS
Preface                                                     ii-l
Abstract                                                     iv
Figures                                                     vii
Tables                                                       -jx
Acknowledgement                                               x

1.   INTRODUCTION                                            1
     Health and Welfare Effects                              1
     Sulfur Emissions from Manmade Sources                   2
     Concentration Distribution                              4
     Atmospheric Chemistry and Transport                     5
     Removal of Sulfur Compounds from the Atmosphere         7
     Effect of Boiler Operating Conditions                   9
     Related Research Projects                              10
     Pertinent Issues                                       12
     Sulfate Measurement at a Point Source                  13

2.   CONCLUSIONS                                            16

3.   PROGRAM DESCRIPTION                                    19
     Description of the Study Area                          19
     Description of the Emission Source                     24
     Description of the Test Program                        26

4.   EMISSION MEASUREMENTS                                  38
     Particulate Measurements                               38
     Total Sulfate and Sulfur Dioxide Measurement           42
     Sulfur Oxides Characterization                         52
     Particle Size Distribution                             54
     Combustion Records                                     55
     Emission Prediction Models                             55
     Diurnal Emission Profile                               79
     Investigation of the Relationship of Sulfate           79
       Formation to Combustion Parameters

5.   AIR QUALITY                                            96

     Total Suspended Particulates                           96
     Particle Size                                          96
     Sulfur Dioxide                                         99
     Photochemical Pollutants                              103
     Carbon Monoxide                                       112
     Sulfate Analysis                                      113
                                v

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6.    METEOROLOGY
     Climate
     Daily Synoptic Situation
     Winds
     Upper Atmospheric Measurements
     Visibility

7.    RELATIONSHIPS BETWEEN AIR QUALITY AND METEOROLOGY     150
     Daily Pollutant Distribution                          150
     S04 = Daily Isopleth Charts                           150
     Diffusion Modeling                                    150
     Analysis of Air Quality Measurements                  180
     Air Quality Analysis of Upwind-Downwind Measurements  190
     Statistical Ambient Sulfate Prediction Estimates      198

REFERENCES                                                 202
                               VI

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                             FIGURES

Number                                                     Pag*

  1.     Hudson River Valley                                20
  2.     Layout of Study Area                               22
  3.     Sectional View of Sampling Network                 23
  4.     Particle Size Distribution-Unit 1 High  Load        58
  5.     Particle Size Distribution-Unit 1 High  Load
         Soot Blow                                          59
  6.     Particle Size Distribution-Unit 2 High  Load        60
  7.     Particle Size Distribution-Unit 2 High  Load
         Soot Blow                                          61
  8.     Particle Size Distribution-Unit 3 High  Load        62
  9.     Particle Size Distribution-Unit 4 High  Load        63
 10.     Particle Size Distribution-Unit 4 High  Load
         Soot Blow                                          64
 11.     Particle Size Distribution-Unit 1 Low Load         65
 12.     Particle Size Distribution-Unit 2 Low Load         66
 13.     Particle Size Distribution-Unit 2 Low Load
         Soot Blow                                          67
 14.     Particulate Emission Estimate                      81
 15.     Paticulate Soluble Sulfate Emission Estimate       82
 16.     Total Soluble Sulfate Emission Estimate            83
 17.     Acid Sulfate Emission Estimate                     84
 18.     Sulfur Dioxide Emission Estimate                   85
 19.     Diurnal Analysis-Particulate                       86
 20.     Diurnal Analysis-Particulate Soluble Sulfate       87
 21.     Diurnal Analysis-Total Soluble Sulfate             88
 22.     Diurnal Analysis_-Sulfur Dioxide                    89
 23.     Vanadium vs. SO|:/SOX=                              93
 24.     Additive Ratio vs. SO4/SO                          94
 25.     Days of Operation vs. S04/S0?                      95
 26.     SC>2 Diurnal Variation-Sites 1,3,4, Rennselaer     104
 27.     SC>2 Diurnal Variation-Sites 5,6, Base Station     105
 28.     Photochemical Pollutant Diurnal Variation-Sites
         1 and 3                                           110
 29.     Photochemical Pollutant Diurnal Variation-
         Rennselaer and Base Station                       111
 30.     Long Term Sulfate Concentration Frequency         114
 31.     Daily Sulfate Concentrations-Sites 1,3,4          120
 32.     Daily Sulfate Concentrations-Sites 5,6,
         Base Station                                      121
 33.     Wind Direction-Oct. 9                             126
 34.     Average Diurnal Temperature Profiles              129
 35.     Typical Pibal Trajectory                          136
 36.     Visibility vs. Relative Humidity-Newburgh, NY     145
                               vn

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Number
 37.     Diurnal Nephelometer Values                       148
 38.     Sulfate vs. Scattering Coefficient-Site 5 and
         Base Station                                      149
 39.     Daily SOJ Isopleth Charts                       151-178
 40.     Sulfate vs. Vanadium-Site 5                       186
 41.     Sulfate vs. Sulfur Dioxide-Site 5                 187
 42.     Sulfate vs. Vanadium-Site 1                       188
 43.     Sulfate vs. Sulfur Dioxide-Site 1                 189
                             vm

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                             TABLES




Number                                                   Page
1.
2.
3.
4.

5.
6.
7.
8.

9.
10.
11.
12.
13.
14.
15.
16.
17.
18.

19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.

37.
38.
39.
40.
41.
42.
43.
Particulate Tests In Specific Fuel Use Ranges
Combustion Parameters and Particulate Test Results
Compositional Analysis of Particulate Emissions
Combustion Parameters and Particulate Sulfate Test
Results
SOX Test Results
Combustion Parameters and SO Test Results
Sulfate Characterization Test Results
Combustion Parameters and Particle Size Test
Results
Summary of Mass Median Particle Diameter
Average Daily Combustion Parameters - Unit 1
Average Daily Combustion Parameters - Unit 2
Average Daily Combustion Parameters - Unit 3
Average Daily Combustion Parameters - Unit 4
Fuel Oil Specifications
Fuel Additive Analysis - Metals
Summary of Emission Prediction Models
Summary of Regression Analyses
Long Term Total Suspended Particulate
Concentrations
Cascade Impactor Results
Dichotomous Sampler Results
Long Term Sulfur Dioxide Concentration
Long Term Photochemical Pollutant Concentrations
NO, NO2, N0x Concentrations
Long Term Carbon Monoxide Concentrations
Annual Variation in 304 _
Seasonal Variation in SO^, Albany
Seasonal Variation in SO^, Troy
Daily Synoptic Situation
Average Diurnal Temperature Aloft
Frequency Distribution of Stability Class
Upper Air Program Data Log
Summary of Mean Wind Directions and Speeds
Frequency Distribution of Wind Speed & Direction
Temperature Change With Height
Albany Airport Visibility
Ratio of Estimated to Observed (Less Site 6)
Concentrations
Site Analysis - Mean Concentrations
Ambient TSP Measurements Upwind -Downwind
Sulfur Dioxide Measurements Upwind-Downwind
Ambient Vanadium Measurements Upwind-Downwind
Ambient Sulfate Measurements Upwind-Downwind
Summary of Ambient Upwind-Downwind Measurements
Results of Multiple Regression Analysis
39
40-41
43-44

45-46
48-49
50-51
53

56-57
68
69
70
71
72
73
74
80
92

97
100
101
102
106
109
112
115
117
118
123-124
128
131
132-135
137
138-141
142-143
146

181
185
192
193
194
196
197
200

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                        ACKNOWLEDGEMENT
The assistance and cooperation of Mr. Ben Madison  and  Mr.  Ray
Cummings of the Niagara Mohawk Power Corporation  is  gratefully
acknowledged.  Mr. Madison, as Superintendent  of  the Albany
Steam Station, was helpful in the planning  stages  of the  pro-
ject and rendered assistance throughout  the  field  work.   The
Project Coordinator, Mr. Cummings, paved the way  for the  acqui-
sition of valuable data and aided the pursuit  of  problems  dur-
ing the transaction of this research investigation.

Technical editing was furnished by Ms. Barbara Drummond  and
Mr. Barney Corcoran.  Coordination of ambient  air  quality  data
and meteorological studies was performed by  Mr. Bruce  Wuebber.

On behalf of York Research Corporation,  I would like to  express
our thanks and appreciation to Mr. James Homolya  for his
thoughtful guidance as project officer.  Without  his invaluable
assistance this project could not have succeeded.
                              Peter L. Cashman
                              Executive Vice President
                              York Research Corporation
                              x

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                            SECTION  1
                           INTRODUCTION
The suspected adverse  effects  of  atmospheric  suspended sulfates
has been of increasing  concern to the  Environmental Protection
Agency.  As a result of  recent ambient atmospheric studies,
particularly in the Northeastern  United States,  the contribu-
tion of acid aerosol sulfates  to  the  total  ambient loading has
raised some serious questions.  It  has generally been accepted
that about one to  ten  percent  of  the  sulfur in  fuel is emitted
from the combustion process  as S04  (sulfate)  or  acid.  However,
during the transport process  from the  point of  emission to the
point of effect, sulfur  diox-ide can be transformed into various
sulfates.  The ability  to  predict relationships  between emis-
sions and ambient  air  quality—as influenced  by  physical,  chem-
ical and meteorological  parameters—is an  essential ingredient
in the development of  cost effective  control  strategies.   This
has become increasingly  important with the  realization that
emissions affect not only  the  air quality  in  their immediate
vicinity, but may  extend their influence for  hundreds of  kilo-
meters .

HEALTH AND WELFARE EFFECTS

Toxicological studies provide  evidence that S02, in the absence
of other pollutants such as  ozone or  particulates, is a mild
respiratory irritant, while  certain specific  sulfate compounds,
especially submicron-sized sulfuric acid aerosol, are more
severe respiratory irritants  (National Research  Counil, 1978).
Epidemiological studies  conducted in  several  U.S. cities

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suggest that high daily or annual sulfate  levels  are  associated
with increased attack frequency  in asthmatics, worsened  symp-
toms in cardio-pulmonary patients, decreased  ventilatory func-
tion in school children and symptoms of acute  and  chronic
respiratory diseases in children and adults.   The  association
of these health indicators with  sulfates was  stronger than  that
for SO2.  When viewed together,  the results of the  toxicologi-
cal and epidemiological studies  suggest that  specific sulfate
compounds may also be responsible for the  observed  excesss
mortality associated with high S02 concentrations  (National
Research Council, 1978).

Economic welfare effects associated with sulfates  are ecologi-
cal and agricultural damage, materials damage, and  visibility
degradation.  Sulfates appear to be a major factor  in producing
damaging acid rain in a large portion of the  Eastern  U.S.

SULFUR EMISSIONS FROM MANMADE SOURCES

Of the total emissions of sulfur from all  sources  in  the United
States ( 17.7 Tg/yr.), about 89% is attributed to  anthropogenic
emissions.  Sulfur emissions from natural  sources  have been
estimated to be less than 2 Tg/yr.  These  anthropogenic  sulfur
emissions are not uniformly distributed as 75% of  the anthropo-
genic emissions have been estimated to occur  east  of  the
Mississippi River (National Research Council,  1978).   Power
plant emissions, which in 1973 accounted for  about  60% of man-
made S02 emissions in the U.S.,  have been  a rapidly growing
component of the SO2 emission complex (National Research
Council, 1978).  While total manmade emissions increased by
approximately 46% between 1960 and 1970, power plant  emissions
increased nearly 92% (EPA, 1973).  During  this period energy
production rose considerably along with the consumption  of  fuel
oil,  while the consumption of coal increased  only  slightly.

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Sulfur in  fossil  fuel  has  long  been  a concern to utility com-
panies because  it  contributes  to  corrosion problems during com-
bustion, forming  compounds  such as  SO3 (sulfur trioxide, H2SC>4
(sulfuric  acid),  and corrosive  metallic  sulfates.   These same
by-products of  fuel combustion  are  named in toxicological
studies as causing pulmonary dysfunction in human  beings and
laboratory animals.

Sulfur is  liberated from  fuel  during combustion, forming mostly
sulfur dioxide  and a very  small amount,  perhaps 1%, sulfur tri-
oxide within  the  furnace  flame.  The furnace gas,  containing
sulfur dioxide  in  concentrations  less than 100 to  greater than
several thousand  ppm  (parts per million),  passes through con-
vective gas passages where  heat is  transferred from the gas to
steel tubes that  carry steam for  superheat and reheat.   The
tubes generally are coated  with ash  deposits of low-melting
point metals; these deposits can  be  extremely active catalysts,
causing SC>2 to  oxidize to  SO^  which  then reacts quickly with
H2O to form H2S04«  Even  the steel  tubes themselves, coated
with an iron  oxide layer,  can  be  strong  catalytic  surfaces.

Barrett's  studies  (1966)  have  shown  that reaction  rates for
catalytic  oxidation of SC>2  to  803 are very high at temperatures
of 1200°F.  The temperatures found  in a  typical convective back
passage in a  utility boiler is  1200°F to 2000°F, and intimate
gas-to-metal  contact is very important to  efficient operation
of these superheat-reheat  steam loops.

Vanadium compounds are a  big concern because of their catalytic
nature and their  low-melting point  characteristics.  Residual
fuel oil contains  vanadium  in  variable concentrations,  depend-
ing on its source.  Asphaltic-base  crude oils, particularly
those from Venezuela,  often contain  more than 300  ppm vanadium
and 2.0% sulfur.   The  chemical  nature of the crude oil  ash is
such that  the vanadium is  stable  up  to 800°F, therefore it is

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not removed by refinery operations,  and  invariably  ends  up  in
the residual fuel oil.

Vanadium pentoxide is an extremely active  catalyst  used  in  the
commercial production of sulfuric acid,  converting  SG>2 to SO3
prior to gaseous absorption in dilute  sulfuric  acid.  Vanadium
pentoxide also has a melting point of  1247°F,  and other  vana-
dium compounds such as the sodium vanadates  have melting points
from 1165°F to 1560°F (Babcock & Wilcox, 1978).  When vanadium
is present in fuel, these low-melting  point  compounds are
formed and readily stick to superheat-reheat steam  tubes.
Sodium is also troublesome because it  forms  complex alkali  iron
trisulfate compounds with boiler metal.

Coal generally has a lower concentration of  vanadium (usually
less than 50 ppm) and a higher overall ash content,  resulting
in less concentrated vanadium deposits in  the  critical gas  pas-
sages.  The amount of sulfur converted to  sulfate is  usually 1
to 4% in coal fired boilers and 2 to 10% in  oil-fired boilers.
The vanadium and sulfur content of the fuel  are primarily re-
sponsible for the high sulfate emissions from  oil combustion.

CONCENTRATION DISTRIBUTION

Based on National Air Surveillance Network data, a  large por-
tion of the eastern United States has  recorded  sulfate concen-
trations significantly higher than concentrations generally
observed in other sections of the country.   Urban levels range
from 10 to 24 micrograms per cubic meter  (ug/m3) and non-urban
levels range from 8 to 14 ug/m3  (annual  average)  in a 24-state
region east of the Mississippi, roughly  bounded by  Illinois and
Massachusetts to the north and Tennessee and North  Carolina to
the south.  In this 24-state region, the 1972  average of non-
urban concentrations exceeded 10 ug/m3 (annual  average)  with an
urban concentration average of about 13.6  ug/m3.  The high

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sulfate levels  in  the 24-state  area  appear  to be spatially cor-
related with high  SC^ emission  density,  high  rainfall acidity
patterns, and a high density  of power  plant locations.   The
remainder of the country  does  not  exhibit  similar sulfate con-
centrations on  a regional  scale.   The  1972  urban average out-
side the 24-state  northeastern  region  was  7.9 ug/m ;  whereas
the non-urban annual average  was 4.4 ug/m  .  There are  some
areas, however, such as the Southern California Coastal Basin
and Tampa, Florida,  in which  high  sulfate  levels are  also
observed.  Thus, while these  areas do  not  exhibit the regional
concentration problems characteristic  to the  northeastern U.S.,
they do have high  local sulfate concentrations.

ATMOSPHERIC CHEMISTRY AND  TRANSPORT

Sulfur dioxide  is  oxidized to  sulfuric acid and other sulfur
oxide compounds by several mechanisms, most involving reactive
agents such as  photochemical  smog, ammonia, catalytic metals
(such as V, Mn, Fe and Ni) and  fine  particulates.  Temperature
and humidity also  influence the reaction.   These agents can
complicate the  relationship between  SO2  and sulfates;  for
example, reductions  or increases in  SO2  concentrations  may not
result in proportional reductions  or increases  in sulfate
levels because  of  the presence  of  other  agents  that affect the
formation reaction.  Inadequate knowledge  concerning  formation
mechanisms currently precludes  quantitative assessment  of
catalytic agent influences.

Studies of large point sources  (i.e.,  power plants) before and
after unit start-up  indicate  measureable increases in sulfate
concentrations  as  far as  40 miles  away (OAQPS,  1975).   Investi-
gations of sulfate  formation  in plumes of  coal-fired  plants
with particulate control  suggest that  the  oxidation rate of S02
is negligible for  the first 10  to  20 miles  but  increases to
3%/hr. or more  thereafter  (Newman  et al.,  1974a).  Similar

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studies on oil-fired plants  tentatively  indicate that the oxi-
dation rate may be more  rapid  in  the  first 10 miles (10 to
20%/hr.), with the rate  then becoming comparable to that of a
coal-fired plant plume  (Newman  et  al.  1974b).   This potentially
rapid initial oxidation  rate in the oil-fired plant plume is
most probably the result of  certain components in the emitted
flyash that catalyze the reaction.  Since  sulfates formed in
plumes are very small particles,  the  removal  rate for sulfates
by ground surfaces is much slower  than the removal rate for
S02.  Once formed, these sulfate  particles may be transported
for hundreds of miles,  although their downwind concentration is
diminished by dispersion.

Although urban SO2 levels have  decreased  substantially,  no con-
sistent similar trend has been  observed  for urban sulfates.
Long-range transport and complex  precursor relationships have
been hypothesized as explanations  of  this  phenomenon.   While
S02 emission reductions  in cities  resulted in less locally
formed sulfates, increases in  non-urban  SC>2 emissions (pri-
marily from power plants) may  have caused  regional sulfate
increases that, on balance,  offset the local  decreases.   This
explanation is supported by  the apparent  increase in manmade
sulfates at a limited number of eastern  non-urban sites  for
which data are available.  This increase  roughly parallels the
increase in overall S02  emissions  during  that time.  Although,
in aggregate, urban sulfate  levels showed  little change, vari-
able trends were observed for  different  cities.   Variations in
both the spatial distribution  of  sulfur  oxides emissions and in
atmospheric chemistry could  affect the relative magnitude of
local versus imported sulfates  and account for the variable
trends for individual cities.

Despite the uncertainties concerning  the  relationship between
S02 emissions and ambient sulfate  concentrations, the available
evidence suggests that  further  increases  in SC>2 emissions are

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likely to produce  increases  in  regional  sulfate levels.  How-
ever, sulfate  increases  are  not  likely  to be linearly propor-
tional to the  total SC>2  emissions  increase because of the
spatial distribution of  the  important  sources and the complex
formation mechanisms.

REMOVAL OF SULFUR  COMPOUNDS  FROM THE ATMOSPHERE

Mechanisms of  Removal

Mechanisms for  the removal of  sulfur compounds from the atmos-
phere may be classified  as follows:

     •    Diffusion of  sulfur  dioxide  to soil and vegetation
     •    Rainout  and washout
     •    Dry  removal of sulfate particles

The diffusion  of sulfur  dioxide  to  soil  and vegetation is rele-
vant to the  impact of the power  industry on atmospheric sul-
fates because  it constitutes a  process whereby part of the
conversion of  sulfur dioxide to  sulfates is circumvented.
Unfortunately,  from overall  environmental considerations, this
process has  harmful effects  on  vegetation.

Rainout and  washout are  differentiated as follows:  rainout
refers to processes initiated  in clouds, and washout refers to
processes occurring as  precipitation falls through the region
below clouds.   These processes  are  probably significant as
mechanisms for  the removal of  both  sulfates and sulfur dioxide
from the atmosphere.  Once formed,  sulfate particles may serve
as nuclei for  the  condensation  of water  as either liquid or
ice.

Sulfur dioxide  in  the presence  of water  is oxidized to sulfuric
acid and other  sulfates  through  several  mechanisms.  These

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include photochemical oxidants,  ammonia,  and  catalytic  metals.
Ambient temperature is also  thought  to  be  an  important  factor
(OAQPS, 1975).  A simplified example  of  one of  these  oxidation
mechanisms is the following  reaction  for  ammonia,  sulfur diox-
ide, and water  (humidity).   The  resulting  ammonium sulfate
would have atmospheric removal characteristics  appropriate for
particulates .
          NH3 + H2°
          2S02 + 2H20 + 02
          2NH4OH +
Just as sulfur dioxide can be  removed  from the  atmosphere by
dif-fusion, sulfate aerosols  can  be  removed by diffusion to the
surface of the earth.  Insofar as the  dry  deposition of sul-
fates is concerned, diffusion  is regarded  as more  significant
than the alternative process of  gravitational sedimentation.
Except for the possibility of  sulfate  particles from sea salt,
sulfate particles are generally  too  small  to undergo signifi-
cant sedimentation under  the influence of  gravity.

Residence Times

The residence times of sulfur  compounds  in the  atmosphere are
not known with a great deal  of certainty.   Residence times of
14-33 hours have been estimated  for  sulfur dioxide  and 3-5 days
for sulfate (National Researach  Council, 1978).

Transport Effects

Bearing in mind that the  residence  times are related to the
exponential removal rates, one can  easily  comprehend the fact
that significant fractions of  the sulfur dioxide and sulfate
persist in the atmosphere until  they are transported by wind
for long distances.  Thus, although  deposition  on  the surface

                               8

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of the earth may  be  pronounced  in  the immediate vicinity of a
source of emission,  long-range  influences are also to be
expected.

EFFECT OF BOILER  OPERATING  PARAMETERS

The absorption  of sulfur  oxides, metal oxides, and chlorides by
deposits  in  the boiler  results  in  the subsequent conversion of
these compounds to  sulfates.  Therefore,  any effect aimed at
minimizing these  deposits would  reduce sulfate emissions.  Soot
blowing  removes some of  this  material but momentarily increases
emission  of  sulfates and  particulates.

There is  little evidence  to indicate that combustion modifica-
tion will, in general,  be an  effective procedure for acid aero-
sol abatement although  low  excess  air firing, where practical,
may be an exception.  Existing  data indicates that acid aerosol
can be reduced  by operation with  low excess air.  The reduction
in NO and N02 is  accompanied  by  reduced 803 formation in the
flame and the reduced availability of oxygen pertains through-
out the  system.   This implies extremely good combustion con-
trol.  It must  be kept  in mind  that in low excess air combus-
tion there is the risk  of increased particulate formation which
might lead to an  increase in  catalytic oxidation of SO2«  How-
ever, from the  standpoint of  controlling  both NO/N02 Production
and acid  aerosol  formation,  this appears  to be a possible ap-
proach at the present time.

Another  aspect  of boiler  operation is the use of additives,
which in  effect change  the  metal content  of the fuel.  Gener-
ally, materials are  used  containing either Mg or Zn, both of
which readily form  sulfates.  The  particles thus formed may be
removed  by precipitators  thereby reducing the potential for
acid aerosol emission.  Various  forms of  the additive have been
shown to be effctive, i.e., metals, metal oxides, minerals, or

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organometallic compounds.  There  is  evidence  that  suggests  the
use of additives can deposit a coating  of metallic oxide,  such
as magnesium oxide, on the boiler  tubes  which then deactivates
the catalytic deposits and effects a  reduction  of  sulfate  aero-
sol emissions.  Generally though,  the use of  additives  is  moti-
vated by the reduction of corrosion  and  acid  particulate emis-
sion, through formation of neutral MgSO4 or  ZnS04  or MgSO4.

RELATED RESEARCH PROJECTS

A significant amount of research  into the significance  of  the
effects of acid fallout and their  quantitative  relationship  to
ambient levels of sulfates in the  air is currently in progress
by numerous governmental agencies  and industrial organiza-
tions.  The more important projects  to  date  include:

Project MISTT (Midwest Interstate  Sulfur Transformation and
Transport)

The technical approach of Project  MISTT, initiated by EPA's
Environmental Sciences Research Laboratory  in the  summer of
1974, is to study the transformations of S02  to sulfate in
polluted air masses undergoing transport.  The  intent is to
measure pertinent chemical and meteorological parameters with
sufficient accuracy so that they  may  be  used  with  physical  and
mathematical models to derive rate parameters which character-
ize the transformation processes.

MISTT results to date suggest the  existence  of  both homogeneous
and heterogeneous reactions.  Homogeneous reactions,  which  pro-
bably involve the hydroxyl radical,  predominate in dry daylight
conditions.  The rates vary from  1/2  to 5 percent  per hour,  de-
pending on sulight intensity, water  vapor concentration, ozone
concentration in the background air,  background pollution
levels in general, and the extent  of  mixing  of  the plume with
                               10

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background air.  On  the  other  hand,  heterogeneous reactions in-
volving liquid droplets  may  predominate  during high relative
humidity, at night,  and  in  clouds.   These  rates may be much
higher than the  1/2  to  5 percent  for homogeneous reactions.
Good quantitative data  on this  are  not  yet available but it is
known that with  very  high sulfate  and very high conversion
rates, liquid droplets  do exist.

Project MESO  (Mesoscale  Sulfur  Balance  Project)

The mesoscale sulfur  balance project, also managed by EPA's
Environmental Sciences  Research Laboratory,  involves the deter-
mination of the  proportion  of  aerosol in ambient rural air as-
sociated with sulfates  formed  during long-distance transport.
The relationship among  high  sulfate  measurements, meteorolog-
ical conditions  and  SO2  input  is  also being  examined.  The pro-
ject is designed to  test whether  successive  SO2 sources across
the Midwest cause an  accumulation  of sulfates  at a rate sub-
stantially greater than  overall removal  rates.  The hypothesis
being tested  is  that  as  air  masses move  across the country they
pass over successive  sources of SC>2r generally large power
plants.  Since sulfates  are  only  slowly  removed by natural pro-
cesses, a substantial build-up  of  sulfate  can  occur from re-
peated emissions of  S02.

Project SURE  (The Sulfate Regional Experiment)

Within the United States,  the  highest sulfate  levels occur in
the Northeast.   Concentrations  ranging  from  5-25 ug/m^ are
typical.  (During "episodes" values  up  to  80 ug/m^ have been
recorded).  This is  in  marked  contrast  to  the  3-4 ug/m^ com-
monly measured in the West.  Because of  the  high Northeast
values, the Electric Power Research  Institute  (EPRI) decided to
initiate a regional  sulfate  study  focusing the effort on the
populous Northeast.  Project SURE  is a  scaled  up version of

                               11

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EPA's Project MESO.  It's two primary  purposes  are  to  define
ambient sulfate in terms of  local  SC>2  emissions  and to assess
the contribution of the electric power industry  to  regional
sulfate levels.  The basic elements  of sure  consist of a
ground-based and air-based measurement program,  an  emission
inventory and development of a model to  predict  regional con-
centrations as a function of local emissions.

Project MAP^S  (Multi-State Atmospheric Power Production Pollu-
tion Study)

The goal of MAp3S, the Department  of Energy  (DOE)  sulfate pro-
gram, is to improve simulation capability  for  use  in evaluating
present and future effects due to  power  production  emissions.

Project ACES (Aerosol Composition, Effects,  and  Sources)

The purpose of EPA's Project ACES  is to  determine  the  sources
of urban aerosol.  Measurements of the composition  and size of
ambient aerosols have been made in selected  cities.  The aero-
sol components are assigned  to natural and anthropogenic
sources and classified as primary  or secondary  in  nature.
These results are compared with emission inventory  data.
Models, which include aerosol removal  mechanisms and secondary
aerosol formation mechanisms, are  used to  relate primary
sources of aerosol and precursor gases to  ambient  aerosol con-
centrations.  Thus, it becomes possible  to identify those
sources that need to be controlled to  provide  reduction in
total aerosol loading or specific  aerosol  components.

PERTINENT ISSUES

Under the Clean Air Act of 1970, the Administrator  of  EPA may
establish a National Ambient Air Quality Standard  (NAAQS) for
"any air pollutant which in  his judgment has an  adverse effect

                                12

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on public health and welfare",  and  results  from emissions of
"numerous or diverse mobile  or  stationary  sources."  It is
concern for this responsibility that  necessitates EPA's intense
interest in the sulfate  issue.   The possibility of an ambient
sulfate standard being promulgated  by EPA  is  also a major con-
cern of the electric power  industry as the  impact would be
quite severe.

Promulgation of such a sulfate  standard  requires a considerable
supporting data base.  Among  the areas where  research is war-
ranted  (and in most cases already in  progress)  include:

1.   Reliable monitoring methods for  total  sulfates,  sulfuric
     acid and specific sulfates.
2.   Quantitative  toxicological data  regarding  the relative
     effects of sulfur dioxide  and  specific sulfates.
3.   Investigation  into  sulfate precursor  relationships.
4.   Investigation  into  the  mechanisms of  acid  aerosol forma-
     tion and destruction.
5.   Correlation between sulfate emissions  and  ambient air
     concentrations as influenced by  physical,  chemical and
     meteorological parameters.

Fortunately, an integrated  interagency program  of research to
address the numerous issues  has already  been  formulated.

The discussion presented above  is not intended  to be  a compre-
hensive review of  this program,  but rather  identify some of the
issues which this  study  will  address  in  a  direct or indirect
manner.

SULFATE MEASUREMENT AT A POINT  SOURCE

A growing concern over the emission and  airborne transport of
sulfate materials  stimulated  this research  investigation

                               13

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surrounding a specific point source.  The  point  source  for  this
study was a representative oil-fired  utility  plant  in  the
Northeastern United States using  residual  fuel oil  with 1.9%
sulfur, 200 ppm vanadium and 0.12%  ash.  The  Niagara Mohawk
Power Corporation cooperated in the  four week field program
which consisted of meteorological,  ambient air quality, emis-
sion and combustion data gathering.   The investigation  covered
the period from September 18, 1978,  to October 15,  1978,  and
centered around the Albany Steam  Station in Glenmont,  New
York.

A comprehensive emission characterization  program was  performed
on all four of the 100 MW rated boilers.   Operating data  were
collected continuously on all boilers, supplying  information
necessary to assess the emissions on  an hourly basis.   Daily
ground-level total suspended particulate samples were  collected
at five monitoring sites, ranging 3.0 km to 5.5 km  from the
emission source.  Ground-level particulate samples  were also
collected at the emission source.   Sulfur  dioxide concentra-
tions were measured instrumentally  at all  sampling  sites.  Two
sampling sites included particle  sizing capability, using cas-
cade impactors and virtual impactors  (dichotomous samplers),
and visibility measurement capability using nephelometers.
Four sampling sites included NO/NO2 measurement  capability.

Meteorological measurements included  wind  speed  and direction
on the Hudson Valley floor and at an  elevation above  the  stack
height.  Atmospheric mixing height  measurements were made con-
tinuously with an acoustic sounding  device; calibration was
accomplished with helium-filled balloon sondes.  The  balloons
were tracked with theodolites in  order to  determine upper level
wind speed and direction.

The data were used to identify the  contribution  of  sulfate
emissions from a known point source  to the ground-level

                              14

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concentration of sulfate  in  the  vicinity  of  that same point
source.  The formation of primary  sulfate was  investigated as a
function of operational variables  and  the relationship between
primary sulfate emissions and  the  ambient ground-level concen-
tration was identified.

Wind speed and direction  measurements  were available  from the
National Weather Service  at  Albany Airport.  Wind  speed  and
direction, as well as air quality  measurements,  were  available
from the New York State Department of  Environmental Conserva-
tion's Rennsalaer monitoring site.

A map of the general area and  the  Hudson  River  is  shown  in
Figure 1, and a map showing  the  monitoring network  is shown in
Figure 2.
                               15

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                           SECTION 2
                          CONCLUSIONS
Total sulfate concentration in the plant effluent  ranged  from
22 ppm to 55 ppm as measured with a modified  EPA Method  6 sam-
pling train.  This resulted in emission rates  of 22 kg/hr.  to
82 kg/hr. from each operating boiler.  Sulfur  dioxide  emission
concentration averaged 938 ppm and average  emission rate  was
856 kg/hr.  Sulfuric acid concentration averaged 73.5% of the
total sulfate emission as determined using  a  controlled  conden-
sation sampling train.  However, a discrepancy  exists  between
the test results using the modified Method  6  train and the  con-
trolled condensation train for total sulfate measurement.  The
total sulfate results from the modified Method  6 tests were ap-
proximately twice those from the controlled condensation
tests.  The results of the modified Method  6  tests were  used  in
the sulfate emission correlations because they  are consistent
with data obtained from similar emission sources.

Particulate concentrations ranged from 60 mg/Nm3 to 170 mg/Nm3
and emission rates ranged from 12 kg/hr. to 70  kg/hr.  Between
32% and 67% of the particulate collected at 160°C  was  in  the
form of sulfate.

Mass median particle diameter was 1.8 urn to 4.0 urn during nor-
mal operation at high load.  Slightly lower diameters  were  ob-
served at low loads and slightly higher diameters  were observed
during soot blow.

A proportional relationship was observed between vanadium con-
centration in the stack gases and the emissions of sulfate.  A
reduction in sulfate emissions was implicated  by the  time of
on-line boiler operations, using a fuel additive.  However, the
relationship was not that strong.

                               16

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Local source/sink  effects  can  be  seen in the ambient sulfate
data from the Albany  area.   While the specific local sources
are not quantified,  their  presence is detectable.

The ambient sulfate  data  tend  to  indicate that the higher con-
centrations occur  as  pulses  or spikes.   These ambient pulses or
spikes last on  the order  of  magnitude about one day with lower
sulfate values  preceeding  and  following the 24 hour elevated
ambient concentrations.

Diurnal variations  in both meteorological and air quality para-
meters were found  to  exist.  These variations suggest that sul-
fate due to local  sources  would be minimally observed in the
Albany area.  The  night  time surface stable areas would tend to
retard the dispersion of  elevated sources to the ground.  The
surface levels  of  ozone  and  sulfur dioxide tended to have day
time maximums but  at  different times of day.  Thus, photochemi-
cal SC>2 to SC>4  conversions incorporating ozone were probably
minimal.

There were limitations  in  the  air sampling network.  During the
sampling period,  the  plume from the Albany Steam Station tended
to pass over or between  monitoring stations resulting in little
or no impact at these monitoring  stations.

Sulfate transported  into  the study area was higher during
periods of southwesterly  flow  aloft.  Ambient sulfate measure-
ments demonstrated a  high  variability in sulfate levels.  On
the three days  when  the  winds  were blowing directly towards a
monitoring site for  at  least 12 hours,  the average increase of
downwind sulfate concentration over upwind concentration was
from 3 ug/m3 to 26 ug/m3  or  from  34% to 60% of the total down-
wind sulfate concentration.
                                17

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In the study area during the study period, daily  ambient  sul-
fate concentrations ranged from 3 ug/m  to greater  than  40
ug/m3.  Annual geometric mean sulfate concentrations  for  down-
town Albany range from 8.0 ug/m  to 13.0 ug/ m3 and  7.1  ug/m3
to 11.0 ug/m3 for Troy.
                               18

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                            SECTION  3
                      PROGRAM  DESCRIPTION
DESCRIPTION OF THE  STUDY  AREA

General

The macrosphere of  this  investigation  includes the greater
Adirondack Mountain Region,  bordered on  the East by the Hudson
River, on the South by  the  Mohawk  River,  and on the West and
North by Lake Ontario and the  St.  Lawrence Seaway.  The Hudson
River Valley extends to  the South,  draining into the Atlantic
Ocean at New York City;  the Hudson  is  bordered on the West by
the Catskill Mountain Region and on the  East by gently rolling
terrain.  The Catskill  Mountain Region's  Northern border is a
rolling area extending  50 miles to  the Mohawk River.

Topography

The greater Albany  area  lies at the confluence of the Mohawk
and Hudson Rivers.   These rivers lie  in  broad valleys sur-
rounded by the Catskill  Mountains  to  the  Southwest, the
Adirondack Mountains to  the Northwest  and the Green Mountains
to the East.  These mountain-valley terrain features tend to
produce North-South surface winds.   The  topography in the study
area is shown in  the terrain cross-sections in Figure 3.  These
cross-sections illustrate the  small river bottom valley within
the larger Hudson River  Valley.  The Hudson River bottom land
is confined in a  shallow  valley about  200 m deep and about 2 km
wide.  The terrain  on the East side of the river above the bot-
tom land is somewhat higher than that  on  the West side.  The
West side above the river bluff is  relatively flat compared to
the more rolling East side.
                               19

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                                   FIGURE   1
                          THE HUDSON RIVER VALLEY
                                                                VKBMONT
'/s         & -r-
                                                                         Aprox. 1000
                                                                         foot contours
                                         Aprox. 2000 ft. contours
                                     20

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The Albany-Troy-Schenectady Metropolitan  area  is  the  reception
point for airborne materials  carried  by South  winds  from the
Newburgh-Kingston-Poughkeepsie  industrial areas  of  the  Mid-
Hudson Valley.  The New York  City-Philadelphia-Baltimore area
sources are still further South.  Westerly winds  transport air-
borne materials from Buffalo-Rochester-Syracuse  and  from indus-
trial areas along the shores  of Lake  Erie and  Lake Ontario.
Northwest winds may transport materials from  the  St.  Lawrence
Valley area, a major paper manufacturing  industrial  center.

The three cities of Albany, Schenectady,  and Troy and their
environs form one of the major metropolitan areas of  the
country.  This area, located  near the juncture of the Mohawk
and Hudson rivers, is one of  the nation's oldest  industrial  and
commercial centers.  From early colonial  days, ocean-going
ships ascended the Hudson River to  Albany,  which  served  as a
transhipment point to and from  the  interior.   The opening  of
the Erie Canal between Buffalo  and  Albany in  1825 provided
further incentive for growth.

The land between Albany and Troy is completely built  up  and  the
area between Albany and Schenectady is nearly  so. Manufactur-
ing employs about one-third of  the  total  labor force. One of
the main industries is the manufacture of electrical  equipment,
mostly in Schenectady.  Other manufacturing in the  area  in-
cludes textile mills, locomotives,  paper  products,  chemicals,
meat products and foundries.  Albany, the State  Capital  con-
tains a sizeable number of professional and clerical  workers
(Bogue and Beale, 1961).  Between Albany  and Poughkeepsie, to
the South, are several cement plants.

In addition to the present Port of  Albany,  other  transportation
facilities include Interstate Highways 87 and  90. The Penn
Central maintains railroad tracks on  both sides  of  the Hudson
River.   There is a sizeable railroad  marshalling  yard to the

                               21

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      FIGURE 2
LAYOUT OF STUDY AREA
          22

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                                              SECTIONAL  VIEW OF SAMPLING NETWORK
NJ
U)
                          Site 01 Cross-Section
   400-

Feet
   200-
Emission Source
Cross-Section            Met  g
           ..Site  06     Tower
                    w
                     km 4
                 400-
              Feet
                 200-
                    3       2

           Site 05  Cross-Section
                                                            |l  Emission
                                                            ||+Source
                                                             O
                    W    I
                      kr> 4
                                                             Site  05
       Site 04

_Site.03.-
                                                         FIGURE 3

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South of Albany as well as another  marshalling  yard  in the Port
of Albany area.  The Albany airport  is  served by  scheduled air
carriers, and airport services  include  an  FAA Air Traffic
Control Tower, Flight Service Station,  and  an office of the
National Weather Service.

DESCRIPTION OF THE EMISSION SOURCE

General

The emission source under study  is  an oil-fired utility power
plant consisting of four boilers with a  total net steam gener-
ating capacity of 400 MW, and 140 MW capacity using  gas tur-
bines.  The plant is part of the Niagara Mohawk Power Corpora-
tion's generating system, which  serves  the  Northern  section of
New York State, including the Syracuse  and  Albany areas and the
Adirondack Region, and a portion of  the  Western tip  of the
State, including Buffalo.  One  component of the generating
system is an oil-fired plant with 1136 MW  of  net  generating
capacity at Oswego in the Mohawk Valley.   Also  included in the
system are two coal-fired plants in  the  Buffalo area with a
combined total of 1040 MW of net generating capacity-  Numerous
hydro-electric plants also supply power  to  the  customers in the
Adirondack Mountain Region (Electrical World, 1978).

Albany Steam Station

Each of the four boilers at the Albany plant  is a Combustion
Engineering unit with tangential combustion,  rated at 675,000
Ibs. steam per hour and 100 MW  net  power output.   During the
28-day time period under study,  three boilers were operating
normally on 17 days, four boilers were operating  normally on 10
days, and two boilers were operating on  one day.
                                24

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The boilers are housed  in  a  large  brick building, approximately
50 meters high; each  boiler  exhaust  is  vented to an individual
stack, the base of which  is  supported  by the power plant struc-
ture.  The top of each  stack is  approximately 100 meters above
ground and has an inside  diameter  of 3.86 meters.

During the period of  study the  plant was firing residual fuel
oil of Venezuelan origin  with  an average sulfur content of
1.9%; vanadium and ash  concentration was 200 ppm and 0.12%
respectively.  Since  the  object  was  to  study the point source-
related contribution  sulfates  have on  ambient levels,  this
plant was chosen because  its fuel  is likely to have a  signifi-
cant effect on primary  sulfate  emissions.  Fuel was transported
via ocean-going tank  ships up  the  Hudson River to the  plant
site.  Two fuel handling  circuits  transported oil from the
three storage tanks  to  the four  boilers as it was combusted.
Each fuel circuit was capable  of drawing oil from any  combina-
tion of the three storage  tanks.

A fuel additive, consisting  of  magnesium and magnesium oxide in
a petroleum liquid,  was added  to the oil just prior to combus-
tion to inhibit corrosion  caused by  sulfuric acid.   The addi-
tive was stored in a  bulk  tank  outside  the plant structure.
The liquid was periodically  transferred from the main  tank to
holding tanks from which  it  was  drawn  and injected into the oil
lines at a nominal ratio  of  2500:1 (oil:  additive by  volu-
metric measure).

The operating boilers produced  an  average of 67 percent maximum
generation capacity  from  2200  hours  through 0500 hours during
the study period, with  an  average  of 80 percent maximum genera-
tion capacity from 0900 hours  to 1600  hours.  Transition to a
peak 'approaching 90 percent  maximum  generation capacity oc-
curred in the intermediary time  periods.
                                25

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The boiler plant operates on a rotating  schedule  with  each
boiler out of service for four to  six weeks  to  perform pre-
ventive maintenance at least once  anually.   During  the outage
the various boiler-turbine-generator components are disas-
sembled, cleaned, inspected, repaired or  replaced,  and reas-
sembled.  At the initiation of the  study  period,  Boiler Unit 3
was out of service to perform a  four-week maintenance  program/-
Boiler Unit 4 had been in service  for two weeks since  its
annual overhaul; Boiler Unit 1 had  been  in  service  six weeks
since an outage for replacement  of  a transformer:  and  Boiler
Unit 2 had been in service ten weeks since  annual  overhaul.
Boiler Unit 3 was returned to service after  the 18th day of the
study period.

DESCRIPTION OF THE TEST PROGRAM

Emission Measurement Boiler Operations

In order to quantify the rate of sulfate  and  other  specific
materials emitted from the point source  stacks,  samples were
extracted from the stack effluent  concurrent  with  the  meteoro-
logical and ground-level concentration measurements.  Through-
out the investigation, combustion  and operational  variables,
which can have a significant effect on the  quantity of ejected
materials, were continuously documented  by  recording instru-
ments.  Using statistical methods,  the simultaneous operational
variables and emission test results were  correlated in order to
assess the quantity of materials emitted  on  a continuous real-
time basis.

Samples of particulate matter were  obtained  by  filtration of
the boiler exhaust gas according to EPA  Particulate Test Method
5 (40 CFR 60 App. A).  The glass fiber medium was  kept at 160°C
to prevent condensation of sulfuric acid.   The  samples of flue-
gas were extracted isokinetically  through an  electrically
                               26

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heated glass-lined probe with  a  stainless  steel nozzle pointing
into the gas stream.   Discrete annuli  were established at the
centers of concentric  equal  areas  within  the  stack
cross-section.

Each annulus was sampled at  the  center of  each of four quad-
rants.  The particulate sample consisted  of a sum of material
extracted from twelve  representative points.   The material was
analyzed for total weight  and  composition, including sulfate
and other water soluble ions,  and  specific metallic content,
i.e., nickel, calcium, sodium, potassium,  vanadium, iron, mag-
nesium, and manganese.

The particulate sampling method  was  used  to quantify the spe-
cific materials in terms of  mass per unit  volume of gas ejected
from the stack.  Simultaneous  measurements of the physical gas
characteristics (velocity  pressure and temperature) and quanti-
tative analysis of the major gas constituents (water vapor,
oxygen, nitrogen, carbon dioxide)  resulted in an assessment  of
the volumetric rate of total flue  gas  emission.  Specific con-
centrations of ejected materials were  then computed in terms of
mass per unit time.

The discharge of particulate sulfate materials was quantified
using the method described above.   However, a large portion  of
the sulfate materials  leaving  the  stack can be in the form of
sulfuric acid, which may be  gaseous  at the filtration
temperature.  An additional  test method was used whereby the
flue gas was extracted through a heated glass-lined probe; par-
ticulate matter was removed  from the sample stream with a
quartz wool plug prior to  flowing  into the probe.  Collection
of the gaseous sulfate materials was accomplished by bubbling
the sample gas through an  aqueous  solution of isopropyl alco-
hol.  Gaseous sulfate, a hygroscopic material, was absorbed  in
the aqueous solution,  while  sulfur dioxide passed through
                               27

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solution, while sulfur dioxide passed  through  unchanged.   A
second bubbling solution of hydrogen peroxide  and  water was
used to oxidize and absorb the sulfur  dioxide.   Both  solutions
were immersed in an ice bath to enhance  condensation  and  col-
lection.

The sampling and analysis was performed  in  accordance with EPA
Sulfur Dioxide Test Method 6 (40 CFR 60  App. A).   The plug
filter, probe washings, isopropyl alcohol,  bubbler exit plug
filter, and hydrogen peroxide solution were  analyzed  separately
for sulfate using barium-thorin titration with  cation removal
pretreatment of the plug filter and probe washings.   Results
were obtained in units of mass per unit  volume  and volume per
unit volume of total flue gas emission.  Since  these  tests were
performed concurrently with the gas volumetric  assessment, the
results could be converted to mass emission  per unit  time.

A sulfate characterization system was  used  by  EPA  personnel
during the field sampling to assess the  quantity of  primary
sulfate that was emitted as sulfuric acid.   The system con-
sisted of a high-temperature heated quartz  probe,  followed by a
high-temperature quartz filtration device.   The filtration de-
vice was enclosed with a custom made heating mantle,  and  had
a coarse quartz frit for support of the  filtering  pad. Follow-
ing filtration, the gaseous sulfuric acid was  converted  to the
aerosol form in the temperaturecontrolled Goksoyr-Ross conden-
sation coil (Cheney and Homolya, 1979).

The acid aerosol was collected in a Greenburg-Smith  bubbler
containing an 80% solution of isopropyl  alcohol and  water.
Following this the sulfur dioxide was  collected in an impinger
containing 3% peroxide and water.  The recovered samples  were
analyzed using the barium-thorin procedure  described  in EPA
Sulfur Dioxide Test Method 6 (40 CFR 60  App. A).
                               28

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The particle size distribution  of  ejected  materials also be-
comes an important  factor  in  the  analysis  due  to air transport
considerations.  Cascade  impactors were  used  to obtain samples
of particulate matter within  specific  size ranges concurrent
with the samples of  total  particulate.   The impactors each con-
tained eight fractionating  jet  plates  in series, with collec-
tion substrates below them.   The  substrates were composed of
glass fiber material and  served as impingement  surfaces for the
particles exiting through  the jet  directly above.  Each jet
plate has a design  cut point  with  a 50%  probability that a par-
ticle with that aerodynamic diameter will  impinge on the sub-
strate below it.  Smaller  particles follow the  gas streamlines
through the successive jets until  the  jet  with  the appropriate
size is reached.  Particles below  about  .5 urn  are collected on
the backup glass fiber filter.   The filter and  substrates were
analyzed for net particulate  material  and  presented as the per-
centage of particulate per  stage.

Samples of particulate size range, total particulate, sulfate
and sulfur dioxide  were procured  from  each boiler concurrently
with the documentation of  operational  variables.  No attempt
was made to modify  the combustion  controls from the normal
operational procedures.   The  load  generation was purposefully
lowered on several  days in  order  to obtain samples under this
type of normal operation,  however  no alterations were insti-
tuted.  The normal  soot blowing schedule was not changed, how-
ever each occurrence was  documented and  several samples were
obtained during soot blow  conditions.  Samples  of fuel oil and
chemical oil additive were  obtained on a daily  basis.  Fuel
sulfur content was  determined daily with more  detailed analyses
including metals content  analyses  performed weekly.

The volumetric concentration  of gaseous  sulfur  dioxide, oxygen,
carbon dioxide, and gas temperature was  measured continuously
                              29

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on two stacks using instrumental  analyzers.   These data pro-
vided a general representative profile  of  ejected  materials on
a daily basis.

Ambient Air Quality Assessment

The distribution of sulfate materials  in  the  ambient ground-
level atmosphere was determined concurrently  with  meteorolo-
gical air transport factors in order  to ascertain  the source of
such materials.  A network of monitoring  stations  was necessary
to assess the impact of source-emitted  materials on ground-
level concentrations.  The emission source had  been the subject
of previous and ongoing studies and was surrounded by several
satellite monitoring stations.  Seven  stations  (see Figure 2)
were equipped with continuous sulfur  dioxide  analysis capabil-
ity: two stations to the North and one  to  the South in the
Hudson Valley; one station to the West  above  the West bank of
the river? two stations to the East above  the East bank of the
river; and one station was located immediately  to  the North of
the plant.

Six of the monitoring sites were  supplied  with  the capability
of measuring  total suspended particulate  concentration on a
24-hour basis.  Throughout the time interval  during which this
experiment was performed, a sample of  total  suspended particu-
late matter was obtained each day at  each  of  these sites.
These samples were analyzed for sulfate composition, other
water-soluble constituents, and acid-soluble  metallic constitu-
ents .

The mass fraction of airborne particulate  matter within certain
size ranges was determined with the use of cascade impactors.
The impactors separate the particles  according  to  individual
aerodynamic diameter by impaction upon  a  glass  fiber material.
The impactors were located at the base  site  immediately North
                               30

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of the emission source,  and  at  site  5  to  the  South of the emis-
sion source.

Two dichotomous samplers were used  to  discriminate between par-
ticles with aerodynamic  diameters  above  and  below a specific
diameter.  The dichotomous sampler  accelerates  the particulate
matter through a nozzle; particles  with  an  aerodynamic diameter
smaller  than 3.5 urn  follow the  gas  streamlines  and are removed
by a Teflon micropore  filter while  the larger (greater than 3.5
urn) particles impact upon a  separate filter  medium.   The dicho-
tomous samplers were also located  at the  base site and site 5.

One obvious factor concerning air  quality is  visibility.
Nephelometers were used  to quantify  the  amount  of light-scat-
tering particulate (other than  condensed  water  vapor) present
in the atmosphere during the test  program.   These instruments
were located at the  base site and  site 5.

Nitrogen oxide analyzing instruments operated at  sites 1, 3,
and the  base site.   Ozone analysis  capability was included at
the base site.  Most of  the  ambient  measurement capability
mentioned above was  also available  at  the NYSDEC  station in
Rensselaer.  Total suspended particulate  historical data was
available from NYSDEC  at downtown  Albany,  Schenectady, and Troy
on a one day in six  basis.

Sulfate Artifact Experiment

Ground-level concentrations  of  sulfate as measured with high-
volume sampling apparatus can consist  of  primary  sulfates
emitted  from point sources plus  secondary sulfate formed by the
conversion of sulfur dioxide during  airborne  transport.  A pos-
sibility also exists for the formation of sulfate artifact to
occur during or after  the sampling  period by  chemical reactions
with sulfur dioxide, metallic oxides,  and moisture.   A program
                              31

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was conducted to isolate the effects of  sulfate  artifact  forma-
tion and to evaluate the contributory  factors  involved  in meas-
urement error caused by this conversion.   The  results  of  this
series of tests are presented separately.

Filter media, handling procedures,  and gas  dosage  with  sulfur
dioxide were evaluated.  Three types of  filter media were in-
vestigated:  01-Gelman Type A/E glass  fiber;  02-Gelman Type A
glass fiber; 03-Gelman Microquartz.  A collection  device  was
designed and fabricated, consisting of a modified  high-volume
sampler motor with four identical  stainless  steel  inlet tubes;
each tube contained mating surfaces fitted  between the  two
halves of a 90 mm diameter filter  holder,  enabling a maximum of
four identical simultaneous samples of total  suspended  particu-
late.  The openings of the four inlet  tubes  extended five feet
above the roof of the monitoring trailer.

An overhanging cap was designed so  as  to comply  with specifica-
tions for collection of suspended  particulate  less than 100
urn.  The exhaust of the high-volume motor  was  ducted outside
the trailer with flexible tubing.

As part of the operational procedure,  at least two different
types of filters were simultaneously exposed  during the sampl-
ing interval.  After exposure, certain filters were placed in
glassine envelopes and sealed in air tight polyethylene enve-
lopes.  The remaining filters were  placed  in  glassine envelopes
and manila envelopes (standard procedure for  all high-volume
sampling).  The protected filters  had  minimum contact with the
atmosphere prior to removal for analysis,  whereas  the unpro-
tected filters were subject to such atmospheric  conditions as
could penetrate the standard envelopes.  These filters were
evaluated to determine if there were any significant contribu-
tions attributed to the handling and storage  procedures.
                                32

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In addition, provisions  were  made  on  several test days to in-
troduce sulfur dioxide gas  into  the  sampling tube.   The sulfur
dioxide injection  tests  were  performed  on three separate days
using type 01 filters.   All  filters  on  these days were sealed
in air tight polyethylene  envelopes  until analysis.

Meteorological Assessment

In order to assess  the impact of  source emissions on the
ground-level concentration  of sulfate materials,  an  understand-
ing of the local meteorology  is  essential.   To a  certain extent
the transport of airborne  materials  is  dependent  upon the topo-
graphy of the area  under study,  however the  measurement of
physical characteristics of  the  atmosphere  is the prime method
of understanding this airborne transport mechanism.

The emission source  comprising the subject  of this  investiga-
tion is part of an  area  that  has,  on  a  continuous basis,  exten-
sive meteorological  documentation.   The National  Weather Ser-
vice has a station  at the  Albany  County Airport located in the
center of the triangle formed by  Albany, Schenectady, and
Troy.  The New York  State  Department  of Environmental Conserva-
tion operates an air quality  and  meteorological monitoring sta-
tion at Rensselaer,  across  the river  and in  a north-north-
easterly direction  from  the  emission  source.  The Niagara
Mohawk Power Corporation maintains a  meteorological  tower on
the slope of the West bank  of the  Hudson River Valley bottom
land just above the  emission  source.

In addition to the  existing meteorological  network,  two moni-
toring stations were added  on the  floor of  the Hudson River
bottom land; one approximately three  hundred meters  North of
the plant and another approximately  five and one-half kilo-
meters South.
                               33

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Significant knowledge of the  air  transport  factors was avail-
able from the instrumented  tower  located  on the slope above the
emission source.  Wind factors  on  the  floor of the river valley
may have been affected by the steep  slopes  on either side,
causing a wind-channel effect within the  valley quite different
from the wind pattern above the slopes.   The upper level in-
struments on the tower are  one  hundred  meters above grade; the
grade on the slope is 33 meters above  the grade of the valley
floor, resulting in measurements  at  a  point that is 33 meters
above the stack exit.  Wind and temperature are measured at
this point (top of the tower) and  at a  lower point (90 meters
below the top of the tower).  In  addition to wind speed and
direction, air temperature  and  the  temperature difference
between the two instrument  levels  are  obtained.

An acoustic sounder was used  to determine the height at which
upward rise of pollutants terminates.   An acoustic signal
directed upward rebounded from  the  atmospheric layer at which
the temperature change occurred.   The  length of time necessary
for the signal to return was  proportional to the mixing
height.

The acoustic instrument operated  continuously and was augu-
mented by the use of balloon-borne  temperature sensors.  While
a radio receiver-recorder plotted  the  signals from the sensor,
the balloon was tracked manually  by  two theodolites, precision
optical instruments capable of  measuring  both the elevation
angle and azimuth angle of  the  balloon  at 15 second intervals.
A computer was used to translate  angles into wind speed and
direction with height using the method  of Norman Thyler
(1962).
                              34

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Meteorological and Ambient Air Quality  Site  Descriptions

Base —

The base site was located 600 feet  North  of  the  Albany Steam
Station.  It consisted of one of  the  York Research  trailers
equipped with ambient air intakes.  These intakes  included a
glass manifold for sampling  of gaseous  SO2,  NO,  N02,  NOX and
03; a stainless steel sampling device for the  multi-head high
volume sampler; and  an air intake  for use by the nephelometer.
The trailer was kept at  a constant  temperature (25° _+ 5°C).
Outside the trailer  the  solar radiometer  was mounted  at a
height of 5 feet; a  10 meter tower  was  erected with wind direc-
tion and speed at 10 meters  and  temperature  and  dew point at
the 8 meter height.  Other instrumentation included a rain
gauge, an acoustic sounder with  transceiver  located within a
lead enclosure, and  2 high volume  samplers located  8  feet above
the ground.  On the  roof of  the  trailer at a height of approxi-
mately 12 feet were  the  dichotomous sampler  and  the cascade
impactor with flow control.   Balloon  launchings  were  also
carried out at this  location.  Satellite  stations  surrounding
the plant were equipped  as follows:

Site 1 —

Located at a Niagara Mohawk  Substation  on Delaware  Avenue in
downtown Albany, it  consisted of  a  Meloy  SO2 monitor, a Teco
NO, N02, NOX monitor and two 24-hour  high volume samplers.

Site 3 —

Located on Hays Road in  a rural  environment  this site included
a Meloy S02 unit and a Teco  NO,  N02,  NOX  unit  along with two
24-hour high volume  samplers.  (Site  2  designation  was not used
                                35

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as it represents an inactive monitoring  site  owned  by  Niagara
Mohawk).

Site 4—

Located in the Greenbush Power Substation  it  contained a Thermo
Electron S02 monitor and two 24-hour high  volume  samplers.

Site 5—

This site was located in Bethlehem Park  approximately  100 feet
from the shore line of the Hudson River.   There were two
shelters located here, one contained the Meloy SC>2  and the
dichotomous sampler, while the other contained the  recorders
for wind speed and direction located on  a  30  foot  tower as  well
as temperature sensor, a nephelometer, and a  multi-head high
volume particulate sampler.  Also located  here were two 24-hour
high volume samplers, a cascade impactor and  flow  control unit,
and a rain gauge.

Site 6—

Site 6 was located in the Bethlehem substation and  contained a
Meloy S02 unit as well as two 24-hour high volume  samplers.

Meteorological Tower—

The tower was located approximately 1,000  feet Northwest of  the
plant.  Wind speed and direction were taken  from  two levels:
upper level 462 feet above mean sea level, lower  level 150  feet
above mean sea level.  Delta-T was also  measured  here  with  a
height difference of 312 feet.
                               36

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Rensselaer  (Port of Albany)—

The NYSDEC monitoring  station  in  Rensselaer was located on the
Northern side of the ship  turning basin  for the Port of
Albany.  To the South  of this  station  on both sides of the
river are the docking  facilities  and  tank farms of the port.
To the North of this monitoring  station  extends an industrial
district.
                               37

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                           SECTION  4
                     EMISSION MEASUREMENTS
PARTICULATE MEASUREMENTS

Samples of particulate matter were  extracted  on glass fiber
filters using EPA Particulate Test  Method  5.   The filters were
kept at 160°C or greater to prevent condensation of sulfuric
acid during sampling.  Gas and particulate  samples  were ex-
tracted isokinetically from twelve  sampling points  through a
heated glass-lined probe.  The particulate  material was ana-
lyzed for total weight, water soluble  ions, sulfate, nitrate,
ammonia, chloride, and specific metals,  nickel,  calcium,
sodium, potassium, vanadium, iron,  magnesium,  and manganese.
Measurements were made that permitted  calculation of the  volu-
metric rate of gas flow.

Test Schedule

Tests were performed at various points  along  an operational
line from 50% to 100% maximum load,  with the  majority of  tests
performed at the upper end.  No combustion  optimization was
performed and the boilers operated  routinely  depending on
system demand.  Only during specific periods  when a boiler was
off the automatic load control for  lowload  tests did any  insti-
tuted controls occur.  A breakdown  of  the  fuel  use  ranges and
the tests performed in those ranges is  shown  on Table 1.
                               38

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                            TABLE  1
         PARTICULATE TESTS  IN SPECIFIC  FUEL  USE  RANGES

                   Unit  1       Unit  2      Unit  3     Unit 4
58-62
(7)
54
(3)
34
(3)
60-62
(8)
43-56
(3)
31-32
(6)
59-63
(7)
42
(1)
-
-
59-65
(14)
-
-
32
(2)
100 gal./hr.
(No. of tests)
100 gal./hr.
(No. of tests)
100 gal./hr.
(No. of tests)

Test Results
Results of  individual particulate  tests  are  presented  with
simultaneous combustion parameters  on  Table  2.   Results  of
filterable  particulate varied  from  about  60  mg/Nm3  at  low load
conditions  to about  170 mg/Nm3  at maximum load  conditions.   One
extreme occurred during soot blow when the particulate concen-
tration was in excess of  300 mg/Nm3 (Unit 2, 9-26,0950).   This
may also have been contributed  by  blockage of  ash  in  the
cyclone hoppers.  Total (filterable plus  condensible)  particu-
late concentration ranged 70-225 mg/Nm3.   Filterable  particu-
late emission rate ranged 12-70 kg/hr. and total particulate
emission rate ranged 17-85 kg/hr.

A model of  particulate emission was developed  using oil  con-
sumption, boiler oxygen concentration, and fuel  additive  ratio
as the independent variables.   The  model  can be  found  in
Section 4.

Particulate Composition

The particulate samples were analyzed  for water  soluble  SO^,
Cl~, N-NH4", N-NO~3  and for metals  Na, K,  Mg,  Ca,  Ni,  Mn, Fe,
                               39

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                 TABLE 2
COMBUSTION PARAMETERS AND PARTICULATE TEST  RESULTS
Date

Unit 1
9-18
9-19**
9-19
9-19
9-20
9-20**
9-20
9-29
9-29
9-29
9-30
10-01
10-01
Unit 2
9-21
9-21
9-22**
9-22
9-23
9-23
9-23**
9-24
9-24
9-24**
9-25
9-26**
9-26
9-26
9-27
* EOT
** Soot
Time *


1430
1040
1240
1515
1005
1210
1430
1110
1305
1500
1045
1015
1200

1300
1449
0955
1400
0951
1155
1416
0945
1130
1340
0950
0950
1155
1340
0940

Blow
Oil Flow
gal/hr

5900
6100
6100
6100
6000
6100
6200
5400
5400
5400
3400
3400
3400

6150
6100
6100
6050
3100
3100
3100
3200
3100
3100
6150
6000
6200
6100
5600

Test
Fuel
S-%

1.95
1.98
1.98
1.98
1.78
1.78
1.78
2.00
2.00
2.00
2.05
1.80
1.80

1.70
1.70
1.75
1.75
1.90
1.90
1.90
1.50
1.50
1.50
1.97
1.95
1.95
1.95
2.05


Boiler
0,.-%-
£,

3.1
3.1
3.1
2.6
3.0
2.5
2.5
3.8
3.8
3.8
3.6
3.2
3.2

2.2
2.0
2.3
2.2
4.6
4.6
4.5
3.6
3.5
4.0
2.2
2.0
2.0
1.9
2.2


Stack
0 -%
£.
5.8
5.6
5.9
5.4
5.6
5.7
5.8
7.1
7.2
7.2
7.7
7.6
7.7
5.5
5.6
5.4
5.3
8.1
8.3
8.2
7.6
7.8
7.4
6. 3
6.1
6.0
5.9
6.3
Stack
Temp-°C
161
166
161
160
160
160
159
163
159
161
154
152
150
188
188
179
177
148
148
153
150
149
157
177
170
177
185
165
Front-h
rag/Am
89.79
99.27
89.78
95.93
96.82
115.44
106.58
66.93
65.32
72.27
60.40
49.47
52.50
102.55
83.90
104.19
73.53
58.12
55.23
68.45
52.78
54.54
66.94
69.86
183.84
81.49
69.28
76.10
Total
mg/Am3
120.98
122.59
139.52
137.13
126.57
137.94
119.04
72.00
91.95
90.80
86.83
81.50
69.81
123.12
94.22
115.16
83.35
66.38
60.14
80.35
90.77
74.56
73.35
80.52
191.61
96.91
88.92
82. 14
Front-Jj
mg/Nm
146.26
160.06
146.55
156.75
159.24
189.09
174.45
107.81
106.72
115.10
96.74
79.13
84.88
181.38
150.08
178.84
124.05
89.99
85.83
107.41
84.02
86.60
107.51
119.47
302.14
136.42
118.84
125.51
Total
mg/Nm3
197.07
197.68
227.. 74
224.08
208.18
225.95
194.85
115.97
150.22
144.62
139.08
130.36
112.87
217 .77
168.54
197.67
140.62
102.79
93.46
126.08
144.29
118.40
117.80
137.70
314.91
162.22
152.52
135.48
Front-is
kg/hr
53.66
61.95
53.59
57.87
56.45
66.86
64.36
40.61
37.33
43.41
21.61
17.89
19.03
67.09
56.77
69.26
48.93
23.18
21.14
26.00
21.30
21.29
25.83
45.90
114.20
54.66
45.18
45.29
Total
kg/hr
72.30
76.50
83.28
82.72
73.80
79.90
71.89
43.68
52.54
54.54
31.07
29.48
25.30
80.55
63.75
76.56
55.46
26.47
23.02
30.52
36.64
29.11
28.31
52.91
119.03
65.00
57.98
48.88

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                   TABLE  2
COMBUSTION PARAMETERS AND PARTICULATE TEST RESULTS (CONTD.)
Date
Time* Oil Flow
gal/hr
Unit 2
9-27
9-28
Unit 3
10-11
10-11
10-11
10-12
10-13**
10-13
10-13
10-15
Unit 4
10-03
10-03
10-03
10-04
10-05
10-05
10-05**
10-06
10-06
10-06
10-07
10-07
10-08
10-08
10-09
10-09
* EOT
** Soot
(Contd.;
1145
0950

1002
1150
1335
1010
0930
1125
1315
1005

1010
1209
1410
1325
0940
1125
1330
0950
1145
1340
1025
1240
1105
1304
1055
1440


5600
4300

6300
6300
6300
5900
6200
6200
6300
4200

6300
6400
6300
6000
6150
5900
6300
6100
6000
6100
6200
6050
3200
3200
5950
6500

Fuel
S-%

2.05
2.25

2.10
2.10
2.10
2.28
2.20
2.20
2.20
2.14

2.10
2.10
2.10
2.20
1.50
1.50
1.50
1.40
1.40
1.40
1.40
1.40
1.70
1.70
1.96
1.96

BoiL
°2~
	
2.3
3.8

2.3
2.1
2.2
2.6
2.1
2.1
1.9
3.5

2.7
2.7
2.5
2.0
1.9
1.8
2.1
1.9
1.6
1.7
2.1
2.4
5.5
5.0
3.5
3.2

Blow Test
                     Stack
                      6.4
                      7.4
                      6.3
                      6.0
                      6.1
                      6.4
                      6.2
                      6.2
                      6.0
                      7.8
                      6.8
                      6.4
                      6.7
                      6.6
                      6.2
                      7.2
                      6.4
                      6.6
                      6.3
                      6.6
                      5.9
                      6.3
                      9.6
                      9.7
                      6.4
                      6.4
Stack
Front- !j.
Temp-°C mg/Am"*
166
158
145
148
149
146
146
143
146
119
157
160
156
153
157
150
155
157
158
160
166
161
131
133
157
160
73.42
60.41
94.73
79.07
92.87
107.99
93.81
77.23
101.75
39.23
70.38
64.96
53.76
74.16
75.57
60.65
87.22
79.37
79.63
72.48
63.65
65.67
43.83
39.87
66.47
95.74
Total 3:
mg/Am
101.45
83.63
102.82
105.71
115.53
127.22
112.47
87.56
108.28
56.96
98.01
84.60
64.51
97.70
96.01
85.89
126.31
88.96
89.98
77.99
89.17
72.25
51.27
42.51
102.64
103.81
Front-^- Total,, Front-Jj
mg/Nm
121.70
97.17
148.59
125.82
149.49
170.39
149.18
120.85
161.55
57.44
114.04
106.21
87.37
118.80
123.45
94.81
141.27
129.63
130.77
120.52
115.00
108.25
65.96
60.21
107.10
154.14
mg/Nm
168.17
134.52
161.28
168.23
185.97
200.75
178.85
137.01
171.93
83.39
158.82
138.33
104.85
156.52
156.82
134.27
204.58
145.29
147.77
129.68
149.38
119.11
77.16
64.19
165.37
167.51
kg/hr
45.12
30.98
58.26
47.58
54.75
64.38
52.97
48.08
59.56
12.11
47.67
43.45
32.78
41.58
43.94
28.95
51.67
45.70
48.32
43.42
43.81
40.31
17.52
15.75
39.85
60.58
Total
kg/hr
62.35
42.89
63.24
63.61
68.10
75.85
63.51
54.51
63.38
17.59
66.39
56.59
39.34
54.79
55.82
41.00
74.82
51.22
54.61
46.72
56.91
44.35
20.49
16.79
61.53
65.71

-------
and V.  These results are shown  in Table  3.   An unusual set of
tests occurred on Unit 2, where  very  high levels of Na, K,  Ca,
and Cl~ were observed.  These elements  are  common in sea water,
indicating that some stratified  water was present in the fuel
tanks during these tests.  The abrupt decrease  of the anomolous
elements on 9-27 indicates a fuel supply  switch to a different
tank.  Consistently high values  of vanadium are present due to
the high vanadium content in the  fuel oil (see  Table 14).
Sodium and magnesium are also high, although not quite as  con-
sistent as vanadium.  The consistency with  which vanadium  is
present in the particulate emissions, combined  with the fact
that vanadium is not a common element in  airborne particulate,
makes it an excellent tracer when measured  in the ambient  air.
Magnesium and sodium do not share this  distinction, being  com-
mon elements of windblown dust.

Particulate Sulfate

The particulate sulfate results  have  been tabulated with simul-
taneous combustion parameters on Table  4.   The  emission of  par-
ticulate sulfate ranged from less than  10 kg/hr. at 50% load to
somewhat less than 30 kg/hr. at  full  load with  soot blowing.
Particulate sulfate fraction of  filterable  particulate ranged
from 32% to 67% and an inverse relationship with fuel consump-
tion was apparent.

A model of sulfate fraction of particulate  was  developed using
fuel consumption, boiler oxygen  concentration,  fuel oil
additive ratio, and days of operation since the last boiler
wash.  The model can be found in Section  4.

TOTAL SULFATE AND SULFUR DIOXIDE  MEASUREMENT

The particulate sulfate materials discharge was quantified  by
analysis of EPA Method 5 samples.  However,  a large portion of
                               42

-------
                                                          TABLE 3

                                            COMPOSITIONAL ANALYSIS OF  PARTTCULATE  EMISSIONS
co
            Date
            Unit 1

            9-18
            9-19*
            9-19
            9-19
            9-20
            9-20*
            9-20
            9-29
            9-29
            9-29
            9-30
            10-01
            10-01
            Unit 2

            9-21
            9-21
            9-22*
            9-22
            9-23
            9-23
            9-23*
            9-24
            9-24
            9-24*
            9-25
            9-26*
            9-26
            9-26
            9-2V
            9-27
            9-28
                      Time**
1430
1040
1240
1515
1005
1210
1430
1110
1305
1500
1045
1015
1200
1300
1449
0955
1400
0951
1155
1416
0945
1130
1340
0950
0950
1155
U40
0940
1145
0950
Na
*_
2.95
2.45
2.40
1.85
1.77
2.38
1.70
2.16
2.96
2.29
2.68
3.94
4.14
3.27
3.14
3.39
3.58
4.63
6.27
5.28
6.86
7.44
7.60
4.75
3.17
4.46
4.38
7.59
5.22
3.86
K
%
.02
.04
.02
0.0
0.0
.02
.01
.02
.04
.02
.04
.03
.04
.18
.17
.14
.16
.20
. 33
.26
.31
. 42
. 33
.33
.12
. 22
.25
. 73
.29
.12
Mg
%_
1.91
4.70
3.11
2. 34
2.09
4.93
2.27
1.05
1.25
1.06
1.70
2.29
2.42
2.88
2.86
4.87
3. 18
2.93
3.64
3.71
2.83
4.08
4.78
3.45
4.60
2.27
2.64
2.76
1.92
1. 54
Ca
%_
.146
0.0
0.0
0.0
0.0
.033
0.0
0.0
0.0
0.0
0.0
0.0
0.0
1.33
1.43
.76
1.47
1. 75
3.38
2.38
3.28
4.78
2.85
1.93
.19
1.04
1.98
2.15
0.0
0.0
Ni
%
1.84
1.47
1.14
.92
.93
.99
1.02
.927
1.27
.91
.99
1.13
1.27
1.13
1.00
1.59
1.24
1.13
1.29
1.39
1.11
1.08
1.61
1.31
1.47
1. 33
1.05
1.11
1.16
1.25
Mn
%
.03
.01
.05
.02
.02
.02
.01
.02
.02
.01
.02
.03
.03
.04
.03
.04
.02
.02
.02
.02
.02
.02
.02
.02
.03
.01
.01
.01
.01
.02
Fe
%
. 83
.69
. 33
.29
. 30
.60
1.25
.24
.12
.09
.47
.36
.18
.49
.29
.29
. 38
. 39
.59
.40
.28
.18
.24
.42
.29
.34
.18
. 30
.17
. 25
V
%
3.65
4.92
4.24
3.68
3.17
4.10
3.15
3.46
4. 32
3.65
4. 36
4.66
5.15
4.93
4.42
7.10
5.33
5.26
5.60
5.95
5. 32
4.94
7.83
5.85
8.24
6.06
4.57
5. 36
5.01
4.42
Cl
%
.21
.23
. 36
.19
.24
.18
.20
.03
.03
.03
.68
.46
.49
2.39
2.03
2.12
3.03
2.98
5.19
3.45
4.22
6.00
4. 13
3. 97
1.00
2.53
2.72
3. 31
.45
.41
S04
%
45.1
33.7
27.7
42.2
47.8
48.2
43.6
60.6
56.1
50.6
46.9
53.9
62.6
36.3
40.6
44.0
56.1
53.2
51.5
53.0
52.2
56. 3
50. 1
53.2
46.1
51.4
54. 5
48.8
43. 5
46.6
N
as NH4
%
1.98
1.62
.71
1.38
.80
.45
.38
.55
.68
.73
.48
.57
1.13
. 72
. 74
.67
.77
2.35
1. 80
.90
1.09
.68
.41
.63
.21
.57
.56
.52
.43
1. 27
N
as NO 3
%
.05
.05
.02
.02
.03
.05
.04
.02
.02
.01
.04
.02
0.0
.04
.03
.06
.07
.04
.06
.07
.05
.04
.07
.13
.04
.04
.02
.04
.06
.04
             *   Soot Blow  Test

             **  EOT

-------
                                           TABLE 3




                             COMPOSITIONAL ANALYSIS OF  PARTICULATE EMISSIONS
Date Time
Unit 3
10-11
10-11
10-11
10-12
10-13*
10-13
10-13
10-15
Unit 4
10-03
10-03
10-03
10-04
10-05
10-05
10-05*
10-06
10-06
10-06
10-07
10-07
10-08
10-08
10-09
10-09

1002
1150
1335
1010
0930
1125
1315
1005

1010
1209
1410
1325
0940
1125
1330
0950
1145
1340
1025
1240
1105
1304
1055
1440
Na
%_
2.24
2.43
2.06
2.17
2.45
2.26
2.33
4.32
4.87
4.34
4.34
3.89
3.07
3.16
3.09
3.04
2.84
3.60
3.78
3.44
4.10
4.56
3.83
2.68
K
%
.02
.02
.02
.02
.04
.02
.02
.03
.06
.15
.06
.04
.11
.03
.07
.02
.03
.03
.03
.04
.04
.05
.04
.04
Mq
%_
4.01
3.94
2.41
4.00
5.07
4.43
4.53
2.88
3.61
4.03
2.56
3.68
3.16
2.21
4.20
3.55
3.97
3.57
3.22
3.46
3.28
2.18
2.47
5.37
Ca
%_
0.0
0.0
0.0
0.0
0.0
.03
.02
.03
0.0
0.0
0.0
0.0
.07
0.0
0.0
0.0
0.0
0.0
0.0
0.0
.03
.05
0.0
0.0
Ni
L_
1.37
1.41
1.32
1.20
1.31
1.36
1.30
1.56
1.82
1.73
1.64
1.56
1. 37
1.33
1.61
1.55
1.68
1.59
1.52
1.40
1.12
1.20
1.54
1.95
Mn
%_
.02
.03
.0-2
.02
.03
.03
.03
.05
.02
.02
.02
.02
.02
.02
.02
.02
.01
.02
.02
.02
.03
.04
.03
.02
Fe
%
.35
.30
.27
.29
.43
.32
.34
.35
.44
. 31
.23
. 36
.17
.22
.24
.20
.29
.22
1.12
.19
.18
.27
.27
.34
V
%
5.60
5.82
5.00
4.99
6.07
5.23
5.17
6.62
7.33
6. 77
5.44
6.38
5.33
4.88
5.97
6.17
6.40
6.01
5.16
6.77
5.26
5. 39
6.77
7.96
Cl
%
.24
.29
.39
.36
.45
.27
. 32
.76
.07
.09
.11
.36
.27
.07
.04
.04
.10
.09
.28
.51
.72
.85
.47
. 37
SO4
% 	
36.0
37.8
34.0
29.0
34.4
26.6
32.3
60.6
48.8
53.2
61.7
46.7
50.7
50.2
40.3
47.0
41.4
43.5
51.2
52.7
66. 7
67.6
43. 3
45.3
N
as Nil 4
.27
.21
.21
.22
.25
.32
.27
.90
.55
.32
.62
.55
.52
.81
.39
.44
.33
.44
.81
.21
1.03
.81
.99
.41
N
as NO
.09
.05
.10
.07
.08
.08
.13
.05
.09
.08
.03
.04
.04
.05
.05
.08
.08
.07
.06
.04
.16
.07
.05
.11
*   Soot Blow Test




**  EOT

-------
                                                    TABLE 4
                                   COMBUSTION PARAMETERS  AND PARTICLE SIZE TEST RESULTS
               Date  Time Oil Flow Fuel Boiler Stack Stack Stage Stage  Stage  Stage  Stage  Stage  Stage  Stage  Back
,01


Unit 1
9-18*1636
9-19*1202
9-19 1523
9-20 1150
9-20 1350
9-20 1615
9-29 1310
9-30 1128
10-01 1053
Unit 2
9-21*1246
9-21 1521
9-22*1000
9-22 1450
9-22 1554
9-23*1412
9-24 1035
9-24*1313
9-25 1030
9-26*1030
9-26*1145
9-26 1245
9-27 1028
9-27 1140
9-28 1008
gal/hr

S-%

0-,-%
£.
O0-%
z.
T.-°C

o-%

1 -%

2 -%

3 -*

4 -%

5 -%

6 -%

7 -%
1
Up
C1 -I 1 4-e* v
%
5900
5900
6100
6100
6150
6100
3500
3400
3400

6150
6100
6050
6150
6000
3100
3150
3100
6100
6100
6150
6100
5600
5600
4300
1.95
1.98
1.98
1.78
1.78
1.78
1.97
2.05
1. 80

1.70
1.70
1.75
1.75
1.75
1.90
1.50
1.50
1.97
1.95
2.00
2.03
2.05
2.05
2.25
3.1
3.1
2.6
2.7
2.5
2.4
3.6
3.7
3.2

2.2
2.0
2.3
2.2
2. 3
4.5
3.6
3.8
2.2
2.0
2.0
2.0
2.2
2.3
3.8
5.8
5.6
5.4
6.2
5.7
5.8
7.2
7.7
7.6

5.5
5.6
5.4
5. 3
5. 3
8.2
7.6
7.4
6.3
6. 1
6.0
6.0
6.4
6.4
7.4
161
161
160
160
159
159
159
152
150

188
188
179
177
177
J53
150
157
177
177
177
180
166
166
158
38.43
26.67
9.06
9.56
4.16
11.40
3.78
2.43
8J12

10.95
10.34
13.06
9.05
10.70
8.28
6.12
7.22
10.23
13.16
14.48
10.00
8.39
7.97
9.66
10.06
13.45
7.37
9.60
4.56
14. 34
8.05
2.63
7. 11

10.30
12.52
13.58
10.71
9.67
10.80
6.08
4. 11
10.23
8.70
14.95
10. 38
9.79
13.19
11.32
8.14
6.00
10.28
11.38
5.91
10.97
11.22
2.20
8.51

9.98
12.34
14.28
13.08
11.19
14.25
7.31
9.65
13.47
7.99
13.11
9.91
11.04
12.26
11.84
7.22
7.74
8.98
9.50
5.57
9.23
11.25
5.20
7. 39

11.17
10.47
11.13
9.83
8.60
9.66
5.02
9.40
10.01
9.36
11. 50
10.11
8.15
10.60
9.47
7.37
2.48
8.67
10.26
8.06
8.74
6.22
8.64
8.26

9.29
10.68
12. 18
8.80
11.13
11.00
6.43
8.80
10.31
12.70
11.70
10.03
7.18
9.43
9.05
8.55
8.21
5.83
8.95
10.93
6.16
16.70
7.04
9.15

9.40
7.84
8.10
7.14
7.27
7.99
8.19
11.91
9.15
14.65
8.69
9.95
7.18
7.93
8.60
5.35
5.69
5.59
6.60
7.01
4.43
10.17
4.30
6.24

6.74
5. 12
6.24
6.26
4.87
5.42
8.28
3.75
7.10
10.63
4.92
7.56
5.85
4.37
5. 32
3.31
9.67
6.23
4.57
8.10
2.35
7.33
8.60
7.16

5.46
4.59
4.95
4.43
3.89
3.50
8.94
7.26
5.27
6.32
4.09
6.56
3.98
3.97
3. 96
11.58
20.10
37.98
29.59
45.71
32.37
25.29
58.95
38.06

26.71
26.10
16.47
30.71
32.70
29.09
43.64
37.90
24.23
16.48
16.56
25.49
38.44
30.27
30.78
               *  Soot  B.low  Test
               **  EOT

-------
                                  TABLE  4
                COMBUSTION PARAMETERS AND PARTICLE SIZE TEST RESULTS  (CONTD.)


Unit 3
10-11 1055
10-11 1208
10-11 1320
10-12 1021
Unit 4
10-03*1302
10-04*1440
10-05 1045
10-06 0955
10-06 1110
10-06*1230
10-07 1115
10-07 1235
10-08 1105
10-08 1335
10-09 1100
10-09 1440
gal/hr


6300
6300
6300
6100

6400
6200
5600
6100
6050
6050
6200
6100
3200
3200
5950
6600
S-%


2.10
2.10
2. 10
2.28

2.10
2.20
1.50
1.40
1.40
1.40
1.40
1.40
1.70
1.70
1.96
1.96
O0-%
£

2. 1
2.1
2.3
2.6

2.5
2.0
2.7
1.9
1.6
1.7
2.3
2.4
5.0
5.0
3.5
3.2
o2-%
£,

6.3
6.0
6.1
6.2

6.7
6.6
6.4
6.6
6.3
6.6
5.9
6.3
9.6
9.7
6.4
6.4
T.- C


145
148
149
146

156
152
154
157
157
160
166
160
135
135
157
157
0-%


25.62
22.01
22.68
31.85

11.39
11.66
16.19
19.23
16.93
20.73
10.71
13.90
6.15
4.48
13.31
13.70
1 -%


10.59
9.96
11.49
10.72

10.74
9.03
13.81
11.77
10.75
11.94
8.29
11.11
5.21
5.36
8.91
9.86
2 -%


6.23
7.71
7.56
8.45

11.12
10.36
12.16
7.56
11.71
9.64
2.64
10.92
5.96
5.97
8.38
9.60
3 _%


6.10
8.87
6.82
6.78

8.53
7.21
4.00
7.31
9.39
7.08
8.46
5.60
4.11
5.16
6.72
9.45
4 -%


6.51
6.33
9.38
7.90

10.90
9.25
3.85
5.52
11.01
7.40
9.72
9.61
8.68
8.49
8.05
10.30
5 -%


6.04
6.90
7.49
6.18

9.15
8.10
3.94
7.08
6.29
7.50
9.88
7.24
10.27
9.40
10. 13
10.07
6 -%


3.53
3.81
3.71
2.86

6.43
5.05
3.43
2.75
4.25
4.35
7.98
5.25
8.16
5.94
7.29
6.70
7 -%


5.02
2.93
3.72
3.26

5.71
3.86
2.14
3.10
2.71
2.87
7.58
2.88
7.48
10.39
6.47
5.26
Up
Pi 1 f- O T"
f -L j- Lt: -L

30.35
31.49
27.15
21.99

26.03
35.48
40.48
35.70
26.96
28.49
34.74
33.49
43.98
44.81
30.74
25.06
* Soot Blow Test
** EOT

-------
the sulfate materials  leaving  the  stack  can  be  in  the form of
gaseous sulfuric acid.  Total  gaseous  plus  particulate sulfate
emissions were determined  using  a  modification  of  EPA Sulfur
Dioxide Test Method 6  (40  CFR  60 App.  A).   The  flue  gas  was
extracted through a heated  glass-lined probe normal  to the flue
gas flow; particulate  matter was removed  from the  sample stream
with a quartz wool plug prior  to flowing  into the  probe.  Gas-
eous sulfate was collected  by  bubbling the  sample  gas through
an 80% solution of isopropyl alcohol  and  distilled water in a
midget bubbler.  The aqueous solution  absorbed  the gaseous sul-
fate, while sulfur dioxide  passed  through  unchanged.   A  3%
solution of hydrogen peroxide  and  distilled  water  in  a series
of two midget impingers oxidized and  absorbed the  sulfur diox-
ide.  Both solutions were  immersed in  an  ice bath  to  enhance
condensation and collection.   The  probe  filter,  probe washings,
bubbler exit plug filter,  and  hydrogen peroxide  absorbing solu-
tion were analyzed separately  for  total  sulfate  using the pub-
lished barium-thorin titration with pretreatment of  the  plug
filter and probe washings  for  cation  removal.   The analysis
procedure is described  in  EPA  Sulfur  Dioxide Test  Method 6 (40
CFR 60 App. A).

Sulfur Oxides Test Results

Sulfur oxides concentration are  shown  on Table  5;  combustion
parameters and sulfur  oxides test  results  are shown  on Table
6.  Total sulfate concentration  ranged from  22  to  55  ppm and
the emission rate ranged from  22 to 82 kg/hr.   Mean  values were
37 ppm and 51 kg/hr.   Sulfur dioxide  concentration ranged from
700 to 1100 ppm with boiler oxygen concentrations  slightly less
than 2% to greater than 5%  and fuel sulfur  content from  1.4% to
2.2%.  Emission rate of sulfur dioxide ranged from 500 kg/hr.
to 1200 kg/hr; mean emission concentration  was  938 ppm and mean
emission rate was 856  kg/hr.
                                47

-------
                            TABLE
                           SO  TEST RESULTS
                             x
Date

Unit 1
9-19
9-20
9-20
9-20
9-29
9-29
9-29
9-30
10-01
10-01
Unit 2
9-21
9-21
9-21
9-22
9-22
9-22
9-23
9-23
9-24
9-24
9-24
9-25
9-26
9-26
9-26
9-27
9-27
Unit 3
10-11
10-12
10-13
10-13
10-15
Time *


1040
1005
1210
1430
1110
1305
1500
1045
1015
1200

1040
1249
1441
0941
1422
1539
1220
1400
0930
1050
1215
0949
0940
1119
1256
0929
1108

1154
0946
1049
1223
0950
SO
ppm/v

918.0
894.7
948.4
944.6
10 &8. 4
1032.1
1068.8
927.0
902.0
389.3

933.6
950.0
931.4
943.9
943.9
951.8
944.9
834.3
887.1
909.8
911.7
979.3
954.7
932.5
944.5
926.1
983.9

1068.2
1099.8
1155.7
1125.4
953.3
SO^
mg/flm

2435.2
2372.1
2512.9
2505.6
2869.9
2732.9
2840.6
2459.8
2389.6
2360.7

2476.7
2517.6
2472.7
2522.6
2509.2
2527.9
2502.2
2214.1
2355.8
2397.2
2413.0
2597.2
2529.8
2480.3
2509 .6
2459.7
2611.3

2834.1
2915.1
3068.6
2937.1
2533.2
T-SO(
ppm/v

26.696
42.790
44.267
44.198
55.309
44.023
49 .615
32.121
33.754
32.787

29.736
29.425
31.928
43.256
29.354
25.767
35.979
28.248
24.648
29.003
23.825
36.329
37.794
41.874
40.969
38.348
35.849

36.141
43.440
42.863
42.787
62.535
                                             106.1
                                             182.7
                                             175.7
                                             175.6
                                             219.9
                                             131.7
                                             138.3
                                             127.7
                                             133.9
                                             130.4
                                             113 .2
                                             116.9
                                             127.1
                                             171.9
                                             117.9
                                             102.5
                                             144.3
                                             117.7
                                             101.4
                                             114.5
                                              94.6
                                             144.3
                                             150.0
                                             166.8
                                             163.0
                                             152.5
                                             142.5
                                             143.6
                                             172.4
                                             170.4
                                             170.1
                                             245.9
S04/S0
v/v
2.83
4.56
4.46
4.47
4.84
4.09
4.44
3.33
3.61
3.56
3.09
3.00
3.31
4.36
3.02
2.64
3.67
3.24
2.70
3.09
2.55
3.58
3.31
4.30
4.16
3.93
3.52
3.27
3.80
3.53
3.66
6.16
S°4/SO
w/w
4.18
6.69
6.54
6.56
7.03
6.01
6.51
4.94
5.31
5.24
4.56
4 .44
4.39
6.40
4 .46
3.90
5.40
4.33
4.00
4.56
3.77
5.27
5.61
6.31
6 .11
5.85
5.18
4.83
5.83
5.26
5.40
8.96
SDT
 Total Water  Soluble  Sulfate
                                    48

-------
                                TABLE   5
                         SO  TEST RESULTS  (CONTD.)
                           X
Date   Time *
       1150
       0950
       1122
       1253
       0950
       1127
       1257
       0957
       1131
       1313
       1029
       1202
       1026
       1421
10-03
10-05
10-05
10-05
10-06
10-06
10-06
10-07
10-07
10-07
10-08
10-08
10-09
10-09
so
2
pm/v
979
855
841
837
884
975
891
962
939
913
701
742
823
934
.6
. 4
. 7
. 4
.6
. 3
.9
.2
.3
.3
.8
.4
.3
.2
SO
2,
mg/Nm"1
2600
2272
2226
2221
2348
2590
2367
2554
2490
2429
1860
1971
2186
2485
.4
.0
.9
.6
.2
.9
.8
.7
.3
.2
.4
.3
.5
.8
**
T-S04
ppm/v
35.
44.
30.
35.
33.
43.
35.
41.
41.
35.
30.
22.
36.
47.
576
794
265
558
762
498
579
003
624
098
407
331
467
938
                                                T-SO,
141.4
178.2
119.9
141.3
134.2
173.1
141.5
163.0
165.3
139 .8
120.7
 88.8
145.0
191.1
                                                          SO
                                                            4/SC)
                                                                     SO
                                                           v/v
  50
  98
3.47
4.07
3.68
4.27
3.34
4.09
4.24
3.70
4.15
2.92
4.24
4.88
                                                                       4/SO.
                                                                       w/w
5.17
7.28
5.12
  99
  41
6.27
5.65
6.01
6.23
5.45
6.10
4. 32
6.23
7. 15
* EOT
** Total Water Soluble Sulfate
                                     49

-------
                         TABLE
           COMBUSTION PARAMETERS AND SO  TEST RESULTS
Date


Unit 1
9-19
9-20
9-20
9-20
9-29
9-29
9-29
9-30
10-01
10-01
Unit 2
9-21
9-21
9-21
9-22
9-22
9-22
9-23
9-23
9-24
9-24
9-24
9-25
9-26
9-26
9-26
9-27
9-27
Unit 3
10-11
10-12
10-13
10-13
Time*



1040
1005
1210
1430
1110
1305
1500
1045
1015
1200

1040
1249
1441
0941
1422
1539
1220
1400
0930
1050
1215
0949
0940
1119
1256
0929
1108

1154
0946
1049
1223
Oil Flow
gal/hr


6000
5800
6100
6200
540.0
5400
5400
3400
3400
3400 -

6200
6150
6100
6100
6150
5800
3000
3100
3300
3200
3100
6100
6000
6200
6100
5600
5600

6300
6200
6200
6100
Fuel
S -%


1.98
1.78
1.78
1.78
2.00
2.00
2.00
2.05
1.80
1.80

1.70
1.70
1.70
1.75
1.75
1.75
1.90
1.90
1.50
1.50
1.50
1.97
1.95
1.95
1.95
2.05
2.05

2.10
2.28
2.20
2.20
Boiler
_0


3
3
2
2
3
3
3
3
3
3

2
2
2
2
2
2
4
4
3
•J
3
2
2
2
1
2
2

2
2
2
2
2- %


.0
.0
.8
.5
.8
.8
.8
.6
.3
.2

.4
.2
.0
.2
.2
.3
.6
.5
.6
.6
.5
. 1
.0
.0
.9
.2
.2

.1
.1
.1
.0
Stack
o2-%


5.6
5.6
5.7
5.8
7.1
7.2
7.2
7.7
7.6
7. 7

5.5
5.6
5.6
5.4
5.3
5.3
3.3
8.2
7.6
7 .8
7.4
6.3
6.1
6.0
5.9
6.3
6.4

6.0
6.4
6.2
6.0
Stack.
Temp-


166
160
160
159
163
159
161
154
152
150

183
188
188
179
177
177
143
153
150
149
157
177
170
177
185
165
166

148
146
143
146
o S02
°C ppm
V

918.0
894.7
948 .4
944.6
1088.4
1032.1
1068.8
927.0
902.0
889 .3

933.6
950.0
931.4
943.9
943.9
951.8
944.9
834.3
887.1
909.8
911.7
979.3
954.7
932.5
944.5
926.1
983.9

1068 .2
1099 .8
1155.7
1125.4
SO
kg/hr


942.4
840.9
888.5
924.4
1081.0
955.8
1071.2
549.5
540.4
529.2

916.1
952.3
935.3
954.1
989.6
997.0
616.4
536.0
597.3
589.4
581.0
997.9
956.3
993.8
954.0
887.4
968.3

1071,6
1101.4
1220 .7
1101.2
* it
so4
ppm
V

26.696
42.790
44.267
44.198
55.309
44.023
49.615
32.121
33.754
32.787

29.736
29.425
31.928
43.256
29.354
25.767
35.979
23.248
24.648
29.003
23.325
36 .329
37.794
41.874
40 .969
38.348
35.849

36.141
43. 440
42.863
42.787
**
SO
kg/fir


41.1
64.8
62.1
64.8
82.3
46.1
71.0
28.5
30.3
29.2

43.7
44.2
48.1
65.0
46.5
40.4
35.7
28.5
25.7
28.1
22.7
55.3
56.7
66 .3
62.0
55.0
52.8

54.3
65.2
67.8
62.7
EDT
*  Total Water Soluble Sulfate
                                    5Q

-------
                           TABLE    6
        COMBUSTION PARAMETERS AND SOX TEST RESULTS  (CONTD.)
Date

Unit 4
10-03
10-05
10-05
10-05
10-06
10-06
10-06
10-07
10-07
10-07
10-08
10-08
10-09
10-09
Time*


1150
0950
1122
1253
0950
1127
1257
0957
1131
1313
1029
1202
1026
1421
Oil Flow
gal/hr

6400
6000
5000
6300
6100
6100
6100
6200
6200
6000
3200
3200
5900
6400
Fuel
S- %

2.10
1.50
1.50
1.50
1.40
1.40
1.40
1.40
1.40
1.58
1.70
1.70
1.96
1.77
Boiler
0 -%
£.

2.7
2.1
3.0
2.0
2.0
1.9
1.8
2.0
2.3
2.4
5-5
5-3
3.2
3.1
                                     Stack  Stack,  SO-
                                                          SO
                                                                       SO*
°2
£,
6.
6.
7.
6.
6.
6.
6.
5.
6 .
6 .
9.
9.
6.
6.
-%

4
2
2
4
6
3
6
9
3
3
6
7
4
4
Temp-

160
157
150
155
157
158
160
166
161
161
131
133
157
160
C ppm

V
979
855
841
837
884
975
891
962
939
913
701
742
823
934


.6
.4
.7
.4
.6
.3
.9
.2
. 3
.3
.3
. 4
.3
.2
kg/fi

1063
808
680
812
827
957
853
973
927
904
494
515
814
975
r

.8
.7
.0
.6
.9
.4
.1
.2
. 4
.7
.0
.6
.2
.1
ppm k


35
44
30
35
33
43
35
41
41
35
30
22
36
47


.576
.794
.265
.558
.762
.498
.579
.003
.624
.098
.407
.331
.467
.938
g/Rr

57
63
36
51
47
64
51
62
61
52
32
23
54
75

.9
.4
.6
.7
.3
.0
.0
. 1
.6
.1
.1
.2
.0
.0
* EOT
** Total Water Soluble Sulfate
                                     51

-------
Sulfur dioxide and total sulfate emission  models  were  developed
and can be found in Section 4.

SULFUR OXIDES CHARACTERIZATION

A sulfate characterization was performed by  EPA personnel  dur-
ing the field sampling, using a controlled condensation  sampl-
ing system.  The system consisted of a  high-temperature  quartz
probe, followed by a quartz filter.  The filter was  enclosed
within a custom made heating mantle, kept  at 260°C or  greater,
and had a coarse quartz frit for support of  the filtering  pad.
Following filtration,  the gaseous sulfuric acid was  converted
to the aerosol form in a temperature-controlled Goksoyr-Ross
condensation coil, maintained at 60°C.  Sampling  rate  was  main-
tained at 10 1/min. or greater  (Cheney  and Homolya,  1979).   The
acid aerosol was collected in a Greenburg-Smith impinger con-
taining an 80% solution of isopropyl alcohol and  water.

Following this the sulfur dioxide was collected in an  impinger
containing 3% hydrogen peroxide and water.   The recovered  sam-
ples were analyzed using the barium-thorin procedure described
in EPA Sulfur Dioxide  Test Method 6.

Characterization Results

The results of the sulfate characterization  using controlled
condensation are shown on Table 7.  The percent of H2SO4 ranged
from 63.1% to 85.3% with a mean value of 73.5% of the  total
sulfate.  Total sulfate measurements obtained using  the  con-
trolled condensation technique averaged 19.5 ppm, which  was
significantly below the 37 ppm average  of  the measurements made
with modified Method 6.  The tests were performed under  similar
conditions and at the  same point in the flue gas  flow stream,
therefore it is possible that there is  an  inherent  interference
in comparing the test  methods.  The isopropanol used in  the
                                52

-------
                                                       TABLE    7



                                             SULFATE CHARACTERIZATION TEST RESULTS

                                               (CONTROLLED CONDENSATION SYSTEM)
Date
Unit 1
9/19
9/19
9/19
9/20
9/20
9/20
*
Time
1139
1258
1350
0908
1033
1132
Oil Flow
gal/hr
6100
6000
6100
5900
6000
6100
Fuel
S-%
1.98
1.98
1.98
1.78
1.78
1.78
Boiler
o2 - %
3.1
3.1
2.6
3.0
3.0
2.7
so2
ppm
865
872
934
859
770
876
so4
ppm
20.0
23.5
21.0
23.9
16.8
19.9
H2S04
% of
so4
73.6
74.8
63.1
73.3
76.3
85.3
01
U)
Unit 2

9/21
9/21
9/21
9/21
9/21
9/22
9/22
9/22
9/22

Unit 4

10/5
10/5
10/5
10/5
10/6
10/6
10/6
10/6
10/6
1005
1107
1205
1312
1407
0915
1011
1103
1202
                           1010
                           1135
                           1239
                           1322
                           0817
                           0911
                           0952
                           1055
                           1154
6200
6150
6150
6150
6100
6100
6050
6000
5650
            6000
            5000
            5000
            6300
            5900
            6000
            6100
            6100
            6000
  70
  70
  70
  70
  70
  75
1.75
1.75
1.75
            1.50
            1.50
            1.50
            1.50
            1.40
            1.40
            1.40
            1.40
            1.40
2.4
2.4
2.2
2.2
2.0
2.1
2.3
2.3
2.3
                                                                 2.1
              3.0
              3.0
              2.1
              2.4
              2.1
              1.9
              2.2
              1.6
897
928
896
916
813
927
910
912
904
26.9
25.5
23.6
25.2
19.0
19.7
17.5
20.4
17.0
71.7
78.4
77.3
76.7
75.1
77.2
70.4
70.0
70.8
896
807
868
901
867
861
911
885
913
16
12
18
18
15
20
16
16
14
.3
.7
.5
.5
.1
.6
.6
.8
.1
69
67
77
67
71
77
77
65
76
.1
.9
.5
.4
.5
.1
.8
.1
.2
              EOT

-------
modified Method 6 tests was  checked  for oxidants and found to
be free of oxidants.  Quartz wool  was  used to filter the sample
gas so that an SC>2—glass  wool  reaction is not possible.  A
possible explanation of the  discrepancy lies in the sampling
rate; the controlled condensation  system uses a large diameter
probe and a 10 1/min. rate while  the modified Method 6 test
uses a small diameter probe  and a  0.4  1/min. sampling rate.
Nozzles were not used and  the samples  were not extracted iso-
kinetically, therefore sampling velocity may have affected the
influence of particles and particulate sulfate, thereby modify-
ing the total sulfate measurements.

PARTICLE SIZE DISTRIBUTION

In-situ cascade impactors  were  used  to obtain segregated sam-
ples of particulate matter within  specific size ranges.  The
impactors each contained eight  fractionating jet plates in
series, with collection substrates below them.  The substrates
were composed of glass fiber material  and served as impingement
surfaces for the particles exiting through the jet directly
above.  Each jet plate had a design  such that a particle with
unit density and a diameter  equivalent to the design cut point
(DSQ) impinged on the substrate below  it with a 50% probabil-
ity.

Smaller particles are able to follow  the gas streamlines
through the successive jets  until  the  jet with the appropriate
size is reached.  Particles  below  about .5 urn are collected on
the backup glass fiber filter.  The  filter and substrates are
analyzed for net particulate material  and presented as the per-
centage of particulate per stage.   The filters and substrates
were transmitted to EPA for  further  analysis.
                               54

-------
Particle Size Test Results

The results of the individual  particle  size determinations are
shown in Table 8.  The  tests were  also  grouped  by unit,  (high
or low) load, and  (normal or soot  blow)  operating conditions.
Each grouping is represented on  a  graph  of  cumulative particle
size less than the D5Q  cut  point on  the  ordinate and DSQ Par-
ticle size on the abscissa.  The maximum, minimum,  and mean
(average of all  tests  in that  grouping)  are plotted in Figures
4 through 13.  The mass median diameter  (or size where 50% of
the weight is greater  and 50%  is smaller) are  summarized on
Table 9.  Median particle size  is  inversely proportional to
load and is greater  during  soot  blow than during normal  opera-
tion.

COMBUSTION RECORDS

The chart recordings of several  important combustion parameters
were reduced to  hourly  summaries for use in characterizing the
operating schedule of  the boilers.   These parameters are steam
flow, oil flow,  fuel sulfur content, boiler gas-oxygen content,
air heater temperatures, and oil/additive ratio.  The average
daily values for each  of the boilers are presented in Tables 10
through 13.  A summary  of the  weekly fuel oil  analysis is pre-
sented on Table  14 and  the  summary of weekly additive analysis
is shown on Table  15.

EMISSION PREDICTION  MODELS

Methodology

Quantitative and qualitative experiments were  performed  daily
on the source-emitted  materials  in concert  with the valuation
of ground-level  concentrations and meteorological factors.
Samples of gaseous and  particulate materials were extracted
                               55

-------
                                       TABLE
                     COMBUSTION PARAMETERS AND  PARTICLE  SIZE  TEST  RESULTS


Unit 1
9-18*1636
9-19*1202
9-19 1523
9-20 1150
9-20 1350
9-20 1615
9-29 1310
9-30 1128
10-01 1053
Unit 2
9-21*1246
9-21 1521
9-22*1000
9-22 1450
9-22 1554
9-23*1412
9-24 1035
9-24*1313
9-25 1030
9-26*1030
9-26*1145
9-26 1245
9-27 1028
9-27 1140
9-28 1008
gal/hr

S-%

0,,-%

Op-% T.- C 0-%



I -%

2 -%

3 -%

4 -%

5 -%

<"> -%

7 -%
t
Up
;' 4 1 4- rt v
%
5900
5900
6100
6100
6150
6100
3500
3400
3400

6150
6100
6050
6150
6000
3100
3150
3100
6100
6100
6150
6100
5600
5600
4300
1.95
1.98
1.98
1.78
1.78
1.78
1.97
2.05
1.80

1.70
1.70
1.75
1.75
1.75
1.90
1.50
1.50
1.97
1-95
2.00
2.03
2.05
2.05
2.25
3.1
3.1
2.6
2.7
2.5
2.4
3.6
3.7
3.2

2.2
2.0
2.3
2.2
2.3
4.5
3.6
3.8
2.2
2.0
2.0
2.0
2.2
2. 3
3.8
5.8
5.6
5.4
6. 2
5.7
5.8
7.2
7. 7
7.6

5.5
5.6
5.4
5.3
5.3
8.2
7.6
7.4
6.3
6.1
6.0
6.0
6.4
6.4
7.4
161
161
160
160
159
159
159
152
150

188
188
179
177
177
153
150
157
177
177
177
180
166
166
158
38.43
26.67
9.06
9.56
4. 16
11.40
3.78
2.43
8J12

10.95
10.34
13.06
9.05
10.70
8.28
6. 12
7.22
10.23
13.16
14.48
10.00
8.39
7.97
9.66
10.06
13.45
7.37
9.60
4.56
14.34
8.05
2.63
7. 11

10. 30
12.52
13.58
10.71
9.67
10. 80
6.08
4. 11
10.23
8.70
14.95
10.38
9.79
13. 19
11. 32
8.14
6.00
10.28
11. 38
5.91
10.97
11.22
2.20
8.51

9.98
12.34
14.28
13.08
11.19
14.25
7.31
9.65
13.47
7.99
13.11
9.91
11.04
12.26
11.84
7.22
7.74
8.98
9.50
5.57
9.23
11.25
5.20
7.39

11.17
10.47
11.13
9.83
8.60
9.66
5.02
9.40
10.01
9.36
11.50
10.11
8.15
10.60
9.47
7.37
2.48
8.67
10.26
8.06
8.74
6. 22
8.64
8.26

9.29
10.68
12. 18
8.80
11.13
11.00
6.43
8.80
10.31
12.70
11.70
10.03
7.18
9.43
9.05
8.55
8.21
5.83
8.95
10.93
6.16
16.70
7.04
9.15

9.40
7.84
8.10
7.14
7.27
7.99
8.19
11.91
9.15
14.65
8.69
9.95
7.18
7.93
8.60
5.35
5.69
5.59
6.60
7.01
4.43
10. 17
4.30
6.24

6.74
5. 12
6.24
6.26
4.87
5.42
8.28
3.75
7.10
10.63
4.92
7.56
5.85
4.37
5.32
3.31
9.67
6.23
4.57
8.10
2. 35
7. 33
8.60
7.16

5.46
4.59
4.95
4.43
3.89
3.50
8.94
7.26
5.27
6.32
4.09
6.56
3.98
3.97
3.96
11.58
20. 10
37.98
29.59
45.71
32 .37
25.29
58.95
38. OG

26.71
26.10
16.47
30.71
32.70
29.09
43.64
37.90
24 .23
16.48
16.56
25.49
38.44
30.27
30.78
* Soot Blow Test
** EOT

-------
                                                    TABLE
                             COMBUSTION PARAMETERS AND PARTICLE  SIZE  TEST RESULTS (CONTD.)
UI
             Date  Time Oil Flow Fuel Boiler Stack Stack Stage  Stage  Stage  Stage  Stage Stage Stage Stage Back
                         gal/hr  S-%   Q.,-%   O,-%T.-C  0-%   1-%   2-%   3-%   4-%   5-%   f, -%   7-%   Up
- ^; i *-„,
Unit 3
10-11 1055
10-11 1208
10-11 1320
10-12 1021
Unit 4
10-03*1302
10-04*1440
10-05 1045
10-06 0955
10-06 1110
10-06*1230
10-07 1115
10-07 1235
10-08 1105
10-08 1335
10-09 1100
10-09 1440

6300
6300
6300
6100

6400
6200
5600
6100
6050
6050
6200
6100
3200
3200
5950
6600

2.
2.
2.
2.

2.
2.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.

10
10
10
28

10
20
50
40
40
40
40
40
70
70
96
96

2. 1
2. 1
2.3
2.6

2.5
2.0
2.7
1.9
1.6
1.7
2. 3
2.4
5.0
5.0
3.5
3.2

6.3
6.0
6.1
6.2

6.7
6.6
6.4
6.6
6. 3
6.6
5.9
6.3
9.6
9.7
6.4
6.4

145
148
149
146

156
152
154
157
157
160
166
160
135
135
157
157

25.
22.
22.
31.

11.
11.
16.
19.
16.
20.
10.
13.
6.
4.
13.
13.

62
01
68
85

39
66
19
23
93
73
71
90
15
48
31
70

10. 59
9.96
11.49
10.72

10.74
9.03
13.81
11.77
10.75
11.94
8.29
11.11
5.21
5. 36
8.91
9.86

6.
7.
7.
8.

11.
10.
12.
7.
11.
9.
2.
10.
5.
5.
8.
9.

23
71
56
45

12
36
16
56
71
64
64
92
96
97
38
60

6. 10
8.87
6.82
6.78

8.53
7.21
4.00
7.31
9. 39
7.08
8.46
5.60
4. 11
5. 16
6.72
9.45

6.51
6.33
9. 38
7.90

10.90
9.25
3.85
5.52
11.01
7.40
9.72
9.61
8.68
8.49
8.05
10. 30

6.04
6.90
7.49
6. 1R

9.15
8.10
3.94
7.08
6.29
7.50
9.88
7.24
10.27
9.40
10. 13
10.07

3.53
3.81
3.71
2.86

6.43
5.05
3.43
2.75
4.25
4.35
7.98
5.25
8.16
5. 94
7. 29
6.70
l
5.02
2.93
3.72
3. 26

5.71
3. 86
2.14
3.10
2.71
2.87
7.58
2.88
7.48
10.39
6.47
5.26
. -L. J- U'-: L.

30.35
31.49
27. 15
21.99

26.03
35.48
40.48
35. 70
26.96
28.49
34. 74
33.49
43.98
44 .81
30.74
25.06
             * Soot Blow Test
             ** EOT

-------
00
         98

         95

         90-
         80-
 o, 70~
Q
C
j?  60-
H
en  50
en
®  40 -
^  20

3  10
         5

         2
                FIGURE 4  PARTICLE SIZE DISTRIBUTION
               Mean
                              Maximum
                                                           Minimum
                                                                  Unit 1
                                                                  High Load-Normal Operation
                                                                  4 Tests
                      I
                      .5
                          1.0        2.0         5.0
                                                    *
                     Aerodynamic Particle Diamter- D
  I
10.0
  I—
20.0

-------
Ul
         Q

         C
         01
   98-

   95-


   90-




   80-




   70-



   60
en  50
(0
Q)
J  40
            20-
            ID-
                                   FIGURE 5  PARTICLE SIZE DISTRIBUTION
                                                         Minimum
                                                           Unit 1
                                                           High Load-Soot Blow
                                                           2 Tests
                                    I
                                                           l

                                                           5.0
                5         1.0        2.0

                   Aerodynamic Particle Diameter- D
 I

10.0
  I

20.0

-------
O"!
o
      Q
      C
0)
w
      d*>
      0)
      3
      U
98 -
95 -

90 _


80 -


70 _

60
50
40
30 -

20

10

 5
 2
                                FIGURE  6  PARTICLE SIZE DISTRIBUTION
          Mean
                                                          Minimum
                                                             Unit 2
                                                             High Load-Normal Operation
                                                             7  Tests
                       .5
                            I
                            1.0
                                  I
                                 2.0
5.0
                              Aerodynamic Particle  Diameter- D
10.0
  pro
  I
20.0

-------
rt
W
w

-------
ro
   98-

   95-


   90-



   80-



   70-


  W


   50~
S  40-
a)
           o,
0)



(0
iH
3
             30
            20-
                                    FIGURE  8   PARTICLE SIZE DISTRIBUTION
                                                                           Minimum
                                                                                  Mean
                                                                 Unit 3
                                                                 High Load-Normal Operation
                                                                 4  Tests
    1.0        2.0         5.0

Aerodynamic  Particle Diameter-  D
                                                                   —I	
                                                                    10.0

                                                                     um
                                                                    —,	

                                                                     20.0

-------
U)
         Q

         C
   98

   95



   90 -





   80




  ,70 -



   60 -
         co  50
         CO
         Q)
         ^  40
>  30


(TJ  .-| n
M  20
d


U
   10 -
             5
             2
                                 FIGURE  9  PARTICLE SIZE DISTRIBUTION
                                                                                  Mean
                                                                  Unit  4
                                                                  High  Load-Normal Operation
                                                                  8 Tests
                                    I          I             I          I
                                  1,0        2.0          5.0       10.0

                             Aerodynamic  Particle Diameter- D       ym
                                                                     20.0

-------
nt
st
to
01
0)
a)
>
-M
4J
o
    98

    95



    90 ~
80




70 -




60 -



50


40



30



20




10 H



 5


 2
                     FIGURE 10 PARTICLE SIZE DISTRIBUTION
                                                   Minimum
                 I

                 .5
                       1.0
 1

2.0
  I

5.0
                    Aerodynamic  Particle Diameter- D
  T

 10. 0


lam
                                                                         Mean
                                                                    Unit 4
                                                                    High Load-Soot Blow

                                                                    3 Tests
 1

20.0

-------
Ul
        Q

        C
        nj
        to
        in
        0)
0)
>

-p

rH
a


u
 98-

 95-



 90-





 80'




 70.


-i


 60'


 scr

 40-



 30"



 20'




 10-




  5-

  2-
                       FIGURE  11 PARTICLE SIZE DISTRIBUTION
                                         Maximum
       Mean
                                                              Minimum
                                                                Unit 1
                                                                Low Load-Normal  Operation

                                                                3 Tests
                            "	1	1	1	1	

                                  1.0        2.0          5.0        10.0

                            Aerodynamic Particle Diameter-  D     pm
                                                                     ~T	
                                                                      20.0

-------
O1
CTl
       Q

       C
       rtJ
       .C
        to
        in
       dp


       0)



       -U

       rH

       3
            98'

            95


            90-
80-





70


60


50


40


30



20-
             FIGURE 12  PARTICLE SIZE DISTRIBUTION
         Minimum
            10-



             5-


             2-
                        T
                                 I—
                                  2.0
                                                     Unit  2
                                                     Low Load-Normal Operation
                                                     2  Tests
1	

5.0
                         5         1.0

                            Aerodynamic Particle Diameter- D
10.0
	1—
 20.0

-------
    98
    95-

    90.
    80

Q
C   70-
CO
CO

-------
             TABLE
SUMMARY OF MASS MEDIAN PARTICLE DIAMETER

Unit 1


Unit 2



Unit 3
Unit 4

Operating
Conditions
High Load
Normal
High Load
Soot Blow
Low Load
Normal
High Load
Normal
High Load
Soot Blow
Low Load
Normal
Low Load
Soot Blow
High Load
Normal
High Load
Normal
High Load
Soot Blow
Number
of tests
4
2
3
7
4
2
2
4
8
3
Mass Median
Particle Dia-
meter urn
1.8
5.5
0.8
3.0
3.5
1.4
1.9
4.0
2.2
3.0
                    68

-------
                                               TABLE    10
                                   AVERAGE DAILY COMBUSTION PARAMETERS

                                                UNIT 1

Date
9-18
9-19
9-20
9-21
9-22
9-23
9-24
9-25
9-26
9-27
9-28
9-29
9-30
10-1
10-2
10-3
10-4
10-5
10-6
10-7
10-8
10-9
10-10
10-11
10-12
10-13
10-14
10-15
Steam Flow
1000 Ib/hr
522
599
606
665
584
000
361
590
601
606
598
553
465
422
543
643
648
664
646
372
360
473
577
619
614
622
600
543
Oil Flow
gal/hr
4900
5254
5415
5867
5088
-
3625
5450
5488
5440
5325
4954
4190
3792
4871
5736
5796
5946
5673
3450
3400
4415
5244
5577
5467
5583
5442
4944
Sulfur
%
1. 94
1.94
1.82
1. 72
1.69
-
1.73
1.94
2.01
2.06
2. 11
2.01
2.00
2.01
1. 95
2.00
2.08
2. 10
2.04
2.09
2.04
1.99
2.03
2. 09
2.17
2.12
2.00
2.12
Boiler
o2-%
4. 33
3.15
2. 88
2. 29
3.53
-
4.36
2.89
2.98
3.23
3. 37
3.97
3.67
3.54
3.18
3.21
3.00
2.91
2. 79
4.63
5.30
4.40
3.21 .
2.84
3.00
3.11
3.13
3. 80
Temp. -In
OF
599
616
613
629
599
-
524
607
615
619
619
614
589
562
604
630
635
640
630
564
565
598
620
628
628
635
G29
615
Temp. -on
Op.
311
320
321
325
312
_
293
317
317
320
317
320
314
315
317
319
325
325
324
314
320
317
323
326
324
324
320
323
                                                                         Adcli tive
                                                                         Ratio
                                                                         gal oi.l/gal add.
Days *
of
Operation
                                                                             2] 30
                                                                             2171
                                                                             2216
                                                                             2261
                                                                             2327

                                                                             2378
                                                                             2408
                                                                             2430
                                                                             2443
                                                                             2449
                                                                             2446
                                                                             2433
                                                                             2413
                                                                             2379
                                                                             2347
                                                                             2305
                                                                             2257
                                                                             2206
                                                                             2151
                                                                             2097
                                                                             2044
                                                                             1994
                                                                             1922
                                                                             1902
                                                                             1922
                                                                             1953
                                                                             2012
   44
   45
   46
   47
   48

   50
   51
   52
   53
   54
   55
   56
   57
   58
   59
   60
   61
   62
   G3
   M
   65
   fir,
   6 7
   6R
   09
   70
   71
*Since last holler wash

-------
                                         TABLE
                                             11
                               AVERAGE DAILY COMBUSTION PARAMETERS

                                            UNIT 2
Date
 9-18
 9-19
 9-20
 9-21
 9-22
 9-23
 9-24
 9-25
 9-26
 9-27
 9-28
 9-29
 9-30
 10-1
 10-2
 10-3
 10-4
 10-5
 10-6
10-7
10-8
10-9
10-10
10-11
10-12
10-13
10-14
10-15
Steam Flow
1000 Ib/hr
   630
   622
   619
   678
   666
   506
   438
   627
   635
   614
   543
   630
   634
   562
   593
   674
   678
   676
   665
   622
   558
   604
   649
   669
   662
   682
   651
   630
Oil Flow
gal/hr
 5683
 5604
 5583
 6050
 5925
 4638
 4013
 5658
 5679
 5500
 4900
 5619
 5681
 5029
 5354
 6129
 6046
 6117
 5950
 5602
 5008
 5615
 5846
 6067
 5917
 5992
 5794
 5337
                                Fuel
                                Sulfur
1.94
1.94
1.82
1.72
1.69
  ,76
  .73
  .94
  .01
  .06
2.11
2.01
  99
  90
  95
  00
  08
  10
  04
  09
  04
  99
  03
  09
2.17
2.12
2.08
2.12

Boiler
02-%
2.86
2.83
2.96
2.35
2.25
3.73
3.34
2.49
2.29
2.39
3.23
2.79
2.56
3.00
3.37
2.56
2.43
2. 33
2.53
3.06
3.38
3.12
2.78
2.52
2.60
2.66
2.72
3.39
AH
In- Temp.
OF
625
627
624
646
640
595
570
635
632
625
604
631
633
617
627
646
647
649
646
639
619
636
645
650
647
651
637
620
AH
Out-Temp .
OF
353
354
355
359
363
348
343
359
359
354
347
358
358
356
355
359
360
360
360
361
353
361
361
365
364
365
350
345
Additive
Ratio
gal oil/gal add.
2387
2406
2424
2440
2431
2471
2484
2496
2506
2516
2530
2642
2539
2542
2502
2550
2548
2444
2554
2554
2552
2550
2550
2628
2535
2527
2510
2499
Days*
of
Operation
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
*Since last boiler wash

-------
                                            TABLE
12
                                AVERAGE  DAILY COMBUSTION  PARAMETERS




                                               UNIT  3
Fuel
Date
10-6
10-7
10-8
10-9
10-10
10-11
10-12
10-13
10-14
10-15
Steam Flow
1000 Ib/hr
551
596
527
624
653
662
556
635
643
514
Oil Flow
gal/hr
5029
5415
4902
5704
5875
6092
5092
5708
5754
4826
Sulfur
%
1.
1.
1.
1.
1.
2.
2 .
2.
2.
2.
52
54
67
83
97
09
24
20
15
18
Boiler
o2-*
3.
3.
3.
3.
2.
2.
3.
2.
'->
3.
33
21
37
01
51
25
11
74
62
34
AH
Temp. -In
bF
515
566
558
586
588
591
571
591
598
571
All Additive
Temp. -Out Ratio
°F gal oil/gal add.
307
318
316
325
331
335
334
331
328
318
2107
2118
2375
2385
2395
2502
2550
2597
2645
2691
1 \-v.-s*
of
Opt'rntion
1
2
3
4
r^
6
/
3
-•>
10
'Since last boiler  wash

-------
                                         TABLE    13



                                AVERAGE DAILY COMBUSTION PARAMETERS

                                             UNIT 4
Date
9-18
9-19
9-20
9-21
9-22
9-23
9-24
9-25
9-26
9-27
9-28
9-29
9-30
10-1
10-2
10-3
10-4
10-5
10-6
10-7
10-0
10-9
10-10
10-11
10-12
10-13
10-14
10-15
Fuel
S team Flow
1000 Ib/hr
620
654
637
657
635
567
479
605
606
588
510
510
595
548
566
646
645
663
635
587
450
592
612
639
644
654
643
569
Oil Flow
gal/hr
5646
5908
5823
5950
5733
5225
4512
5533
5413
5500
4679
4767
5517
5058
5275
5971
5900
6096
5796
5400
4306
5908
5654
5879
5867
5946
5 796
5278
Sulfur
?
2 .
2.
2.
i.
2.
2.
2.
2.
2.
2.
2.
2.
2.
2.
2.
1.
1.
1.
1.
1.
1.
1.
1.
2.
2.
2.
2.
2.

00
01
05
15
23
16
20
08
07
08
05
09
13
02
00
95
87
60
52
54
67
83
97
09
22
20
15
18
Boiler
02-%
2. 92
2.58
2.42
2.17
2. 75
3.26
4. 38
3.23
3.15
3.02
3.28
3.08
2.67
3.00
3.01
2.68
2.25
2.24
2.13
2. 39
4 .07
3.44
3.12
2. 40
2.11
2. 38
2,90
3.51
AH
Temp. -In
OF
595
602
597
597
607
592
582
599
595
594
586
587
594
582
610
613
608
605
593
609
579
604
610
607
606
603
625
624
AH
Temp. -Out
0F
333
334
339
353
355
340
329
342
337
331
327
329
327
338
338
330
338
348
355
362
332
348
351
359
359
367
363
351
Add Ltive
RaUo
gal oil/gal add.
     1976
     2070
     2016
     2176
     2171
     2092
     2038
     2006
     2009
     2002
     2002
     2021
     3505
     3630
     3641
     3846
     3581
     3404
     3333
     3337
     3425
     3497
     3560
     3793
     2581
     2557
     2502
     2419
of
Opera t i on
   1 5
   ] 6
   1.7
   18
   T<1
   20
   21
   i.l
   23
   24
   27
   ,'H
   29
   30
   31
   32
   33
   34
   35
   30
   37
   38
   39
   40
   41
*Since last boiler wash

-------
                                                       TABLE
                                                     14
                                                   FUEL  OIL  SPECIFICATIONS
U)
9-18
9-18
9-18
9-19
9-19
9-19
9-25
9-25
9-25
10-02
10-02
10-02
10-09
10-09
10-09
10-09
10-15
10-15
10-15
10-15
BTU/lb

18,581
18,586
18,670
18,587
18,653
18,672
18,633
18,670
18,628
18,571
18,584
18,846
18,641
18,620
18,646
18,555
18,658
18,538
18,773
18,501
Ash
%
.14
.11
.13
.13
.11
.12
.14
.12
.11
.14
.10
.11
.13
.11
.15
.12
.11
.10
.09
.09
S
%_
1.91
2.00
1.99
1.96
1.99
2.00
2.01
1.93
2.00
1.91
2.02
1.94
1.94
1.96
1.92
1.96
2.04
2.05
2.11
2.14
C
%_
85.9
85.5
85.9
85.7
86.1
S6.2
85.1
84. 8
85.4
85.9
85.7
85. 8
85.8
85.5
85.6
85.4
86.0
86.0
85.8
86.0
H
%_
12.4
13.8
13.6
13.2
13.1
12.2
11.2
11.2
11.0
12.0
11.5
12.1
11. 8
12.2
11. 8
12.3
12.1
12.2
12.4
12.4
N
%_
.79
.40
. 30
.40
. 30
.24
.35
.20
.30
.27
.28
.27
.33
.34
. 33
.27
.21
.20
.18
.17
Cl
%
.01
.02
.01
0.0
0.0
0.0
0.0
0.0
0. 0
.02
.02
.02
.02
.02
.02
.02
.02
.03
.02
.02
Na
ppm
64
72
59
55
48
47
-
-
-
66
41
61
53
50
56
36
42
36
39
40
K
ppm
2
1
2
1
7
1
-
-
-
2
2
1
1
2
2
2
4
2
2
3
Mg
ppm
153
110
133
136
113
129
-
-
-
160
160
110
190
130
260
180
170
140
150
120
Ca
ppm
8
6
8
7
6
7
-
-
-
8
5
5
7
6
9
6
7
5
5
6
Hi
ppm
48
45
45
35
49
35
-
-
-
5?
76
45
81
84
81
84
42
54
53
55
Mn
ppm
2
1
2
2
1
2
-
-
-
2
2
1
2
1
2
1
1
1
1
1
Fe
ppm
9
7
6
8
7
6
-
-
-
8
q
6
S
7
3
1
5
8
7
9
V
ppm
212
203
207
231
203
223
-
-
-
235
212
216
165
169
224
182
160
14*1
175
176

-------
                             TABLE
15
                     FUEL ADDITIVE ANALYSIS  -  METALS
Date
9-18
9-20
9-25
10-02
10-09
10-15
Na
PJP"L.
1180
1130
1120
1000
900
1000
K
gpm
260
240
250
260
250
240
Mg
%
25.51
25.93
25.97
25.98
25.95
26.05
Ca
ppm
8390
6270
7210
7300
7700
7700
Ni
p_pm
3
8
4
2
3
3
Mn
ppm
2081
2008
1948
1930
1890
1980
Fe
ppm
923
1014
965
1160
1190
1190
V
ppm
N.D
N.D
N.D
N.D
N.D
N.D
N.D. - less than 1 ppm
                                   74

-------
from the stack effluent  near  the  point  of  discharge.   Simul-
taneous documentation of  the  combustion parameters was accom-
plished, as well as  the  daily acquisition  of  oil and  additive
samples.

Since the samples of emitted  materials  were  taken over a short
time span with each  24-hour day,  and  the emissions from the
boilers varied over  a wide range  during each  day, it  was bene-
ficial to use these  data  to predict  the quantity of ejected
materials on a continuous real-time  basis.   Statistical tech-
niques were used in  making these  predictions,  in particular was
the multiple stepwise regression  analysis  using  emission test
data and simultaneous operational combustion  parameters.  A
regression analysis  was  used  to quantify the  relationship
between a dependent  variable,  y,  and  one or  more independent
variables, x • .  The  model with regression  coefficients, P^, is
written as follows:

y = 60 + 61*! + 32X2 +  •  •  •  • +  SpXp + E

A stepwise regression method  was  used for  the  analysis.

The stepwise regression  procedure is  a  modification to forward
selection regression.   Independent variables  are entered until
a satisfactory regression equation is obtained.   Independent
variables are inserted  in order according  to  their partial cor-
relation coefficient.  At each stage  in the  regression the in-
dependent variables  previously entered  are  re-examined.  The
test statistic or partial F criterion for  each variable in the
regression is evaluated  and compared  with  a  pre-selected per-
centage point of the appropriate  F distribution.  Any indepen-
dent variable providing  a non-significant  contribution is
removed from the model.  This process is continued until no
more independent variables are added  or deleted.  Through this
procedure, an independent variable important  at  an early stage
                               75

-------
can be dropped because  of  relationships between it and other
independent variables brought  into the equation at a later
stage.

At each step the variables are  removed and/or entered into the
equation according  to the  F value  criteria.  The variable with
the smallest F value  is  removed from the equation if the F-to-
remove is less than the  chosen  lower limit.  If no value meets
this criterion,  the variable with  the largest F value is
entered into the equation  if the  F-to-enter is larger than the
chosen limit.  This allows selectivity of the variables in the
equation in as many steps  as there are variables.

An analysis of variance  (ANOVA) is used to test the null hypo-
thesis that the  regression coefficients are zero.  That is, the
F value is used  to  test  the statistical significance of the
regression equation.

The standard error  of estimates,  which is the square root of
the deviations mean square, provides a measure of how closely
the regression model  fits  the  data.   Since the purpose is to
find a more accurate method of  predicting y,  the size of the
standard error of estimates is  of  primary importance.  The
smaller the standard  error of  estimates, the  better the regres-
sion equation fits  the  data.

The correlation  coefficient, r, for a simple  linear regression
analysis indicates  how  closely  the dependent  variable, y, is
related to the independent variable, x.  The  range of cases can
be from r=0 where y is  independent of x and there is no rela-
tionship between the  variables  to  r=+1.0 where any change in x
is accompanied by a proportionate  change in y.  The multiple
correlation coefficient,  R, is  a measure of the joint relation-
ship of all the  independent parameters, x-, to the dependent
parameter y.
                                76

-------
The adjusted R2 value  is  used  to  estimate  the  fraction of the
variance of y that  is  attributable  to  the  regression.   An ideal
regression model would  have  an adjusted  R2 value equal to 1.0.
The adjusted R2 value  is  translated  as:

               Adjusted R2 = 1 -  (MSD/MST)
                                  A  0
               Where    MSD  =  Z(y-y)_
                                n-p-1
                        MST  =  E (y-y)_2_

Particulate Model

Multiple regression analyses were performed using emission
rates of specific materials  derived  from emission tests and
simultaneous operational  and combustion  parameters.   Each emis-
sion test was considered  to  be one  data  point.   For  the parti-
culate discharge regression  analysis,  forty-six data points
were available.  Independent variables  consisted of:  oil flow,
boiler oxygen content,  fuel  sulfur  content, additive ratio,
(gallons of oil/gallons of additive),  and  days  of operation
since the last boiler  wash.  Since  this  was a  stepwise regres-
sion analysis, the  results were  documented after each  parameter
was entered, with decreasing order  of  consequence.   The lowest
standard error appeared after  oil flow,  gallons of  oil/gallons
of additive, and boiler oxygen content  had been entered.

Particulate Sulfate Model

Particulate sulfate emissions  were  correlated  with  the same
parameters as particulate emissions.  Fiftyfour data points
were analyzed (soot blow  test  data  were  eliminated  from the
particulate prediction  analysis  but  not  from the particulate
sulfate prediction  analysis).   The  lowest  standard  error
appeared after oil  flow,  gallons  of  oil/gallons of  additive,
                                77

-------
days of operation since the last  boiler  wash,  and  boiler oxygen
content had been entered.

Sulfur Dioxide Model

Sulfur dioxide emission rates were  correlated  with the  weight
rate of fuel sulfur entering the  firebox.   Forty-six data
points were available.

Total Sulfate Model

Total sulfate emission data were  correlated with oil flow,
boiler oxygen content, gallons of oil/gallons  of additive,  fuel
sulfur content, and days of operation  since the  last boiler
wash.  Forty-six modified Method  6  test  results  were
available.  The lowest standard error  appeared after all the
parameters had been entered.

Summary of Regression Coefficients

The summary of regression coefficients for  the prediction
models is shown on Table 16.  Units are  Ib./hr.  for  filterable
particulate, sulfur dioxide, and  total sulfate;  percent of
filterable particulate for particulate sulfate.  The standard
error of estimates in each case is  15% or less of  the mean
value, indicating reasonable, but not  exceptional,
correlation.

Emission Estimates

The models were applied to the actual  data  in  the  form  of
hourly averages.  However, fuel sulfur content and gallons  of
oil/gallons of additive were not  available  hourly, therefore
representative daily values were  substituted.  Since particu-
late emissions during soot blowing  were  approximately 40%
                               78

-------
higher than during normal  operation,  a factor was inserted into
the parameter data files which  caused the  particulate rate to
be multiplied by  a 1.4 whenever soot  blowing was performed.
The hourly emission  rates  were  summed on a daily basis for cor-
relation with 24-hour ground-level  concentration measurements.
The results of  these summations are shown  in Figures 14, 15,
16, 17, and 18  in the form of  average hourly rates each day for
particulate, particulate sulfate,  total  sulfate, acid sulfate,
and sulfur dioxide,  respectively.   These graphical presenta-
tions reflect the day when Unit 1 was out  of service due to an
economic outage  (Day 6) and the period when Unit 3 came on-line
after an extended maintenance  outage  (following Day 19).

DIURNAL EMISSION  PROFILE

The diurnal analyses of emission estimates for particulate,
particulate sulfate, total sulfate, and  sulfur dioxide are
presented in Figures 19, 20,  21, 22,  respectively.

INVESTIGATION OF  THE RELATIONSHIP OF  SULFATE FORMATION TO
COMBUSTION PARAMETERS

Several individual operational  and  combustion parameters were
investigated in order to gain  knowledge  of primary sulfate
formation in these combustion  furnaces.  The high variability
of sulfate emissions observed  is probably  due to a complex
interaction of  specific variables.   The  most likely causes of
high sulfate emissions are high oxygen levels, high sulfur and
metals content  of the oil,  burner  and boiler configuration,
cleanliness of  boiler internals, degree  of air leaks, and to a
certain extent, the  collection  efficiency  of the particulate
collectors.  In the  case of these  boilers, the burner and
boiler configurations, fuel sulfur  and metals content, and
operation of the mechanical collectors are similar between
boilers.  The oxygen levels are variable but in all cases are
                                 79

-------
                                                       TABLE   16
                                           SUMMARY OF EMISSION PREDICTION MODELS
                                                                   Additive
                                                                     Ratio                                  Standard
                                           Oil Flow  Fuel   Boiler oil/addi-  Days  of    Multiple Adjusted  Error of
                             Y-Intercept   gal/hr    S %    0? %    tive	Operation	_R	R^	Estimates
           Filterable
           Particulate
           Mean,92.5 Ib/hr
-15.2
              .028
+4.9    -.021
                                                            .91
                                                                    .81
                                                                               14 .1
00
           Particulate
           Sulfate
           Mean,47.5%
           of  Particulate
+ 25.7
             -.002
+2.0    +.009
                                                + .12
                                                            .72     .47
                                                                                6.6
           Sulfur Dioxide     +492.3
           Mean,1893  Ib/hr
                                           +.145*
                                                            .89     .78
                                                                              202.0
           Total  Sulfate      +115.1
           Mean,114.0  Ib/hr
             +.033    +16.1  +20.1   -.008     -.18
                                                            .87
                                                                    .73
                                                                                                              17.5
            Multiplied  times  %  Fuel  Sulfur

-------
                                              PARTICIPATE  EMISSION ESTIMATE

                                        24-HOUR AVERAGE  OF PLANT AGGREGATE TOTAL
00
•H
4J
in
w

o
•H
tn
in
                 w
                 0)
                  o
                  -H
                  4J
                      300  -
                      250  -
                      200  -
                      150  '
     100  -
      50
                                                             Maximum
                                                             Hourly
                                                             Average


                                                             Mean
                                                             Hourly
                                                             Average
                                                                                   Minimum
                                                                                   Hourly
                                                                                   Average
                         9-18
5          10            15           20

Day of Field Measurement Program

           FIGURE  14
                                                                                          25
                                                                                10-15

-------
                  M
                 si
                 3  150 -\
                                        PARTICULATE SOLUBLE SULFATE EMISSION ESTIMATE



                                          24-HOUR AVERAGE OF PLANT AGGREGATE TOTAL
00
NJ
VI
U

d
o
-,-t
in
ui
•o4
e
w
                  n)
                 >M
                 05


                 <0
                  O

                  W
                     125
                     100
                      75
     50
    25
                                                               Maximum

                                                               Hourly

                                                               Average


                                                               Mean

                                                               Hourly

                                                               Average
                                                               Minimum

                                                               Hourly

                                                               Average
                 -P
                 M
                 n)
                 tx,
                                                 -r
                                                         T — i — i
                        9-18
5             10              15


    Day of Field Measurement Program


                FIGURE  15
                                                                                20
                                                                             25   10-15

-------
                                       TOTAL SOLUBLE SULFATE  EMISSION ESTIMATE

                                      24-HOUR AVERAGE OF  PLANT AGGREGATE TOTAL
00
              -P
              m
              w
              w
              o
              W)
                  300
                  250
                  200  .
                  150
                  100
                   50
                                                                                                 Max.
                                                                                                 Hourly Ave.
                                                                                                 Mean
                                                                                                 Hourly Ave.
                                                 Min.
                                                 Hourly Ave.
              o
              EH
                      9-18
10           15            20

Day of Field Measurement  Program

          FIGURE  16
                                                                                      25
                                                                                              10-15

-------
00
                     200
                     175
                     150
                     125
 I
 «
 *  100
•H
 0)
W
                   4)
                   •P
                   n)
                  3
                      75
                      50  '
                      25
                          ACID  SULFATE EMISSION ESTIMATE

                     24-HOUR  AVERAGE OF PLANT AGGREGATE TOTAL
                             T	1	r~

                          9-18
                                 10
-i	1	1—r

    15
i — i — i

 20
                                                                                     i — r
                                                                                          25
                                                   Day of Field Measurement Program

                                                             FIGURE 17
                         Maximum
                         Hourly
                         Average
                                                                                  Mean
                                                                                  Hourly
                                                                                  Average
                                                                                  Minimum
                                                                                  Hourly
                                                                                  Average
                                                                                                '—r
                                                                                                10-15

-------
00
Ln
                    I
                    
-------
     300 ~
                       DIURNAL ANALYSIS OF EMISSION  ESTIMATE


                                    PARTICULATE


                      28-DAY AVERAGE OF PLANT AGGREGATE  TOTAL
 I
 c
 o
•H
 W
 (n
•H
 g
W
.H
3
O
(0
     250
     200
     150
     100 -
      50  -
                                                                            +a
                                                                            Me an
                             i  I   T  I
                                          i  i   r
                                                    I   I  I   1   I  I   I  I   I
             12  345   67   89 10 11 12 123   45   6  789 10 11  12

                                        NOON


                            Hour — Eastern Standard  Time


                                    FIGURE  19

-------
00
        d
        o
        •H

        U)
        •H
        6
        W

        0)
        -p
        to

        0>
        0)
        -P
        03
        O
       •H
                              DIURNAL ANALYSIS  OF EMISSION  ESTIMATE


                                    PARTICULATE  SOLUBLE SULFATE


                             28-DAY AVERAGE OF  PLANT AGGREGATE TOTAL
            100 -
           Cn
             50 -
             25  -
                                        Mean


                                   -1- J-  -a
i   I  i   i   I   i  i   i   i   i  i   i
                                                                                I   I
                    1   23  45   67  89 10  11 12 12   345  6  789  10 11 12

                                                 NOON



                                    Hour — Eastern Standard  Time


                                            FIGURE  20

-------
                                DIURNAL ANALYSIS OF EMISSION  ESTIMATE

                                        TOTAL SOLUBLE SULFATE

                               28-DAY AVERAGE OF PLANT AGGREGATE TOTAL
CO
00
        I
        fl
       tn
       •H
       e
       
                                                              i   r  i   i   7  T
                       123  4  567   8   9  1011 12 123   4   567  8   9  1011 12

                                                  NOON

                                      Hour—Eastern Standard Time

                                               FIGURE 21

-------
00
 I
 fl
 O
•H
 W
 cn
•H
 e
 w


 <8
 •H
 X
 O
 •H
 Q
                              DIURNAL ANALYSIS OF  EMISSION ESTIMATE


                                          SULFUR  DIOXIDE


                             28-DAY  AVERAGE OF PLANT AGGREGATE TOTAL
           3000  -
           2000  ~
           1000  -
-r  +0



   Mean



—  -a
       CO
                     ii   ii  ii   iiii  if  i   i   r  i   i

                     12  345   6   789 10 11  12  123  456   7   89  10 11 12

                                                NOON


                                     Hour—Eastern Standard Time
                                              FIGURE 22

-------
too high to demonstrate a distinct  change  in  sulfate  emissions
from time to time.  The ratio of  sulfate emissions  to total
sulfur oxides (100 x SO4/SO2 + SO4) was  the  indicator used
because it reduces bias caused by the  variance  of  fuel sulfur.

Vanadium content of the fuel is known  to be a contributory
cause of sulfate formation by catalysis.   However,  there is no
way of knowing how much vanadium  is  in the fuel continuously,
or even how much is in the boiler in  the form of ash  deposits
at any given time.  Therefore, vanadium  concentration in the
stack gas, measured simultaneously  with  the  sulfate measure-
ments, determined the vanadium factor  relating  to  sulfate
formation.

The number of days of operation since  the  last  boiler wash is a
relative indicator of the condition  of the boiler  internal sur-
faces.  The effect may be that longer  operation confers more
ash buildup, therefore more sulfate  formed by catalysis.  How-
ever, a magnesium fuel additive is  used  in the  boilers for cor-
rosion control; some literature cites  that a  magnesium oxide
layer on the boiler internals with  the use of the  additive
(Reid, 1971), will deactivate the catalytic  ash deposits
(Barrett, 1966).  Work has shown  as  much as  50% less  sulfate
emitted when magnesium additives  were  used on boilers firing
low sulfur, low vanadium fuel oil that had previously not used
additives (Boldt and Laube, 1978).

The operational characteristics such  as  burner  and  atomizer
condition, air supply controls, boiler casing and  duct condi-
tion affect the extent of sulfate formation.   The  investiga-
tions of sulfate ratio, compared  to  operational parameters, was
limited to 2 individual boilers to  minimize  interferences.  The
boilers with the largest numbers  of  data points were  Units 2
and 4; a sum of Unit's 2 and 4 data  comprised a third set.
                                90

-------
The results of  regression  analyses  which compare the opera-
tional parameters  to  the sulfate  ratio are shown in Table 17
(explanation of  the regression  terms  can be found in Section
4).  The most significant  relationship exists between sulfate
and the concentration  of vanadium in  the stack gas.  Consistent
y-intercepts, slopes,  correlation coefficients,  and standard
error of estimates are observed between the three data sets
(see Figure 23).   Obviously  this  relationship overshadows any
variations among  the  other parameters.

Weaker relationships  appear  with  additive ratio (gallons oil/
gallons additive)  and  days of operation, but they are apparent
only when the data from two  boilers are combined.   These rela-
tionships are essentially  straight  lines between two data
points, since the  data are clustered  for each boiler (see
Figures 24 and  25).   These data suggest that if more additive
is injected into  the  flame,  less  sulfate is emitted, all other
parameters remaining  equal.   The  mechanism of this reduction
could be either  enhanced collection of magnesium sulfate in the
mechanical collectors,  or  a  long-term deactivation of catalytic
surfaces by magnesium oxide.
                               91

-------
TABLE 17

Independent
Variable
Fuel Sulfur
Unit 2
Unit 4
(Unit 2+4)
SUMMARY
(S04/'s04+S02>
Units of
Independent
Variable

%
%
*
OJF REGRESSION ANALYSES
C 100) AS DEPENDENT VARIABLE
Y-Intercept Slope

- .44
+4.28
+3.60

+ 2.15
- .18
+ .05
R

.69
.07
.02
Adjusted
R2

.45
-.08
-.03
Standard
Error of
Estimates

.43
.57
.64
Stack Gas Temperature
Unit 2
Unit 4
(Unit 2+4)
oc
oc
°c
+1.89
+ .66
+ 3.95
+ .01
+ .02
- .00
.23
.41
.04
-.01
.10
-.03
.53
.52
.64
Boiler Oxygen Content
Unit 2
Unit 4
Unit 2+4)
Additive Ratio
Unit 2
Unit 4
Unit 2+4)
Days of Operation
Unit 2
Unit 4
(Unit 2+4)
%
%
%

1000 gal/ gal
1000/gal/gal
1000 gal/gal

days
days
days
+4.02
+4.46
+4.23

-13.86
+ 5.06
+ 1.93

- 6.54
+ 1.77
+ 4.40
- .22
- .17
- .21

-7.00
- .30
+ .60

+ .13
+ .07
+ .01
.35
.28
.29

.40
.09
.46

.47
.21
.45
.07
-.00
.05

.10
-.07
.19

.17
-.04
.17
.55
.55
.61

.54
.57
.56

.52
.56
.57
Vanadium Concentration
Unit 2
Unit 4
(Unit 2+4)
mg/m
mg/m^
mg/m^
+ 2.02
+ 2.58
+ 2.20
+ .36
+ .31
+ .36
.77
.69
.73
.55
.41
.50
.42
.49
.47
  92

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                                                          UNIT  2
 5.00-


 4.0CT


 3.00-


 2.00"


 i.oo-





5.00


4.00 '


3.00


2.00 '


1.00 '





5.00 -



4.00


3.00 -


2.00


1.00 '
1.0   2.0   3.0   4.0   5.0   6.0   7.0
1.0   2.0   3.0   4.0   S.O   6.0   7.0
                                                Regression
                                                   2.0202+.3563V
                                                   R=.7725
                                                   Adjusted R2=.5463
                                                   Std. Error=.4201
                                                UNIT  4
                                                Regression
                                                   2.5733-I-.3099V
                                                   R=.6872
                                                   Adjusted R =.4063
                                                   Std. Error=.4936
                                                UNIT 2*4
                                                Regression
                                                   2. 1994+.3550V
                                                   R=.7273
                                                   Adjusted R =.5028
                                                   Std. Error=.4716
          1.0   2.0   3.0   4.0   5.0   6.0   7.0
                Vanadium Concentration in Stack Gas - mg/m
                            FIGURE  23
                                  93

-------
5.00 -
                                                    UNIT  2
4.00
3.00 -
2.00 -
1.00 -
Regression
   -13.8635+.0070R
   R=.3960
   Adjusted R =.1006
   Std.  Error=.5428
5.00
               1000
                            2000
                                       3000
                                                    4000
                                                    UNIT  4
4.00
3.00
2.00
1.00
Regression
   5.0596-.0003R
   R=.0907
   Adjusted R =-.0744
   Std. Error=.5658
5.00
4.00
3.00
2.00
 1.00
                1000
                            2000
                                        3000
                                                    4000
                                                    UNIT 2+4
Regression
   1.9340+.0006R
   R=.4643
   Adjusted R =.1885
   Std. Error=.5641
                1000        2000         3000        4000
              Additive Ratio - R - Gal. Fuel Oil/ Gal. Additive
                               FIGURE 24
                                94

-------
5.00
                                                    UNIT  2
4.00
3.00
2.00
1.00
Regression
   -6.5428+.1280Days
    R=.4715
    Adjusted R =.1704
    Std. Error=.5213
5.00  '
4.00
           10
                —I—
                 20
                       30    40    50    60
                                               70
                                                     80
                                                    UNIT 4
3.00
2.00
1.00 -
Regression
   1.7733+.0665Days
   R=.2070
   Adjusted R =-.0369
   Std.  Error=.5359
5.00  '
           10    20
                       30    40    50    60
                                                70    30

                                                    UNIT  2
4.00
3.00
2.00
1.00
Regression
   4. 3970+.0124Days
   R=.4454   2
   Adjusted R =.1707
   Std. Error=.5703
           10    20    30    40    50    60     70
             Days of Operation After Boiler '//ash

                         FIGURE  25
                                                     80
                              95

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                           SECTION  5
                          AIR QUALITY
TOTAL SUSPENDED PARTICULATES

For several years the New York  State  Department  of Environ-
mental Conservation has operated a  high  volume  sampler network
in the Albany area.  The results of several  of  those stations
are shown in Table 18.  The Cohoes  Station  is  located across
the Hudson River from Troy; the Colonie  Station  is located at
the Albany Airport; the Castleton Station  is  located just South
of the Albany Steam Station on  the  East  side  of  the river.

All reporting stations show a general declining  trend in TSP
over the years.  Particulate concentrations  at  the downtown
Albany Station decreased by 50% during the  period  (1966-1978).
Rensselaer,- Troy, and Schenectady show a slight  increase, then
a continued decrease through the 1970's.

PARTICLE SIZE

Experiments to determine particle size were  conducted through-
out the test period.  They were operated at  the  base site and
site 5 (one day run at site 1)  every  even  day  beginning on
September 18 and concluding on  the  14th  of  October.

The procedure for the collection of the  various  size particles
involved the use of a multi-stage cascade  impactor manufactured
by Sierra Instruments, Inc.  This separates  suspended particu-
lates into six size fractions based on flow rates.
                                96

-------
                                        TABLE 18
                  Long Term Total Suspended Particulate Concentrations
                                 Annual Geometric Means (yg/m )
                                 Station/Station Number
Year
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
Rensselaer
4101-02
-
-
-
66
72
75
77
74
62
54
46
42
40
Downtown
Albany
0101-03
82
87
73
64
70
67
59
57
51
50
41
42
37
Troy
4102-02
62
57
52
46
45
51
52
55
53
46
39
36
33
Cohoes
0102-01
-
69
68
53
61
-
-
61
-
63
56
-
-
Colonie
0153-03
-
-
-
-
-
-
-
55
51
52
42
44
43
Schenectady
4601-02
87
-
62
59
60
64
62
72
64
52
46
45
41
Castleton
4124-01
-
72
59
-
51
-
43
34
39
39
32
31
30
Source:  NYSDEC

-------
          Stage          Cut-off Size at  40  CFM  (Microns)
            1                 >7.2 u
            2                  7.2-3.0
            3                  3.0-1.5
            4                  1.5-0.95
            5                  0.95-0.49
            6                  0.49>

The daily particle size distributions were  plotted on lognormal
probability graph paper.  The cumulative.weights (%)  are plot-
ted against the cut-off size  (urn) for that  stage.   The daily
mass median diameters were  then  read off  the curve to give the
results shown  in Table 19.  The  arithmetic  averages of the mass
median diameter for the base  site and site  5 were  0.59 microns
and 0.65 microns respectively.   The one  day  operation at site 1
resulted in a  mass median diameter of 0.70  microns.  Various
scatter type plots were done.  The variables being mass dia-
meter, total suspended particles on the  back-up  filter, SO^,
nephelometer values and total suspended  particles  on  the high
volume sampler filter.

At site 5 a correlation between  SO^ and  the  particle  size range
of 0-.49u (6th stage) was observed.  At  the  base site, however,
there does not appear to be any  simple  relationship between
these two.  A  possible explanation of this  could be that the
downwash at the base site caused large  particles of sulfate to
be retained on the hi-vol filters, thus  increasing SO^ and
negating the correlation between SO^~ and  particle  size.  A pos-
sible explanation for the correlation appearing  at site 5 is
most likely due to the fact that the larger  sulfate particles
would have dropped out before reaching  the  monitoring system,
indicating a very local plant effect.   If this is  the case
then site 5 was representative of the long  distance transport
particles of small size and slow settling velocities.
                               98

-------
The results of  the Energy  Dispersive X-ray (EDX) laboratory
results of the  dichotomous  filters  have not yet been provided
by the EPA's  laboratory  in  Research Triangle Park.   Thus, any
conclusions drawn betweeen  cascade  sizing and hi-vol filters is
tentative.

Studies by Mezaros  (1970),  Whitby (1978), Tanner and Marlow
(1977) have indicated  that  the  great majority of airborne (804
is in the particulate  size  range  of 0.01-0.5 urn.  Mezaros
(1978) has reported  the  results of  a field test in which 90% of
the total sulfate mass measured at  a rural site had a diameter
less than 0.6 um.

The size data reported by  these authors suggest two things.
First, they are  of a size  to  affect visibility, and second,
they could be capable  of  being  transported great distances be-
fore gravitational settling out occurs.  In this study if the
association between  hi-vol  filter data and cascade filter mass
holds true, then a portion  of the emitted SO^ particulate is of
sufficient size  to settle  out within short distances of the
plant.  This  is  a tentative conclusion requiring further effort
to verify this.

SULFUR DIOXIDE

Long term SC>2 data  is  contained in  Table 21.  These data were
provided by NYSDEC;  stations  not  previously identified are the
Town of Bethlehem, located  on Highway 9W South of the City of
Albany and West  of the Albany Steam Station and the Town of
Hudson, located  about  23 miles  South of Albany.

These long term  data indicate there are geographical variations
in the data.  The area along  the  Hudson River to the North of
the Albany Steam Station  shows  higher values of SC>2 than the
rural stations  at Bethlehem and Hudson.  For most of these
                               99

-------
      TABLE  19

 CASCADE  IMPACTOR RESULTS
       BASE SITE
Micrograms per cubic meter

DATE
Sept.






Oct.








18
20
22
24
26
23
30
02
04
06
08
10
12
14

1
4.995
4.327
0.799
0.000
2.143
1.133
2.102
1.392
0.917
3.018
0.443
0.480
5.324
1.010


0.
2.
2.
0.
6.
2.
3.
2.
1.
0.
0.
0.
s,
1.

2
000
308
542
124
017
644
,083
435
,975
,000
,448
.320
.659
.554



STAGE
3 4
0.000
2.019
1.452
0.000
2.225
2.853
2.102
1.739
1.482
0.000
0.179
0.080
5.058
1.243
0.000
2.308
1.162
0.000
5.852
1.740
2.102
2.157
1.834
0.000
0.089
0.160
5.977
1.243
0.
•>
0.
0.
0.
2.
2.
4.
3.
0.
0.
0.
11.
1.

5
000
967
290
062
330
296
382
453
034
000
,089
,000
,494
,476


9.
9.
8.
0.
14.
11.
12.
13.
10.
44.

6
445
304
207
062
177
967
611
Oil
013
264
1.881
2.882
31.341
7.460
MASS MEDIAN
DIAMETER
(MICRONS )
-
0.88
0.56
1.00
1.10
0.41
0.49
0.42
0.54
-
0.32
0.14
0.72
0.55
CASCADE IMP ACTOR RESULTS






Micrograms
DATE

Sept.






Oct.








18
20
22
24
26
23
30
02
04
06
08
10
*12
14

1
0.644
0.851
1.556
0.000
1.C22
1.136
1.043
1.245
0.713

0.318
5.255
•7.307
0.136


1
1
1
0
1
2
1
1
1

0
7
*9
0

2
.611
.914
.738
.000
.294
.248
.780
.305
.485

.572
.434
.150
.327

3
1.095
1.276
0.549
0.000
0.749
1.748
0.798
1.866
1.069

0.000
3.204
*5.003
0.000
SITE 5
per cubic
STAGE
4
1. 353
1.701
0.091
0.000
2.520
2.060
0.859
2.173
1.604

0.254
2.627
•5.727
0.000


meter


1
2
0
0
0
0
1
4
0

0
4
•10
0

5
.933
.836
.914
.000
.681
.874
.412
.107
.000

.381
.101
.993
.340


* Located


3
2
12
0
0
10
7
9
9

3
15
•30
0

6
.157
.056
.438
.000
.000
.927
.120
.645
.360

.113
.124
.611
. 340

at Site 01
MASS MEDIAN
DIAMETER
(MICRONS)
0.94
1.20
0.13
0.00
2.20
0.44
0.42
0.56
0.26

0.20
0.94
•0.70
0.49
              100

-------
DATE
Sept. 18
      20
      22
      24
      26
      28
      30
Oct.  02
      04
      06
      08
      10
      12
      14
                    TABLE 20
               DICHOTOMOUS SAMPLER RESULTS
               Micrograms per cubic meter

                    BASE SITE
<3.5y

33.7
12.8
15.0
11.1
16.7
12.8
12.3
13.2
 5.0
 0.0
14.6
27.4
 3.6
>3.5y

16.8
 9.8
05.0
16.5
17.8
06.1
12. 3
 4.8
 0.7
 0.0
 3.9
14.5
 1.7

<3.5y
3.1
2.0
6.1
3.6
9.2
24.0
14.8
23.0
20.9
18.4
6.1
40. 3
*58.2
9.2
SITE 5
>3.5y
23.4
15.9
21.2
19. 3
24.8
1.8
0.0
0.0
0.0
0.0
3. 3
0.0
* 0.0
1.6
                                             * Located  at  Site  01
                               101

-------
                                            TABLE 21



                             Long Term Sulfur Dioxide Concentration

                                       Annual Means  (ppm)
o
to
Year
1970
1971
1972
1973
1974
1975
1976
1977
1978
Downtown
Rensselaer Albany
4101-02 0101-03
0.020
0.020
0.019
0.017
0.018
0.014
0.014
0.016
0.016
;
-
0.021
0.018
0.017
0.016
0.014
0.016
Troy
4101-02
-
-
-
0.008
0.007
0.005
0.007
0.011
Cohoes
0102-01
-
-
-
0.014
0.011
0.011
0.010
0.008
Schenectady
4601-05
-
0.018
0.016
0.014
0.013
0.013
0.015
0.014
Bethlehem Hudson
0151-01 1001-02
-
- -
-
0.006
0.006
0.008 0.003
0.004
0.005
         Source:  NYSDEC

-------
stations  there  is  insufficient data available to ascertain long
term  trends  in  the SC^ data.

The diurnal  variation  in ambient SO2 concentration during the
study period is  shown  in Figures 26 and 27.  Two of the sites
(site 4 and  6)  showed  very little variation in SO2.  This indi-
cates that these stations were not affected to a great extent
by nearby SO2 sources.   The low levels at sites 4 and 6 also
sustain this conclusion.

The base  site was  affected by the Albany Steam Station's efflu-
ent but only to  a  limited extent.  There was a slight maximum
around 0800.  This was  probably due to inversion breakup or
fumigation effects.

Four of the  sites  showed considerable diurnal variations.
These stations  indicated a diurnal maximum before or during
noon.  The increases generally began around 0800, or the time
of the morning  inversion breakup.  The diurnal decrease was
usually achieved by around 1600-1800 with the onset of the
evening stable  conditions.

This sustains the  supposition that the sites were influenced by
industrial sources  only  during part of the day.   Until the time
of inversion breakup, most of the sites were not greatly af-
fected by the plant, as  the surface stable conditions retarded
the dispersion of  industrial  SC>2 emissions.  Either they were
contained in the surface stable layer or else there was suffi-
cient plume  buoyancy to  rise  above the surface stable layer.

PHOTOCHEMICAL POLLUTANTS

Photochemical pollutants,  nitric oxide (NO), nitrogen dioxide
(N0?), and ozone (O-^) were  measured in the Albany area during
this study.   Table  22 contains historical data collected in
                              103

-------
                       FIGURE    26
               S02  DIURNAL  VARIATION
  0.030-
  0.020-
  0.010-
                                      Site   1
      24  02  04  06    08  10  12   14   16   13  20   22   24
                             HOUR OF DAY
  0.030-
£ 0.020-
  0.010-
                                    Site   5
      24  02  04  06   08  10   12   14   16   13   20   22   24
                             HOUR OF DAY
  0.030-
  0.020-
  0.010-
                                   Rensselaer Site
      24  02  04   06
08   10   12   14   16   18   20   22   24
     HOUR OF DAY
                            10!4

-------
  0.020-
  0.010-
                         FICURE   27
                  S02   DIURNAL  VARIATION
                                       Base   Site
      24  02   04   06    08  10   12   14   IS   18   20    22   24
                              HOUR OF DAY
£ 0.020-
  0.010-
                                       Site     3
      24  02   04   06
08  10   12   14   16   18   20   22   24
      HOUR OF DAY
£ 0.020-
0,
  0.010-
                                      Site   4
       24   02   04  06    08  10   12   14   16   18   20   22   24
                              HOUR OF DAY
 £ 0.020-
   0.010-
                                       Site   6
       24  02  04   06
 08  10   12   14   16   18   20   22   24
      HOUR OF DAY
                               105

-------
the Albany area by the NYSDEC.  Also  included in this table are
total hydrocarbons (HC) measured by flame  ionization at
Rensselaer.

                           TABLE 22
        LONG TERM PHOTOCHEMICAL POLLUTANT  CONCENTRATIONS
                      ANNUAL AVERAGE  (ppm)
          Rensselaer  (4101-02)	    Schenectady (4601-05)
     Year   NO     NO2    03     HC       NO      NO2     O3
1971
1972
1973
1974
1975
1976
1977
1978

-
.014
.015
.011
.010
.012
.013

.013
.018
.018
.015
.016
.014
.015
2.81
2.45
.022
.017 2.74
.022 2.83
.023 3.08
.022
.022

-
.027
.034
.024
.019
.018
.017

.023
.021
.019
.017
.016
.014
.017

-
.022
.019
.017
.020
.022
.029
     Source:  NYSDEC

The hydrocarbons could be emitted  from  the  numerous  tank farms
in the area, from leaks and tanker-to-bulk  storage  and  transfer
operations.  During the study period  a  small  refinery on the
South side of the Port of Albany began  start-up  operations.
Thus, there could have been an additional  source of  hydro-
carbons.  The Albany Steam Station  itself  is  surrounded by
numerous bulk storage tanks for petroleum  products.   The NYSDEC
stopped monitoring for hydrocarbons in  early  1977,  therefore no
hydrocarbon-data was available for  the  test period.
                              106

-------
These pollutants have  long  been  known  to  exhibit  a character-
istic diurnal variation.  This diurnal  variation  has been
observed at various  locations  by Renzetti and  Romanovsky
(1956), Leighton (1961), U.S.  Public Health  Service (1965)  and
by the California Department of  Health  (1966).

During the study period  the NO and N02  concentrations  exhibited
a double maximum double  minimum  diurnal variation at the four
monitoring stations  with NOX monitoring equipment.   These two
pollutants had maximums  during the early  morning  near  sunrise,
and later in the early evening after sunset.   Ozone concentra-
tions did not begin  to increase  until  after  the  morning NOX
maximum.  Ozone decreased in the late  afternoon  with the
decrease in sunlight.

Various models have  been published to  explain  this  diurnal
relationship.  A simplified model is:

     N2 + 02-	^2 NO       (Combustion)
     2 NO + O2	^-2 N02
     NO2 + hy	^-NO + 0     (Sunlight)
     0 + 02 + M—^~°3 + M     (Non-methane  hydrocarbons)
     O2 + NO	^"NO2  + 02

The formation of N02 Proceeds  directly  from  the  plant  emissions
of NO into the atmosphere.  The  presence  of  sunlight (hy),  to-
gether with a suitable catalyst  (M), usually taken  to  be reac-
tive hydrocarbons, results  in  the formation  of O3.   With the
decline in sunlight  in the  late  afternoon,  the formation of O3
decreases and available  03  reacts to form N02,  thus decreasing
03 and causing a N02 Peak in the early  evening.

These pollutant measurements showed a  variation  from one day to
the next.  For the most  part,  the ambient concentrations could
be described as a series of consecutive pulses or spikes.
                              107

-------
While there was no  significant  change in the NO trend at three
of the sites, the base  site  showed  a  decreasing trend during
the study period.   Both NO2  and  O3  showed no change in trend
during the study period at any  of  the sites.  A summary of the
data is contained in Table 23.

There is some indication  by  Larson  et al. (1978) and Penkett et
al. (1978) that elevated  0^  levels  can be influencial in the
conversion of 302 *"° ^04.  Larson  et  al. reported the following
oxidation rate could be significant when 0^ ->0.050 ppm and pH
* 5:

d  [sop  = k4KRO  PQ-   [HSO~]   [H+]  -o.^pi +0.02
                -J   «j
with k4 = (4.4 ± 2.0) X 104  M~°-9S~1
KHO = °-0123 M atm"1, both at 298°K
                              108

-------
                       TABLE  23
            NO, NO.,, O., Concentrations   (ppm)
                 NO                  NO2                0-

                     Standard           Standard           Standard
            Average  Deviation Average  Deviation Average  Deviation
Site 1       0.020     0.035    0.022    0.025
Rensselaer   0.009     0.009    0.010    0.007     0.004     0.008
Site 3       0.012     0.043    0.013    0.010
Base         0.021     0.017    0.007    0.009     0.014     0.015

-------
                          FIGURE   28
 0.030-
 0.020-
 0.010-
      24   02   04   06    03   10    12    14    15    18    20    22   24
                                 HOUK OF
0.030-
0.020-
0.010-
           NO
           NO,	
SITE 3
     24   02    04   06    03   10    12    14    16    18    20    22   24
                                HOUR OF
                Photochemical Pollutant Diurnal Variation
                              110

-------
                              FIGURE   29
  0.030-
£ 0.020-
  0.010-
                RENNSSELAER
            NO
            N02	
       24   02   04   06    08   10    12    14    16   18   20   22    24
                                   HOUR OF DAY
  0.030-
  0.020-
  0.010-
BASE STATION
       24   02   04    06    08    10    12   14   16   IB   20   22   24
                                   HOOR OF DAZ
                    Photochemical Pollutant Diurnal Variation
                                  111

-------
The diurnal variation experienced  in  the  ozone  concentrations
suggests that if this were a  factor  in  S02  to SO4 conversion in
the Albany area, it would be  limited  to a few hours of the
day.  That is, O3 would most  likely  affect  S04  levels during
the 1200 to 1800 time priod.

CARBON MONOXIDE

Carbon monoxide was not measured as  part  of this  experiment.
However, some CO data is available from the NYSDEC.  Table 24
contains long term CO data.

                           TABLE 24
            LONG TERM CARBON  MONOXIDE CONCENTRATIONS
                      ANNUAL  AVERAGE  (ppm)
     Year
     1970
     1971
     1972
     1973
     1974
     1975
     1976
     1977
     1978
           Station/(Station Number)
Rensselaer (4101-02)   Schenectady  (4601-05)
      2.5
      2.8
      2.7
      2.8
      2.5
      1.3
      0.9
      0.7
      0.5
3.0
2.5
2.0
1.2
1.1
0.9
0.8
     Source:
NYSDEC
In a study by Kuhlman  et  al.  (1978)  it  has  been suggested that
the presence of CO decreases  the  rate of  formation of airborne
S04 particulate.  The  CO  was  considered by  Kuhlman et al. to
compete with S02 for the  available OH~  radical thus retarding
                               112

-------
the formation of H2So4.  There  are  insufficient data to test
this hypothesis  in  this  study.

SQLFATE ANALYSIS

The long term (1975-1978)  SO^ distributions  for monitoring sta-
tions run by the NYSDEC  in Troy and  in  downtown Albany are
shown in Figure  29.  This  figure  indicates  that the SO^ tends
to have a log-normal distribution  as  would  be  expected for
ambient particulate concentrations.   The  slopes of  the two
curves appear to be the  same, suggesting  the same sample vari-
ance.  The same variance suggests  that  the  causes of variation
at these two locations may be the  same.   The geometric means
determined from  these distributions  are 10.4 ug/m  for downtown
Albany and 8.1 ug/m^ for Troy.   This  difference of  2.3 ug/m^
suggests local source effect(s).

The long term trend in SO^ is contained in  Table 25.  This
table contains a summary of  available 804 data collected over a
13-year period.  In the  Albany-Troy-Schenectady area there
appears to be a  slowly changing oscillation  with a  wavelength
of about 8 or 9 years and  an amplitude  of about 4 ug/m •  How-
ever, data from New Rochelle near New York  City and Massena in
upstate New York near the  Canadian  border do not show this
oscillation.  If this is true then  this would  suggest that the
Albany-Troy-Schenectady  area possesses  some  uniqueness apart
from either downstate New  York  or Northern  upstate  New York.

A comparison of Albany to  Troy  and  Schenectady indicates that
Albany has higher values of  SO^ than  either  Troy or Schenec-
tady.  The only  exceptions being Troy in  1973  and Schenectady
in 1966.  A comparison of  Troy  to  Schenectady  shows that Troy
was greater than Schenectady 4  times  and  Schenectady greater
than Troy 6 times.  This suggests a  local source/sink phenomena
                                113

-------
    4(
    3C
   20
   10
 _ 9
m  8
P
— 6
 T c
 O D
 Ul

   4



   3
                           1975-1978
                                                                    Downtown  Albany

                                                                   • Troy
                                                     '.Jl  60  /O   M)
                                                                           95
                                                                                98  99
                                                                                           998 999
                                                                                                    •J999
                                    Cununulative Frequency of  Occurance

                                              FIGURE  30

-------
                          TABLE  25
                    Annual Variation  in 304"
                    Geometric Mean  (ug/m  )
0101-03
Downtown  4102-02    4601-02       5904-02      4402-05     1302-04
Year
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
Albany
10.9
10.2
8.9
9.1
8.9
9.6
12.0
10.5
11.7
13.0
11.6
9.9
8.3
Troy
10.3
8.5
8.4
7.7
7.1
7.8
10.4
11.0
10.2
10.7
9.2
7.9
6.8
Schenectady
11.4
-
7.3
8.1
7.3
8.3
10.9
10.0
11.0
9.8
9.1
8.6
7.0
New Rochelle
13.3
12.9
11.6
11.1
10.5
10.2
9.0
8.1
8.9
10.9
-
8.9
7.4
Massena
-
-
3.8
6.3
5.1
5.7
6.3
6.3
5.6
5.7
7.7
7.4
7.0
Poughkeepsie
-
-
-
-
-
-
-
8.8
10.3
11.0
8.9
7.6
_
                                                        Source:  NYSDEC

-------
in the Albany area.  Long range  transport  should not produce
consistently higher geometric means  at  Albany.

Tables 26 and 27 contain data on  the  seasonal  variation of S04
for downtown Albany and for Troy-  As might be  expected, down-
town Albany has consistently higher  values than Troy.  There
appears to be a slight double maximum-double minimum seasonal
variation.  The months of April  and  September  are the minimum
months with the summer and winter  periods  being somewhat
higher.  The 75% values indicate  that large values of S04 are
more likely during the summer months  than  any  other time of the
year.  The differences between  the 50 percentiles and the 75
percentiles are minimal during  spring and  fall  and greater dur-
ing the summer and winter.  This  is  especially  true for Albany
during the summer.  This suggests  that  there is more likely to
be greater differences from one  day  to  the next in the summer
than in the winter.

Figure 30 and Tables 26 and 27  suggest  that the data could be
described as an average level with pulses  occurring from time
to time.  Seasonally these pulses  appear  to be  more frequent in
the summer rather  than the rest  of the  year.  It is these pul-
ses that account for the seasonal  shift in the  monthly average
level  in SO4.  These long term  data  are collected on the one
day in six cycle therefore it is  difficult to  discuss sustained
elevated SO^ episodes.

SO^ data collected during the test period  shows a geometric
distribution similar to that observed for  the  longer period of
record.  The pulse character of  the  data  can be seen in Figures
31 and 32.  The period of record  from September 18 to October
15 contained two significant pulses  as  well as  several lesser
pulses.  The two main pulses occurred on  September 21 and
October 12.  In both cases the  synoptic situation was similar.
There was an elongated high pressure  area  running along the
                              116

-------
                   TABLE  26

    Seasonal Variation in SO.
(ug/m )
                Downtown Albany
         Period of Record:  1975 - 1973
        Cumulative Frequency
Minimum   25%   50%   75%    Maximum
          Sample  Size
Jan
Feb
Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Total
Period
4
5
5
3
3
5
2
4
4
5
4
4
4
.7
.6
.0
.8
.2
.2
.4
.3
.7
.2
.0
.5
.3
7
9
8
6
7
9
7
7
7
7
7
8
7
.7
.8
.5
.6
.9
.3
.8
.7
-0
.5
.8
.4
.8
10.
12.
11.
8.
11.
12.
12.
11.
9-
11.
10.
9.
10.
5
0
0
2
3
5
3
5
0
0
7
6
4
15
15
14
10
14
17
17
21
11
14
13
10
14
.0
.6
.0
.8
.7
.4
.8
.2
.6
.1
.1
.5
.0
57
23
19
26
20
68
24
31
35
20
16
14
68
.0
.1
.2
.2
.3
.6
.8
.5
.0
.4
0
* 
-------
                                    TABLE  2 7
                        Seasonal Variation in SOT (ug/m )
                              Troy,  New York
                         Period of Record:   1975-1978
                         Cumulative Frequency
00
Minimum
Jan
Feb
Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Total
Period
4
6
4
4
5
3
3
5
3
3
4
5
3
.2
.6
.8
.9
.2
.7
.1
.6
.1
.3
.2
.6
.1
25%
6.
8.
6.
5.
7.
8.
5.
7.
5.
5.
6.
6.
6.
7
6
2
7
4
5
2
7
6
0
0
7
2
50%
9
9
8
7
9
10
9
9
6
7
7
7
8
.0
.7
.0
.0
.1
.0
.3
.9
.7
.6
.4
.6
.1
75%
11
12
10
9
11
12
12
16
8
11
8
8
11
.8
.0
.1
.2
.7
.4
.7
.8
.3
.0
.8
.5
.2
Maximum
18
19
16
20
17
25
23
32
30
14
14
10
32
.3
.0
.4
.3
.8
.3
.3
.7
.7
.7
.6
.2
.7
Sample Size
20
15
22
18
21
19
21
16
16
16
18
15
217
                                                                     Source
NYSDEC

-------
Atlantic Coast with  a  cold  front  in the vicinity of the Great
Lakes.  This was  accompanied  by a flow aloft of Southwest
winds.  Local winds  were  from the South on both days.  Thus,
while the Albany  Steam Station might have influenced monitoring
stations to the North,  it  could not have influenced the
Southern stations  and  their pulse is obviously due to some
other source or sources.   It  is  interesting to observe on the
October 12 case that the  Southern stations had higher concen-
trations than the  Northern  sites.

This  feature of elevated  SO^  concentrations on the rear side of
anticyclones or high pressure areas has also been observed by
Y.S.  Chung  (1978).   Chung  noted  these phenomena in Ontario and
in Western Canada.   He specifically mentions the case of May
17-18, 1975 when  Southern  Ontario was under the influence of a
retreating high pressure  area and an advancing cold front.
Maximum values of  both S0^~ and 03 were observed.
                              119

-------
       050-
       040-
       030-.
       020--
       010-
                          FIGURE   31




                   DAILY  SO4  CONCENTRATIONS


                   Sep. 18  -  Oct. 15, 1978



                                   Site   1
              18 19 20 21  22  23 24 25 25 27  23 29 30



                     September
                                                              10 11 12  13  U  15
                                            October
01
31
0
1-1

o
        030-.
020--
        010-
                                       Site   3
              18 19 20  21 22 23 24 25 26  2/  28 29 301



                     September           i
                                     2  3  4  5  6  7  3  «  10 11 12 12 14  L!




                                            October
        020--
        010-1
                             Site   4
              IS  19  20 21 22 23 21  25 26 27 2B 29 30



                     September
                                    1  2  34  5  S  7  3  9  10 11 12  13  14 15



                                            October
                                      120

-------
                          FIGURE   32
                    DAILY  S04 CONCENTRATIONS
                    Sep. 18  - Oct. 15,  1973
020--
010-
                               Site    5
       ,3 19 20 21  22 23 24 25 26  27 J9 29 30

             September            i
                                                3  i ;  i  1  a  J 10 11  12 13 14 15

                                                    October
z
35
030-.
020--
010-
                        Site   6
       18 19 20  21 22 23 2« 25  26 27 28 29 30  1  2 3  4  i  6  7  3  J  10 11 12 13 U  15
              September
                                                     October
020--
 010-"
       18 19 20  21 22 23 24 25  26 27 28 29 30  1  2   ]  4  5  5  7 3  9  10 11 12 13 14  It
              September
                                                     October
                              12.1

-------
                           SECTION  6
                          METEOROLOGY
CLIMATE

The climate is representative of  the  humid  continental  type
prevailing in the Northeastern United States.   The  general  cir-
culation of the atmosphere brings  a variety of  different  air
masses into the region.  Cold dry  air masses  are  brought  in
from the Northern interior of the  continent.  Warm,  humid air
is transported from the Gulf of Mexico  and  adjacent  waters.  At
times air is transported in from  the  North  Atlantic  producing
cool, cloudy and damp weather conditions  (NOAA,  1977).

Many storms and frontal systems moving  eastward  across  the  con-
tinent pass through or in close proximity to  the  State  of New
York.  Two principal storm tracks  can be  identified.  One storm
track moves from the Great Lakes  area Northeast  along the St.
Lawrence River valley.  The second storm  track  is offshore  and
moves Northeast generally parallel to the coast  (Klein,  1957).

A trough of cyclogenesis, centered over the Virginia capes
extends Northeastward offshore along  the  coast.   During  the
September-October time frame this  activity  is at  a  minimum.
Conversely, the Appalachian Mountains are a center  for  the
formation of high pressure areas,  particularly  in October
(Klein, 1957).

DAILY SYNOPTIC SITUATION

For the study period the daily weather  maps prepared by  the
National Weather Service were examined  primarily  with  interest
in the Northeast United States.   A summary  of the synoptic
situation for each day is continued in  Table  28.
                              122

-------
                            TABLE  28
                    DAILY SYNOPTIC SITUATION
Sept. 17  High pressure area centered over Quebec,  Canada,  with
          a stationary front running from  the  Great Lakes
          across Pennsylvania and Maryland.

Sept. 18  High pressure area centered over Quebec,  Canada,  with
          a stationary front East-West over  central Pennsyl-
          vania .

Sept. 19  High pressure area in Canada with  stationary  front
          from the Great Lakes to the Atlantic with cyclo-
          genesis in Pennsylvania.

Sept. 20  Advancing cold front in Great Lakes  with  high pres-
          sure area over New England.

Sept. 21  Advancing cold front along St. Lawrence River Valley
          with retreating high pressure area centered over
          Virginia and North Carolina.

Sept. 22  Frontal passage during night with  cold front  along
          Eastern seaboard.  High pressure area over Great
          Lakes.

Sept. 23  High pressure area over New England.

Sept. 24  Advancing cold front over Great  Lakes with high
          pressure area over New England.

Sept. 25  Frontal passage during night with  cold front  along
          the Atlantic seaboard.  High pressure area over Great
          Lakes.

Sept. 26  High pressure area over New England.

Sept. 27  Advancing cold front over Great  Lakes with retreating
          high pressure area over Nova Scotia.

Sept. 28  Cold front centered over New York  State running from
          mouth of St. Lawrence River Southwest through
          Kentucky.  High pressure area over Great  Lakes.

Sept. 29  High pressure area over New England.

Sept. 30  High pressure area over New England.  Advancing cold
          front over Great Lakes.
                             123

-------
                            TABLE 28

Oct. 1    Advancing cold front over Eastern Great Lakes.   High
          pressure area retreating towards Iceland.

Oct. 2    Frontal passage during night with cold front  over
          Nova Scotia.  High pressure ridge extending  from
          Hudson Bay South through Great Lakes.

Oct. 3    Advancing cold front over Great Lakes.  High  pressure
          ridge along Atlantic seaboard.

Oct. 4    Advancing cold front over Eastern Great Lakes with
          warm front over St. Lawrence River.

Oct. 5    Frontal passage with cold front in New England.
          Advancing cold front vicinity of Great Lakes.

Oct. 6    Remnants of decaying cold front offshore  in
          Atlantic.  Advancing cold front with  front running
          North-South over central New York State.

Oct. 7    Cold front passed with front over Quebec-Nova
          Scotia.  High pressure area over Great Plains.

Oct. 8    High pressure area centered over Mississippi  River.

Oct. 9    Advancing high pressure area centered over West
          Virginia.

Oct. 10   High pressure area centered over Virginia capes  with
          a cold front running East-West over Southern  Canada.

Oct. 11   High pressure area over Maine.  Weak  front running
          from Hudson Bay across New York State into the
          Atlantic.

Oct. 12   High pressure ridge along Atlantic seaboard with
          advancing cold front area Great Lakes.

Oct. 13   Cold front running Southwest from Maine to Arkansas.
          Rain following frontal passage along  entire  front.

Oct. 14   Slow moving cold front running Southwest  from Boston
          to Atlanta accompanied by rain.

Oct. 15   Cold front offshore in Atlantic.  Advancing  low  pres-
          sure area approaching Great Lakes.

Oct. 16   Low pressure area over Ohio with high pressure area
          approaching Great Lakes.


                              124

-------
During the study period  the  usual  pattern was for a series of
cold fronts to advance generally westerly from the Great Lakes
through the study area.  A  series  of  seven such fronts were in
the area and/or passed through  the Albany area during the study
period.
WINDS
The annual wind pattern  as  observed  at  the Albany airport shows
a prevailing southerly wind with  secondary maximums in the
North and West Northwest.   Seasonally there is a shift in this
pattern.  During  the winter months of December through March,
the prevailing winds are  from  the West  Northwest.  During the
months of April through  November, the southerly winds are pre-
vailing.  This is  especially  true during the summer months of
June, July and August.

The wind frequency  distribution  for  Albany airport, Rensselaer
(Port of Albany),  base station,  and  Niagara Mohawk meteorologi-
cal tower all show  similar  patterns  for the study period.  All
stations show a southerly maximum with  secondary maximums
generally out of  the North  to  Northwest.

Concurrent winds  among these  stations show a strong comparison
indicated by Figure 33.   One  of  these figures was prepared for
each day during the study period. This indicates that wind
direction at one  station  is generally similar to wind direction
at another.  Moreover, when the  shift from essentially down
valley flow to up  valley  flow  occurs, it occurs at all stations
at about the same  time.

For the study period, valley winds,  as  a general rule, were not
observed.  By valley winds, it is meant the diurnal shift in
wind direction from up valley  during the day shifting to down
valley during the  night.  Most of the wind shifts that were
                               125

-------
FIGURE  33
 date   October 09

hour
1
2
3
4
5
6
7

8
9
10
11
12
13
14
15
16
17
18
19

20
21
22
23
24

upper
<
<
<
^
<.
^

"*"
N
\
f
(
f
r,
i
r
r
r-
r
___r

/
i
-f
.j
^
WIND DIRECTION
lower base REN ALB
X 	 X -c-
-<-, ^-. \ ±-
	 	 _, 	 \ (
— ^- ^ (—
— ^^ -<- L-
/ /- •*• 9

f f ^* ]~~"
\ / 1 L~'
X X ^ U-

-^ ^ ^ L,
N X ^ !_
\ \ <, k
\ \ ^ • C.
•<, \ ^ ^X
\ \ <. ^
t \ { \
\ ~^ \ s>
— t
^ J
/ / ^ ®
7 744
7 Y \ 4
^ y j -f
/ ./ -f /

site
^
/
S
^-
— •
^

^"
/-
I
-^
\
\
\
V
\
1
\
~^.

•^
i^
-^
-/
A
,/
         126

-------
observed were associated  with  synoptic weather features.  Dur-
ing frontal passages,  the general  pattern was for the wind
direction to shift  from South  to North.   By about the second
day after a frontal  passage,  the winds would shift back to
South again.  Local  features  tended  to impose some perturbation
on this basic North-South flow.

UPPER ATMOSPHERIC MEASUREMENTS

The average diurnal  temperature profile  for the study period is
contained in Table  29  and Figure 34.   There was only one tem-
perature sounding for  the 0400  time  frame,  therefore, it is not
included.  In addition, the  1300 sounding for September 23
appears to be an anomalous sounding  and  is  not included in the
average diurnal presentation.

The upper air diurnal  pattern  appears  to be similar to that
defined by the Niagara Mohawk  meteorological tower.  Stable
conditions are observed at night and  unstable conditions during
the day.  Radiation  cooling  at  the surface  results in the for-
mation of a surface  stable layer by  1900.   The diurnal AT data
indicates this surface inversion is  during  the 1700-1800 time
period.  This surface  inversion extends  through the first 500
feet AGL as measured  from the  Hudson  River  bottom land.
Another stable layer  also forms during the  early evening.  This
second layer lies immediately  above  the  surface stable layer.
This second layer may  be  thought of  as an extension of the sur-
face layer and extends from  about  500  feet  to 1500 feet AGL.
This layer is generally isothermal.

As indicated in Table  29,  by  shortly  after  sunrise the atmos-
phere has become almost isothermal up  through 3000 feet AGL.
The Niagara Mohawk  tower  shows  the transition from stable to
unstable takes place  rather quickly  (Table  30).  During the
                              127

-------
                   TABLE  29
       AVERAGE DIURNAL  TEMPERATURE ALOFT (°C)
               ALBANY STEAM PLANT
PERIOD OF RECORD:  Sept.  22,  1978-Oct.  15,  1978
                 Height Above  Ground (ft)



\->
NJ
00




Time (EST
0100
0400
0700
1000
1300
1600
1900
2200
Surface
11
-
7
13
16
16
13
11
.5

.9
.3
.0
.6
.5
.9
500
11.9
-
8.5
10.9
14.0
1 .3
14.7
13.7
1000
12.1
-
8.7
9.5
12.6
14.2
14.2
13.6
1500
12.1
-
8.4
8.3
11.1
12.8
14.2
13.0
2000
11.3
-
8.6
7.0
10.4
11.9
12.5
12.4
2500
11.0
-
8.1
5.7
9.8
11.0
11.4
11.5
3000
10
-
7
3
9
10
10
11
.5

.6
.9
. 9
.2
.7
.1
Number Soundings
6
-
6
6
5
9
7
7

-------
                          FIGURE  34

                        AVERAGE  DIURNAL


                      TEMPERATURE  PROFILES
  3000-1
  2500-
  2000-
4J

0)
0)
-p
,c
  1500-
  1000-
                                                        Time Of Day
   500-
       05  06
07 08  09   10
                              Temperature  (C)
                                129

-------
day the lower 3000 feet of  the  atmosphere is unstable once the
morning inversion breakup  takes  place.

The significance of  this  is  that the  plume is emitted into
stable air from early  evening  through the morning inversion
breakup.  Consequently the  contents of  the plume would be dis-
persed slowly during the  night  and would have a minimal impact
during these hours.

From the pibal wind  frequency  tables  it can be seen that the
wind did change in regard  to height.   The wind speed at the
ground had a very high percentage of  occurrences at the lower
speeds (0-18 mph).   The 1000 foot level had most of its wind
speeds in the 4-31 mph range,  the 2000  foot in the 8-38 mph
range, and the 3000  foot  level  in the 13-38 mph range.  The
wind direction remained constant with height during northerly
winds.  During southerly  winds,  as height increased, the winds
shifted toward the West.   This  can clearly be seen from Figure
35.  Tables 31, 32 and 33  summarize the upper air wind pat-
terns .

From Table 34 it can be observed that there were definite
diurnal patterns with  regard to  upper air temperatures.  This
can be seen clearly  by looking  at the day of October 12.  At
0100 a stable condition exists,  by 1008 this stable condition
has become unstable  allowing mixing of  the atmosphere, at 1322
the atmosphere has become  adiabatic,  at 1533 it was becoming
stable, and, at 1906 it had  become very stable.  This condition
existed through 2155,  and  by 0100 the atmosphere had become
isothermal.

VISIBILITY

It has been recognized for  many  years that degradation of visi-
bility can be caused by air  pollution.   However, air pollution
                              130

-------
                      TABLE   30

          FREQUENCY DISTRIBUTION OF STABILITY CLASS
            NIAGARA MOIIWAK METEOROLOGICAL TOWER
          PERIOD OF RECORD:  SETP. 17,  1978-OCT.  16,  1978
                   PASQUILL STABILITY CLASS  (delta-T  method)
Hour
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Totals
A
0
0
0
0
0
0
0
6
20
22
23
24
24
25
23
16
1
0
0
0
0
0
0
0
184
B
0
0
0
0
0
0
0
3
1
3
4
3
3
1
0
6
1
0
0
0
0
0
0
0
25
c
1
1
1
2
0
1
1
1
3
1
2
2
1
1
3
0
3
0
0
0
0
0
0
1
25
D
4
8
6
4
11
8
15
14
6
4
1
1
2
z
3
7
22
10
5
5
9
6
6
6
" 165
E
14
11
15
17
12
15
8
6
0
0
0
0
0
1
1
1
3
20
17
18
12
16
12
11
210
F
8
9
7
7
5
4
6
0
0
0
0
0
0
0
0
0
0
0
7
4
6
5
9
8
85
G
2
1
1
0
2
1
0
0
0
0
0
0
0
0
0
0
0
0
1
3
3
3
3
4
24
Missing
1
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
Valid hours
29
30
30
30
30
29
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
718
NOTE: STABILITY CATEGORIES TAKEN FROM NRC SAFETY  GUIDE  1.23
                      131

-------
DATE
9/22/78
9/22/78
9/23/78
9/23/78
9/24/78
9.25. 78
9/25/78
9/25/78
9/25/78
9/25/78
TIME
EST
1432
1555
1000
1300
1000
0735
1750
1006
1320
1540
9/29/78
9/29/78
9/29/78
9/29/78
0730
1015
1420
1608
                                                TABLE   31

                                          UPPER AIR PROGRAM DATA LOG

                                                NIAGARA MOHAWK
                        OBSERVATION
                 PIBAL   SONDE   DOUBLE   DIR
                                           BASE
                                                          1000'
                    x
                    X
                    X
                    X
9/26/78   0720     x
9/26/78   0951
9/26/78   1314     x
9/26/78   1611     x

9/27/78   0726
9/27/78   1019     x
9/27/78   1338     x
9/27/78   1552     x

9/28/78   0731     x
9/28/78   1016
9/28/78   1255     x
9/28/78   1605
x
X
                           X
                           X
                           X
                           X
                             180
                             350

                             030
                             040
                          SPEED


                          08.0
                          06.0

                          04.0
                          04.0
                                        194    05.0
DIR


037
046

019
*

238
                                                              2000'
                                                                  SPEED
                                                                              TOWC R
                                                                              FASQUU.L
                                                                    3000'      STABILITY
                                                                  DIR    SPEED  CLAPS
25.3
21.2

05.5
                                                                            11.9
                                                                                     046
                                                                                     194
                                                                                     279
                                                                                           30. 9
                                                                                           07. 4
                                                                                           07. 4
                        A
                        B











X
X



X



X
150
180
290
315
270
360
050
360
-100
185
180
180
170
300
320
3CTO
320
340
330
360
090
04.0
03.0
20.0
12.0
12.0
03.0
05.0
05.0
05.0
03.0
10.0
11.0
12.0
03.0
20.0
11.0
14.0
03.0
02.0
03.0
02.0
*
306
334
348
319
019
045
034
234
195
197
265
*
237
324
324
037
334
349
059
133
*
09
35
09
40
06
06
01
04
18
24
17
*
04
40
23
39
12
07
07
03

.2
.6
.6
.6
.8
. 9
.9
.1
.4
.9
.9

. 4
.7
.9
.8
. 8
. 3
. 7
. 3
*
*
344
358
331
*
351
336
246
202
200
260
*
*
329
354
040
357
004
350
140
*
*
31.
08.
21.
*
04.
01.
05.
34.
20.
34.
*
*
14.
24.
56.
08.
11.
04.
03.


1
7
9

4
2
7
4
1
2


6
2
3
5
1
7
2
*
*
330
349
345
*
035
295
278
*
218
249
*
*
328
005
047
357
024
339
107
*
*
-10.
21.
26.
*
07.
10.
09.
*
14.
12.
*
*
42.
26.
26.
08.
10.
1.1.
07.


5
1
9

2
6
8

7
5


8
8
5
0
1
3
6
E
E
B
B
D
C
A
B
D
D
A
B
D
D
A
A
D
E
B
C
E
* INDICATES THAT THE PIBAL WAS OBSCURED  FROM  VIEW

-------
u>
                                                            TABLE   31




                                                      UPPER AIR PROGRAM  DATA  LOG




                                                            NIAGARA MOHAWK

DATE
9/30/78
9/30/78
9/30/78
10/01/78
10/01/78
10/01/78
10/02/73
10/02/78
10/02/78
10/05/78
10/05/78
10/05/78
10/05/78
10/06/78
10/06/78
10/06/78
10/06/78
10/06/78
10/06/78
10/06/78
10/06/78
10/07/78
10/07/78
10/07/78
10/07/78
10/07/78
10/07/78
TIME
EST PIBAL
0730
1000 x
1350 x
0955 x
1316 x
1543
0730
1005 x
1306 x
1306
1619
1924
2215
0158
0415 X
0704 x
1005 x
1315 x
1532
1902
2210
0040
0430 x
0700
1003
1310
1615
OBSERVATION BASE
SONDE
x




X
X


X
X
X
X
X




X
X
X
X


X
X
X
DOUBLE DIR
190
180
180
180
180
220
330
350
350
180
x 180
210
140
240
180
180
140
140
x 200
270
220
220
210
x 200
x 090
x 290
320
SPEED
04.0
15.0
18.0
13.0
13.0
05.0
07.0
10.0
08.0
09.0
08.0
04.0
04.0
03.0
Q5.0
05.0
04.0
11.0
06.0
02.0
02.0
04.0
03.0
04.0
03.0
08.0
12.0
1000'
DIR
194
206
196
101
212
236
009
014
010
240
268
165
167
169
*
167
189
203
077
310
235
254
*
295
078
002
334
SPEED
34. 8
19.0
12.1
04. 7
24.0
13.4
23.7
29.9
05.9
03.2
12. 7
19.9
26.0
15.1
it
25.0
08.5
07.0
12. 2
13.2
10. 7
09. 8
*
39. 3
07.0
18.2
23.3
2000'
DIR
210
*
212
212
221
251
*
018
009
*
262
183
173
162
*
170
*
*
078
299
272
279
*
#
013
020
333
SPEED
39.
*
17.
42.
26.
11.
*
34.
14.
*
23.
34.
39.
21.
*
34.
*
*
09.
14.
19.
18.
*
*
33.
16.
21.
1

5
2
2
2

5
1

2
0
2
7

3


2
7
2
4


5
9
8
3000'
DIR
*
*
222
211
236
281
*
019
006
*
251
186
194
*
*
202
*
*
081
289
301
302
*
*
*
012
338
SPEED
*
*
24
47
23
13
*
19
18
*
27
31
35
*
*
26
*
*
13
23
19
24
*
*
*
16
20


. 7
.3
. 7
. 7

.8
. 7

. 7
. 6
. 2


.5


. 9
. 4
. 8
.0



.4
.5
TOWER
PASQUIH.
STABILITY
CLASS
D
A
B
C
D
E
E
D
A
A
D
E
E
E
E
D
D
C
n
E
F
E
E
E
D
C
D
            *  INDICATES THAT THE PIBAL WAS  OBSCURED FROM VIEW

-------
U)
                                                            TABLE   31




                                                      UPPER AIR PROGRAM  DATA  LOG




                                                            NIAGARA MOHAWK


DATE
10/07/7S
10/07/78
10/08/78
10/08/78
10/08/78
10/08/78
10/08/78
10/08/78
10/08/78
10/08/78
10/09/78
10/09/78
10/09/78
10/09/78
10/09/78
10/09/78
10/09/78
10/09/78
10/10/78
10/10/78
10/10/78
10/10/78
10/10/78
10/10/78
10/10/78
10/10/78

TIME
EST
1902
2154
0040
0433
0711
1002
1310
1602
1907
2225
0045
0430
0712
1006
1324
1604
1923
2205
0500
0455
0705
1006
1256
1611
1900
2206


OBSERVATION BASE
PIBAL SONDE DOUBLE DIR
x 330
x 210
x 240
x 300
x 330
x 330
x 290
x 300
x 330
x 300
x 280
x 230
x 210
x 300
x 330
x x 330
x 210
x 180
x 190
x 170
x 180
x 180
x 100
x x 300
x 280
x 200
SPEED
04.0
02.0
01.0
04.0
03.0
08.0
08.0
08.0
05.0
02.0
02.0
02.0
02.0
08.0
09.0
06.0
03.0
04.0
04.0
04.0
06.0
06.0
10.0
05.0
02.0
01.0


1000'
DIR
326
314
319
337
029
031
305
323
341
334
335
325
*
035
032
056
309
221
239
250
248
281
248
027
341
348
SPEED
27.5
15. 3
23.4
24.2
18.5
22.6
29. 3
22.4
26.8
28.1
25.4
25. 7
*
48.0
11.5
10.6
04.7
15.5
19. 2
13. 8
12.2
14.0
11.2
15.0
17.4
14.9


2000'
DIR
327
296
326
*
030
021
314
318
335
344
347
335
*
030
050
033
293
269
269
301
305
*
327
022
329
329
SPEED
35.5
30.6
24.4
*
68.5
17.9
29.1
35.6
24.8
27.4
23.9
27.9
*
57. 2
18.3
11.9
09.9
25.3
47.6
21.9
27.5
*
07.0
22.4
19.5
15.8



3000'
DIR
329
327
331
*
033
026
332
319
336
348
003
340
*
026
032
018
282
297
*
*
*
*
314
017
310
345
SPEED
65.
33.
30.
*
53.
32.
18.
35.
44.
31.
18.
27.
*
82.
19.
35.
15.
28.
*
*
•*
*
19.
29.
23.
23.
2
5
3

8
2
2
2
5
7
0
0

0
5
5
5
5




2
9
0
2
TOWE R
PASQUILL
STABILITY
CLASS
E
E
E
E
D
A
C
D
E
E
E
E
E
A
A
E
F
F
F
E
D
B
C
D
E
E
            10/11/78  0050            x             250   03.0




            *INDICATES THE PIBAL WAS OBSCURED  FROM VIEW
037
                                                                         15. 3
                                                                                   356
                                                                                         15.9
                                                                                                  338
                                                                                                        21. 5

-------
U)
Ul
                                                            TABLE   31

                                                       UPPER AIR PROGRAM  DATA LOG

                                                             NIAGARA MOHAWK
TIME OBSERVATION BASE
DATE
10/11/78
10/11/78
10/11/78
10/11/78
10/11/78
10/11/78
10/11/78
10/12/78
10/12/78
10/12/78
10/12/78
10/12/78
10/12/78
10/12/78
10/12/78
10/13/78
10/13/78
10/13/73
10/13/78
10/13/78
10/13/78
EST PIBAL SONDE
0445 x
0651 x
1005 x
1336
1602 x
1905 x
2155 x
0100 x
0440 x
0710
1008 x
1322 x
1553 x
1906 x
2155 x
0100 x
0450 x
0719 x
1010
1327
1550 x
DOUBLE DIR
190
180
180
x 180
160
190
180
180
170
x 170
x 175
x 170
x 180
180
180
180
240
170
x 175
x 310
330
SPEED
03
03
12
14
14
06
05
03
07
07
12
13
14
06
04
06
05
08
14
07
04
.0
.0
.0
.0
.0
.0
.0
.0
.0
0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
1000'
DIR
192
206
198
261
192
187
202
200
199
*
269
269
269
212
196
201
199
*
262
063
017
SPEED
25.
13.
10.
13.
13.
29.
27.
25.
27.
*
28.
26.
33.
33.
35.
31.
34.
*
20.
07.
14.
0
7
7
3
6
5
0
4
5

6
7
2
5
4
9
3

1
6
8
2000'
DIR
359
190
215
248
*
198
212
196
*
*
278
263
284
207
198
227
202
*
*
092
353
SPEED
17.
08.
17.
22.
*
34.
37.
32.
*
*
36.
21.
26.
18.
24.
26.
50.
*
*
07.
16.
3
4
7
5

0
0
7


7
6
3
4
0
1
6


0
4
3000'
DIR
*
204
197
*
*
201
208
213
*
*
*
270
302
216
233
240
*
*
*
322
316
SPEEI
*
07. 9
11 .4
*
*
32.1
35.8
37.5
*
*
*
22. 7
11.2
15.0
14.1
39. 3
*
*
*
04 . 0
13.G
           10/14/78  1311
           10/15/78
           10/15/78
           10/15/78
1020
1316
1520
x
X
210

300
310
337
03.0

15.0
12.0
24. 7
186

312
329
336
228

17.4
34.0
21.0
196

338
329
339
                                                                                          45. 9
14. 7
45.8
20.6
327   62.5
330   28.0
                                                                                           TOWER
                                                                                           PASOl'ILI,
                                                                                           STAB I!, I TV
                                                                                             CLASS

                                                                                             E
                                                                                             D
                                                                                             B
                                                                                             C
                                                                                             E
                                                                                             E
                                                                                             E

                                                                                             E
                                                                                             E
                                                                                             D
                                                                                             A
                                                                                             C
                                                                                             D
                                                                                             F
                                                                                             E

                                                                                             E
                                                                                             E
                                                                                             n
                                                                                             B
                                                                                             D
                                                                                             E
A
1.1
n
            *INDICATES TIIE PIBAL  WAS  OBSCURED FROM  VIEW

-------
               TYPICAL PIBAL TRAJECTORY
1 minute  intervals
                             6000
                            s
                       FIGURE  35
                           136

-------
                      TABLE  32
       SUMMARY OF MEAN WIND DIRECTIONS AND SPEEDS
Direction
Direction S.D.
Speed
Speed S.D.
                   BASE      1000'
                        NORTHERLY
2000'
3000
341.4
24.5
7.9
6.1
10.2
31.5
18.3
12.0
001.6
26.0
21.8
18.5
349
49.4
27.2
18.8
Direction
Direction S.D.
Speed
Speed S.D.
                        SOUTHERLY
183.4
13.8
7.3
4.3
201. 3
63. 3
20.1
8.9
211.4
58.2
25.5
9.5
226.6
61.1
24.0
11.1
Direction
Direction S.D,
Speed
Speed S.D.
                        WESTERLY
68.9
36.5
6.2
5.0
324
55.5
21.2
10.2
331.2
51.3
23.17
11.5
336. 8
29.6
28.2
14.3
Direction
Direction S.D.
Speed
Speed S.D.
                        EASTERLY
96.6
5.7
5.7
4.0
205
62.7
6.2
4.3
237-7
93.7
5.3
1.9
233
110.6
12.2
6.2
Categories include summation of soundings coincident with
ground level wind direction within that quadrant.
                            137

-------
                                                         TABLE   33
                                           FREQUENCY DISTRIBUTION OF WIND SPEED & DIRECTION

                                                         PIBAL OBSERVATIONS
                                                               30 FEET
U)
00
   WIND
DIRECTION

349-11 N
12-33  NNE
34-56  NE
57-58  ENE
79-101 E
102-123 ESE
124-146 SE
147-168 SSE
169-191 S
192-213 SSW
214-236 SW
237-258 WSW
259-281 W
282-303 WNW
304-326 NW
327-348 NNW
MISSING
                                                           WIND SPEED MPH
0-3
1.90



1.90



4.76
5.71
1.90
2.86
2.86
1.90

2.86
4-7
1.90
0.95
1.90

0.95

1.90
0.95
15.14
3.81
1.90
0.95

1.90
0.95
4.76
8-12 13-18 19-24 25-31 32-28 39-46
1.90



0.95

1.90
0.95
7.61 7.61



0.95
4.76 0.95 0.95
2.86 0.95 0.95
1.90 0.95
47 MISS TOTAL
5-71
0.95
1.90
0.00
3.81
6.00
2. 85
1.90
35.24
9.52
3.81
3.81
3.81
10.48
5.71
10.48
           TOTAL
                               26.67
                                       38.09  21.90   10.48
                                                 2.86
100.00

-------
                                                 TABLE  33
                               FREQUENCY DISTRIBUTION OF WIND SPEED & DIRECTION

                                             PIBAL OBSERVATIONS
                                                 1000 FEET
   WIND
DIRECTION

349-11 N
12-33  NNE
34-56  NE
57-58  ENE
79-101 E
102-123 ESE
124-146 SE
147-168 SSE
169-191 S
192-213 SSW
214-236 SW
237r258 WSW
259-281 W
282-303 WNW
304-326 NW
327-348 NNW
MISSING

TOTAL
0-3
4-7   8-12
      WIND SPEED MPH
13-18   19-24   25-31
                                             32-28   39-46
                                                      47
MISS   TOTAL


0.95



0.95




0.95





2. 86
1.
1.
0.
2.
0.




0.
0.
0.


0.


12.
90
90
95
86
95




95
95
95


95


38

1.
0.
0.




0.
1.
0.
2.
0.

0.
0.

13.

90
95
95




95
90
95
86
95

95
95

33
0.
2.
1.





0.
2.
1.
0.
2.

2.
2.

20.
95
86
90





95
86
90
95
86

86
86

95
0.
0.





0.
0.
2.

0.
0.
0.
1.
2.

14.
95
95





95
95
86

95
95
95
90
86

28

1.





1.
0.
5.


1.

2.
2.

18.

90





90
95
71


90

86
86

09
4.76
9.52
0.95 0.95 6.67
4.76
0.95
0.00
0.95
2.86
4.76
3.81 18.09
4.76
6.67
0.95 7.62
0.95 1.90
1.90 11.43
1.90 11.43
6.67
6.67 3.81 0.95 6.67 100.00

-------
                                              TABLE   33
                               FREQUENCY DISTRIBUTION OF WIND SPEED  & DIRECTION

                                             PIBAL OBSERVATIONS
                                                 2000 FEET
   WIND
DIRECTION

349-11 N
12-33  NNE
34-56  NE
57-58  ENE
79-101 E
102-123 ESE
124-146 SE
147-168 SSE
169-191 S
192-213 SSW
214-236 SW
237-258 WSW
259-281 W
282-303 WNW
304-326 NW
327-7348 NNW
MISSING
0-3
4-7   8-12
      WIND SPEED MPH
13-18   19-24   25-31
32-28
39-46
                                                              47   MISS
                                                                          TOTAL






0.96








0.96

1.92 2.88
0.96 0.96

0.96
0.96



0.96


0.96 1.92

0.96

0.96

3.85
1.92
0.96






1.92
0.96

0.96
0.96

2.88

0.96
0.96
0.96




0.96

1.92

0.96
2.88
0.96
0.96
4.81



0.96







1.92

0.96
1.92
1.92
2.83


1.92






1.92
3.85


1.92

0.96
0.96


0.96
0.96



0.96

0.96
2.88 0.96


0.96


0.96

9.62
7.69
3.85
0.96
0.96
0.00
1.92
0.96
3.85
11.54
2.88
3.85
7.69
4.81
3.85
12.50
21.15
TOTAL
                    1.92
        5.77   8.65   14.42    16.34
                                                        10.58
                                            11.54
                                                                          4.31
                                                    4.81  21.15 100.00

-------
                                              TABLE  33
                               FREQUENCY DISTRIBUTION OF WIND SPEED & DIRECTION

                                             PIBAL OBSERVATIONS
                                                 3000 FEET
   HIND
DIRECTION

349-11 N
12-33  NNE
34-56  NE
57-58  ENE
79-101 E
102-123 ESE
124-146 SE
147-168 SSE
169-191 S
192-213 SSW
214-236 SW
237-258 WSW
259-281 W
282-303 WNW
304-326 NW
327-348 NNW
MISSING
0-3
4-7
8-12
      WIND SPEED MPH
13-18   19-24   25-31
32-28   39-46
                                                              47   MISS   TOTAL


0.




94


0
0



.94
.94



1.
0.
0.

0.
89
94
94

94
0.
1.



94
39



0.
0.
1.


94
94 0.94 1.89
89


0.94



1.


0.

0.





89


94

94





0

0
0
1

0




.94

.94
.94
.89

.94





2.

0.
0.
0.
0.





83

94
94
94
94





1.

0.
2.
1.
2.





09

94
03
89
83



0.
0.

0.

0.

4.



94
94 3.77 0.94

94 0.94

94
0.94
72 1.89 2.83 1.89

4.
7.
5.
0.
0.
0.
0.
0.
0.
8.
4.
2.
3.
6.
4.
16.
33.
72
56
77
00
94
94
00
00
94
49
72
83
77
60
72
04
96
TOTAL
                    0.00
                            5.66  7.54  11.32   13.20   12.26
                                                                  7.54
                                                                          3.77    4.71   33.96 100.00

-------
                           TABLE   34

              TEMPERATURE (C°)  CHANGE WITH HEIGHT @ BASE SITE
         TIME
DATE
10/07/78 0040
10/07/78 1003
10/07/78 1310
10/07/78 1615
10/07/78 1902
10/07/78 2154

10/08/78 0400
GROUND

06.6
13.2
16.1
12.1
08.8
05.8

04.9
10/09/78 1604
10/09/78 1923
10/09/78 2205
10/10/78 0050
10/10/78 1611
10/10/78 1900
10/10/78 2206
10/11/78 0050
10/11/78 1905
10/11/78 2155
10/12.78 0100
10/12/78 1008
10/12/78 1322
10/12/78 1553
10/12/78 1906
10/12/78 2155
13.7
06.0
04.9
03.6
19.9
16.6
14.3
14.3
17.4
16.3
13.7
18.2
20.4
22.7
14.8
41.8
10/13/78 0100     16.1

10/15/78 1020     08.0
10/15/78 1316     09.0

500
07.3
11.6
13.0
10.1
07.9
09.0
08.8
12.0
11.7
07.0
05.2
19.2
19.5
16.2
16.0
17.7
15.7
13.2
15.0
18.7
21.6
17.6
16.2
16.1
05.9
08.0

1000
07.3
10.7
12.0
08.7
06.8
09.1
08.5
11.2
11.6
10.6
09.9
18.0
18.8
16.0
14.5
16.6
14.2
12.2
13.8
17.5
20.6
17.9
15.5
16.1
02.5
07.2
HEIGHT
1500
07.8
09.9
10.6
07.2
06.0
08.6
08.6
09.4
11.0
10.6
09.6
16.5
18.0
15.5
15.3
15.6
13.3
11.8
12.9
15.7
19.2
17.8
14.9
16.2
-0.2
06.0
(ft)
2000
06.4
08.6
09.8
06.8
05.0
07.7
07.4
08.4
10.0
09.9
09.1
16.
16.9
15.4
14.3
14.4
12.3
11.2
11.6
14.8
18.4
16.7
15.6
16.2
-2.9
04.7

2500
05.2
08.0
08.7
05.7
03.8
06.5
06.2
07.3
09.1
08.7
09.0
15.2
16.4
14.7
14.2
13.2
11.4
11.6
10.7
13.8
18.0
15.5
15.4
15.8
-5.7
03.9

3000
04.2

07,2
04.2
02.8
05.5
05.1
06.3
09.0
07.9
08.4
13.9
15.8
14.9
13.5
12.1
10.6
11.4

17.7
17.0
14.9
15.1
14.9
-7.3
03.0
                                  142

-------
               TABLE   34
TEMPERATURE  (C°) CHANGE WITH HEIGHT @ BASE  SITE
DATE
9/22/78
9/22/78
9/23/78
9/23/78
9/24/78
9/25/78
9/26/78
9/27/78
9/28/78
9/28/78
9/29/78
9/29/78
9/30/78
10/1/78
10/2/78
10/5/78
10/5/78
10/5/78
10/5/78
10/6/78
10/6/78
10/6/78
TIME
(EST)
1432
1555
1000
1200
0724
0735
0951
0726
1016
1605
0730
1608
0730
1543
0730
1306
1619
1924
2215
0158
1902
2210
HEIGHT (FT)
GROUND
16.0
15.2
13.5
21.0
01.8
11.5
07.9
07.1
18.8
15.0
03.8
15.8
09.5
17.8
13.9
18.6
16.0
15.6
14.8
14.8
' 15.6
12.3
500
15.1
15.. 4
12.1
13.5
07.1
11.4
04.7
07.3
16.0
13.2
04.3
14.0
08.0
17.0
13.0
15.5
14.7
14.2
14.5
13.6
15.0
17.0
1000
13.2
15.1
11.2
10.4
06.6
12.2
03.8
07.8
14.7
12.5
05.5
13.4
07.9
16.2
12.6
13.2
13.3
14.2
13.5
13.0
13.7
16.2
1500
11.8
15.4
10.6
08.6
05.4
12.3
02.5
07.0
14.1
11.3
06.0
12.0
08.6
15.4
11.2
11.4
11.9
13.9
13.0
11.8
12.4
14.9
2000
10.6
14.9
10.3
04.6
11.7
1.2
08.8
12.9
10.2
05.5
11.1
08.6
14.5
12.4
12.4
10.8
13.3
12.3
10.8
11.3
13.4
2500
10.4
14.1
10.2
04.1
10.4
-0.5
09.4
11.6
9.0
04.6
09.0
08.2
13.4
12.2
12.2
09.8
12.4
11.8
10.3
09.5
11.6
3000
10.8
14.8
09.2
03.6
09.6
-1.6
10.1
10.1
09.0
03.7
08.2
07.4
12.2
11.4
11.1
09.6
11.3
12.0
10.5
08.5
11.3
                     143

-------
is not the only cause  for decreased  visibility.   Atmospheric
moisture is considered to play a  significant  role in visibility
reduction.  This has been reported on  by  Wright  (1935,  1939),
Junge (1963), Buma  (1960) and Winkler  (1973).  Moreover,  the
size of atmospheric particles likely to adversely influence
visibility is small.   Horvath and Charlson  (1969) reported the
optically important aerosols  to be a narrow range centered
about a diameter of 0.50 um.

The importance of relative  humidity  on visibility can be  seen
in Figure 36 representing measurements at Newburgh,  NY  (Reiss
and Eversole, 1978).   This  location  is South  of  Albany  along
the Hudson River about 80 km North of  New York City.

Visibility data in  the Albany area has the  log-normal distribu-
tion mentioned by Reiss and Eversole (1978).   The Albany  data
also shows a seasonal  variation as seen  in  Table 35.  This
table was compiled  from the 3-hourly observations contained in
the Local Climatological Data (LCD)  for Albany and includes
observations with precipitation.  This seasonal  variance  is a
widespread phenomena with much of New  England  experiencing low
visibilities during the summer months.  This  is  partially due
to the shift to southerly winds brought  about  by the northward
shift of the Azores High.

This table shows a  rather abrupt  shift in visibility between
September and October.  September is one  of the  worst months
for visibility and  October  is one of the  better  months.

During the study period, visibilities  were  measured  at  the Base
site and at Site 5  by  nephelometers.  The values presented here
are in units of bsca^.  which is approximately  inversely  propor-
tional to visibility.  The  diurnal variation  in  bscat is  shown
in Figure 37.  The  base site was  found to have somewhat better
visibility than Site 5.  This suggests that Site 5 was  more
                              144

-------
                      FIGURE  36
              50

              40


              JO



              20
                  i   i   i   i  \   r
o    +
    •t-
 o o
                                 -t- + +•
                                     +

                               o      -»•
                                  o
                    O Geometric mean        H

                    +• Geometric mean lone standard
                     deviation
                0  IO  20  JO «0  50  60 70  80  90 IOO

                       Relative humidity,  '/.
        Dependence of daytime  (15Z,  18Z,  21Z)  visibility
on relative humidity at Newburgh,  NY  (1948-1970)  for
observations  in which no precipitation was  observed (all
wind  directions).   (Reiss and Eversole,  1978)
                             145

-------
                       TABLE  35
               ALBANY AIRPORT VISIBILITY  (Miles)
                            1977

            Cumulative Frequency of Occurrence
            25%
              50%
                 75%
Jan
Feb
Mar
Apr
May
June
July
Aug
Sep
Oct
Nov
Dec
6.8
6.7
9.0
9.7
9.1
6.4
6.1
5.1
3.8
9.0
7.2
5.8
11.9
10.5
14.8
22.3
25.0
13.9
14.1
9.6
9.7
14.4
13.8
12.5
20.8
19.9
25.0
33.3
32.8
28.2
30.3
25.0
27.3
24.4
24.2
19.2
Annual
6.7
13.8
27.4
                           146

-------
likely affected by  the  fine  particle  emissions than the close-
in base site.  Moreover  both locations  showed a diurnal vari-
ation consisting of  a double maximum-double minimum.   The
lowest minimum in visibility occurs  about  the time of the morn-
ing inversion breakup.   The  higher  maximum in visibility occurs
in the mid afternoon.  The other  inflection points occur about
midnight and about  0400-0500.

Assuming that bscat  is directly proportional to airborne par-
ticulate mass loading,  then  the dust  loading experienced by a
monitoring station  is not uniform throughout the day-  This
suggests that the greatest impact to  a  24-hour hi-vol filter
could occur about 0900 each  morning.  Moreover, the minimum
particulate loadings are experienced  when  03 shows a  diurnal
maximum.  There appears  to be  an  SC>2  maximum about the same
time as the maximum  particulate loading and a minor SC>2 minimum
about the same time  as  the minimum  particulate loading at Site
5.

The results of ground-level  concentration  of sulfate  were com-
pared to simultaneous bgcat  values  for  the base site  and Site 5
(see Figure 38).  The relationship  is evident that sulfate con-
centration increases significantly  as the  scattering  coeffi-
cient increases.  Since  kscat  is  the  inverse of distance that a
specified amount of  light can  travel  through a particulate sus-
pension, this indicates  an inversely  proportional relationship
between visibility  and  sulfate concentration.
                              147

-------
                    Figure  37
               DIURNAL NEPHELOMETS3S
                      VALUES
  1.50

  1.40

  1.30

  1.20

  1.10

  0.90

  0 .80

  0.70
O
2 0.60
  0 .50

  0.40

  0.30

  0.20

  0.10
Site 05
Base Station
     24   02   04   06
                         03   10   12   14
                             Hour of Day
                             148

-------
             FIGURE   38


    SULEATE/SCATTERING COEFFICIENT
Cn
£[
»
is
.§
i
^3

OS
a.
i
r~\

BASE SITE AND SITE 5
40 -

30 -

20 -
10 -





,

•** * .*.**•
,* •** *•***

           I


  ,1       .2




     Site  5   -
          I    I  I  i    |   I   i  i    I



.3   .4    .5 .6  .8   1.0  1.4    2.0




            -4  -1
 b   ,    (10   777  )      24-Hour1  Average
^
y.
0
i
i
5
-\
CJi
a.

o*
40 -

30 -

20 -


10 -






t"
•
•• * * * •
• .:••' •*'* . •" '
1 | 1 ( I 1 1 1 1 1 ! 1 1
.1 .2 .3 .4 .5 .6 .8 1.0 1.4 2.0
Base Site -  b
       4  -1
   (10   m  )  -  24-Hour Average
                    149

-------
                           SECTION  7
       RELATIONSHIPS BETWEEN AIR QUALITY  AND METEOROLOGY
DAILY POLLUTANT DISTRIBUTION

The 24-hour average S02 and 804 concentrations were plotted on
maps for each day and  isopleths or  lines  of  equal concentra-
tions were constructed.  Sulfur dioxide was  selected due to its
anthropogenic source implications.

These daily maps showed that gradients  in the  observed SO2 and
304 concentrations could be constructed.   While the confidence
in these patterns could be subject  to question,  the fact re-
mains that gradient patterns could  be constructed.   The impli-
cations that can be drawn is there  are  local  effects (sources
and sinks) in the SO2  and 804  in  the Albany  area.  The fact
that at times the nature of the SO2 and 304  patterns were dif-
ferent indicates that  other factors besides  S02 alone is in-
volved in the resulting 304 concentrations.   The fact that
gradients in SO2 could be constructed is  not  surprising as iso-
pleths have been constructed for  such things  as t>sca^ (Lutrick,
1971) and S02 (Turner, 1964).

DAILY so4 ISOPLETH CHARTS

The isopleths that are located on  the following pages have been
drawn using the daily  S04 (sulfate) values at  the six monitor-
ing stations.  The isopleths all  represent observed sulfate
concentrations in micrograms per  cubic meter.

DIFFUSION MODELING

A diffusion model was  used to  estimate  the plant's  contribution
to the ambient concentration measured at  each  of the monitoring
                              150

-------
FIGURE  39
         151

-------
FIGURE  39
        152

-------
FIGURE  39

     153

-------
FIGURE   39
                                              1  MILE
                                      	1
                              'SO     1 KILOMETER

                     TRUE     Sept 21,  1978
                     NOBT11
        154

-------
FIGURE   39
                 TTIL-E   Sept 22, 1978
                 SOUTH
     155

-------
FIGURE   39
                    TRUE   Sept 23, 1978
                    MORTT1
       156

-------
FIGURE   39
                              1   S  0     I KILOMETER
                            Sept 24, 1978
           157

-------
FIGURE  39
    158

-------
Fid I IRK
     159

-------
FIGURE   39
                       n,UE    Sept 27,1978
                       Nonm
            160

-------
FIGURE   39
                                ISO     1 KILOMETER
                        TRUE     Sept 28, 1978
                        sonni
             161

-------
FIGURE   39
                             1   "I  °     1 KILOMETER
                            Sept 29,1978
           162

-------
FIGURE   39
                    TRUE    Sept 30,  1978
                    MORTTI
        163

-------
FIGURE  39
      164

-------
FIGURE  39
                                 ''
         165

-------
FIGURE  39
      166

-------
FIGURE   39
                               0     1 KILOMETER
                 TRUE   Oct4,1978
      167

-------
FIGURE  39
 168

-------
FIGURE   39
                  TBUE      Oct 6, 1978
                  MOBTII
      169

-------
FIGURE  39
                  TRUE    Oct 7,  1978
                  NORTH
     170

-------
FIGURE  39
 171

-------
FIGURE  39
      172

-------
FIGURE  39
       173

-------
FIGURE  39
                    <-;&--  i  %^;-,
                    *&w.    '  h'r.  i

       174

-------
FIGURE  39
                                       I

-------
FIGURE   39
                 •mire     Oot 13, 1978
                 MOBTII
    176.

-------
FIGURE  39
        177

-------
FIGURE   39
                      TRUE     Oct 15, 1978
                      NORTH
          178

-------
locations.  The objective  of  this  analysis  was  not model veri-
fication, but  to obtain a  general  estimate  of  the plant's im-
pact at  these  locations during  the study  period.

The model used was  a Gaussian model (Turner,  1970) that used
the Brigg's plume rise formulae  (Briggs,  1969  and 1972).  The
specific form  of the Gaussian equation  used was equation 3.1 by
Turner (1970).  Topography and  horizontal distances from cen-
terline were used.  Stability was  determined  by the  T measure-
ments taken on the  Niagara Mohawk  tower.  The  stability classi-
fication scheme in  Safety  Guide  1.23  (NRC,  1972)  was used to
convert  the AT measurements to  stability  classes.  Wind speed
and direction  measurements from the tower were  also used.  The
pollutant was  considered as being  chemically  and  physically
inert and that plume loss  by  deposition did not occur.

Hour-by-hour calculations  were  made for each  of the  ambient
monitoring locations other than  the Base  Station.  These hourly
concentrations were then averaged  to  obtain the estimated 24-
hour average plant  contribution  at each monitoring station.

A difficulty was encountered  in  the modeling  estimates.  The
problem  is determining a reliable  estimate  of  the background
concentration.  No  unique  method for  estimating background was
considered to  be universally  applicable in  this study.  The im-
portance of background can be best understood  if  each observed
concentration  is considered as  a sum of its components.  That
is:
                              179

-------
       X obs   =X plant + X ols  + X lrt
where: x obs   =  observed ambient  concentration
       X plant =  concentration increment due to source
       X ols   =  concentration increment due to other
                 local sources
       XIrt   =  concentration increment due to long range
                 transport

The background concentration at  any  station is the sum of  x°ls
and xlrt.  The value xlrt is probably  uniform at the stations
used  in this study, but Xols is  not  uniform at each station.
Therefore, a uniform background  concentration is difficult to
apply  to all stations.

In this study it was noticed that  the  winds rarely carried the
plant  plume towards Site  6.  Thus, one attempt of estimating
background was to  consider  the observed concentration at Site 6
as an  estimate of  the background  concentration.  Table 36 pro-
vides  an analysis  when Site 6  is  used  as an estimate of back-
ground.  The values presented  are  values obtained from the fol-
lowing ratio:
                      	X  Plant	
                      xobs  =  (xols + 'xlrt)
What  Table 36 suggests is that the plant increment in this
study  was a small  value compared  to  the two relatively larger
values of observed and background.   Thus,  any reasonable error
in either of the two is probably  of  equal or greater magnitude
than  the plant's increment.  This  is a condition that exists
for both S02 and 304 as indicated  by  the Site 1 data.

ANALYSIS OF AIR  QUALITY MEASUREMENTS

A statistical analysis of variance was performed, using the
combination of the (upper level)  tower wind direction data and
the ground-level air quality measurements.   The analysis of
                             18Q

-------
 Range
Of Ratio
                            TABLE  36
                 RATIO  OF  ESTIMATED TO OBSERVED
               (LESS  SITE  6)  24-HOUR CONCENTRATIONS
                        CUMULATIVE PERCENT
Rensselaer
SO 2
Site 5
SO 2
Site 1
SO 2
Site 1
S04 =
<0.0001             50.0
0.0001-0.0099       54.1
0.01-0.09           70.8
0.1-0.9            100.0
>1.0               100.0
 59.1
 63.6
 72.7
 81.8
100.8
 32.1
 35.7
 64.3
 89.3
100.0
 48.0
 56.0
 68.0
100.0
100.0
                              181

-------
variance tests is the difference  between  the  means of two or
more groups for significance.  The  sulfate, vanadium, and sul-
fur dioxide measurements were  used  as  observations (or data
points), while the site designation and  the wind direction were
used as groups.  The variance  ratio Crx2/0y2  (or F value) was
the criterion for testing  the  null  hypothesis:   that the means
of the observations were the same in both groups.

Since the prevailing wind  direction travelled the line of the
Hudson Valley, North to South  or  South to North on 21 days of
the 28 day program, the measurements made at  the North and
South sites  (Sites 1 and 5) were  used  exclusively.  A site was
designated downwind when the wind blew toward that site (_+ 45°)
fourteen hours or more on  a particular day.   The complementary
site was designated upwind, and  non-affected  sites were desig-
nated neutral.

A two-way analysis of variance was  performed  on the observa-
tions using  site designation and  wind  direction groupings.  The
result of the analysis of  variance  is  as  follows:

                         SULFUR  DIOXIDE
                       Degrees of Freedom         F Value
     Site                      1                   18.90**
     Wind                      2                    3.33*
     Site x Wind               2                    1.61
     Error                     46

                            VANADIUM
                       Degrees of Freedom
     Site                      1                   34.75**
     Wind                      2                   10.29**
     Site x Wind               2                    9.52**
     Error                     44
                              182

-------
                             SULFATE
                        Degrees  of  Freedom         F Value
     Site                       1                     .13
     Wind                       2                     .74
     Site x Wind                2                    6.04**
     Error                     44

      *Significant at  the  5% level
     **Significant at  the  1% level

The results of the analysis  of  variance  for  vanadium and sul-
fate are significant  for  the interaction  of  wind  direction and
site designation.  The  results  indicate  sulfur dioxide signifi-
cance due to site designation and  wind direction,  but the
interaction does not  indicate significance.   This  means that
the effects of site designation and  wind  direction are addi-
tive.  To illustrate,  the  population mean of sulfur dioxide
concentration, without  regard to site designation  or wind
direction is u.  When  all  sulfur dioxide  values at a particular
site are grouped together,  the  mean  value becomes  u + a.  When
all sulfur dioxide values  are grouped under  a particular wind
direction, the mean becomes  u + B.   If the effect  is additive,
then the mean of all  sulfur  dioxide  values at a particular
site, when the wind is  in  a  particular direction,  is u + a +
B.  This leads one to  the  conclusion that sulfur  dioxide fits a
relatively simple model, which  shows that the concentration is
related to wind direction,  regardless of  whether  the measure-
ment was made upwind  or downwind of  the  plant.

The results of the interaction  of  site designation and wind
direction are significant  with  respect to sulfate  and vanadium
concentration.  This  indicates  a more complex relationship
between the population  and  the  groupings  than the  one described
above.  In order to assess  the  significance  of this relation-
ship, a further one-way analysis of  variance was  performed
                              183

-------
for each designated site using the  sulfate  and  the  vanadium
populations.  Results are as follows:

                             Site 1
Wind
Error
Degrees Of Freedom

        2
       25
                                         F Value    F  Value
                                          304     Vanadium
5.26*
16.15**
                             Site  5
                  Degrees Of Freedom
                      F Value   F Value
                                Vanadium
Wind
Error
        2
       22
2.21
 1.64
*Significant at the 5% level
**Significant at the 1% level

The significant F values at Site  1  indicate  that  a  definite
repeatable relationship exists between wind  direction  and
ground-level sulfate and vanadium concentrations.

Non-significant F-values at Site  5  indicate  that  concentrations
on the upwind days are not necessarily higher  or  lower than  the
concentrations on downwind days.  The mean concentrations  pre-
sented on Table 37 clarify these  results.
                              184

-------
                           TABLE  37
                         SITE ANALYSIS
                      MEAN CONCENTRATIONS

                                         Site  1     Site 5
Sulf ate - ug/m^
Downwind                                 15.504      6.940
Upwind                                    6.063     12.410
Sulfur Dioxide -
Downwind                                 63.537    20.154
Upwind                                   28.352    13.727
Vanadium - ug/m^
Downwind                                  .0605     .0099
Upwind                                    .0162     .0085

It is clear  that  the  concentration  of  sulfate is much higher at
Site 5 when  Site  5  is  the  upwind  site  than at Site 1 when Site
1 is the upwind site.   The  implication is that a considerable
amount of sulfate material  is  carried  from other, possibly dis-
tant, sources with  the  air  movement from South to North.  Both
sulfur dioxide and  vanadium concentrations, however, are at
relatively low levels  at  Site  5 on  both upwind days and down-
wind days.   This  indicates  less contribution of sulfur dioxide
and vanadium than sulfate  from other emission sources.

The distributions of  these  air quality measurements are re-
flected in Figures  40  through  43;  also shown are the relation-
ships between sulfate  and  vanadium, and between sulfate and
sulfur dioxide.   The  high  sulfate and  low vanadium values at
Site 5-upwind  (see  Figure  41), show that while vanadium levels
are quite low, sulfate  levels  are moderate-to-high and are  in-
dependent from vanadium levels.  A  similar relationship exists
between sulfate and sulfur dioxide  measurements upwind at this
site  (see Figure  42);  these results show apparent  independence
of sulfate from sulfur dioxide.  Downwind measurements at Site
                               185

-------
  CO
  Cfc
             FIGURE  40

    SULFATE/VANADIUM AT SAMPLING SITE


         SOUTH OF EMISSION SOURCE
t-o
     40 -
     30 -
     20  -
     10  -
40



30



20



10
           O  O
              O
                  SITE 5
               01  .02   .03  .04   .05  .06   .07   .08

                                    •2
                   Vanadium -  y g/m   -  24-Hour Average
                             Downwind Days
             —i	<	1	1	:	r~
              .01  .02   .03  .04   .05   .06

                                    3
                    Vanadium  -  y g/m
                                          .07   .08


                                      24-Hour Average
                         Upwind or Neutral Days
                           186

-------
                  FIGURE  41
    SULFATE/SULFUR DIOXIDE  AT SAMPLING SITE
o
   40  -
   20  -
   10  -
            SOUTH  OF EMISSION SOURCE
SITE  5
                   i     i      r     i
                                         i     i
            10    20   30    40   50    60    70    80
                             3
                      -   y g/m
                     Average
                       Dowmjind Days
1
1
o
^
^
1
5
3-
§f
40 -
30 -


20 -


10 -



O 0

O

0 g ° 0
0 °
i t i i i i i i
10 20 30 40 50 60 70 80
SO* - y g/m - 24-Hour Average
                     Upwind OP Neutral  Days
                         187

-------
 8,
 £
 CXJ
to
40  1


30


20


10
               FIGURE 42

    SLLFATE/VANADIUM AT  SAMPLING SITE

          NNW OF  EMISSION SOURCE

                      SITE 1              •
                                                           .105
                                                           •
                i      i     i      i     i      i     i      \
               01   .02  .03   .04  .05   .06   .07   .08

                     Vanadium -  y g/m  -  24-Eoia1 Average
                            Downuind Days
s
3
i§
oa
1
to
p.
1
0*
40 ~

30 '

20 -

10 -







0 °
0°
i ; i i i i i i
.01 .02 .03 .04 .05 .06 .07 .08
                     Vanadium  -  \\ g/m   -   24-Hour Average
                           Upwind or Neutral Days
                            188

-------
               FIGURE  43
SULFATE/SULFUR DIOXIDE AT SAMPLING SITE

        NNW OF  EMISSION SOURCE
03
1
s
o
&3
00
1
i
3.
1
•<*
CO
40 -
30 -



20 -
10 -

SI1E I w




^f
9 • 99«10-
9 0 * 122

1 	 r i i i ' \ > i

10 20 30 40 50 60 70 80
?
SO _ - y g/m" - 24-Hour Average
£i
                     Downwind Days
SJ
^
o
i
^
1
CO
f>
3.
'^
O
CO
40 -
30 -


20 -


10 -








0 °
0 °
10 20 30 40 50 60 70 80

?
SO „ - y g/m" - 24-Hour Average
Ci
                Upwind or Neutral Days
                         189

-------
5 result in proportional relationships  between  sulfate and
vanadium and between sulfate  and  sulfur dioxide.   This supports
the conclusion that the downwind  sulfate,  vanadium,  and sulfur
dioxide originate from the same source(s).

Upwind measurements at Site 1  reflect  low-to-moderate sulfate
levels, quite low vanadium levels  (see  Figure  43)  and moderate
sulfur dioxide levels  (see Figure  44).   Too  few data points are
available to draw any  conclusions  about the  relationship be-
tween parameters under these  conditions.

Downwind measurements  at Site  1 show moderate-to-high levels of
all three parameters,  reflecting  the high  sulfate  upwind values
 (at Site 5) plus the plant contribution.   A  proportional rela-
tionship exists between sulfate and both  sulfur dioxide and
vanadium on downwind days, suggesting  that all  three parameters
originate at the same  source(s).

Sulfate materials are  transported  from  other sources in moder-
ate quantities, while  vanadium and sulfur  dioxide  are not.
Since vanadium is a solid metal,  usually  present  in  combustion
effluent in a higher oxide state,  or as a  vanadate combined
with sodium, its weight probably  causes it to  settle to the
ground soon after emission.   Sulfur dioxide  gas disperses with
time, at a rate strongly influenced by  local meteorology.
Although it is not known exactly  how far  the background sulfate
observed in this experiment had travelled  prior to reaching the
study area, it was of  sufficient  duration  to cause dispersion
of any attendant sulfur dioxide and deposition  of  attendant
vanadium.

AIR QUALITY ANALYSIS OF UPWIND-DOWNWIND MEASUREMENTS

The examination of (upper level)  tower  wind  direction meas-
urements resulted in the determination  that  certain  sites
                               190

-------
(primarily sites 1 and  5)  could  be  assigned  the  status  upwind
or downwind, relative  to  the  plant,  during a  major  number of
days.  The following definitions  were  necessary  in  order to
assign the designations:   (1)  whenever the wind  movement
travelled along a course  from the plant to a  particular site,
within tolerance limits,  more  than  12  hours  in  any  day,  that
site was termed downwind  that  day and  (2) whenever  the  wind
movement travelled along  a  coarse from a particular site to the
plant, within  tolerance limits,  more than 12  hours, and the
downwind hours were zero,  that site  was termed  upwind.   Data
was reduced using wind  directional  tolerances of 45°,  20°,  and
10°.  The wide 45° tolerance  resulted  in fifteen days  where the
criteria were  met; 20°  tolerance  resulted in  six days  and 10°
tolerance resulted in  three days.

Four measurement parameters were  identified,  because of their
emission qualities:  particulates (TSP), sulfur  dioxide, vana-
dium, and sulfates.  The  upwind-downwind values  of  these para-
meters are shown on Tables  38, 39 and  40.

The mean downwind air  quality  measurements show  a significant
increase over  the mean  upwind  measurements;  this increase will
be referred to as the  "plant  contribution"  in this  discussion.
The relationships between wind direction tolerance  limits (45°,
20°, 10°) and  plant contribution  were  significant for  emission
parameters sulfate and  TSP, but  not  for vanadium and sulfur
dioxide.  In other words,  the  plant  contribution of sulfate and
TSP was higher when the wind  was  less  variable.   The mean plant
contribution to downwind  sulfate  levels was  11.3% at a 45° wind
variance, and  53.4% at  a  10°  wind variance.   The TSP trends
were similar although  not quite  as  dramatic:   plant contribu-
tion of 12.4%  at a 45°  wind variance and 20.7% at a 10° wind
variance.
                              191

-------
                                                     TABLE  38
                                AMBIENT TSP  MEASUREMENTS UPW1ND-DOVJNWIND OF EMISSION SOURCE
NJ
Date
Wind
9-18
9-20
9-21
9-22
9-24
9-28
9-30
10-2
10-4
10-5
10-6
10-8
10-11
10-12
10-15
Moan
a
Wind
9-18
9-20
9-21
9-22
9-24
9-30
Mean
a
9-21
9-22
9-30
Mean
0
Downwind Upwind
Site Mrs. Site Hrs.
Directional
5
1
1
5
1
3
1
5
1
1
1
5
1
1
5


Directional
5
1
1
5
1
1


1
5
1


Tolerance
23
24
19
23
22
16
22
19
13
19
18
23
22
23
24
21
3
Tolerance
15
20
18
20
21
16
18
2
16
17
13
15
2
=
1
5
5
1
5
6
5
1
5
5
5
1
5
5
1


=
1
5
5
1
5
5


5
1
5


45°
24
24
17
24
22
16
22
21
15
19
19
24
23
23
24
21
3
20°
19
18
17
21
17
16
18
2
14
20
13
16
4
Downwind
TSP
(Ug/m3)

43.
45.
62.
36.
36.
34 .
41.
31.
39.
42.
25.
4 .
73.
76.
10.
40.
19.

43.
45.
62.
36.
36.
41.
44.
9.
62.
36.
41.
46.
14 .

0
8
9
5
2
9
1
4
8
8
7
0
9
0
3
3
9

0
8
9
5
2
1
3
9
9
5
1
9
1
Upwind
TSP
(lig/m3)

39
42
47
39
25
76
24
32
21
30
16
11
48
72
18
36
19

39
42
47
39
25
24
36
9
47
39
24
37
11

.4
.0
.6
.1
. 2
.2
.8
.3
.0
.1
.0
.4
.8
. 3
.2
. 3
.1

.4
.0
.6
.1
.2
.8
.4
.3
.6
.1
.8
.2
.5
Di f ference
(DW-UW)
(gg/m3)

3.
3.
15.
-2.
11.
-41.
16.
-0.
18.
12.
9.
-7.
25.
3.
-7.
5.
15.

3.
3.
15.
-2.
11.
16.
7.
7.
15.
-2.
16.
9.
30.

6
8
3
6
0
3
3
1
8
7
7
4
1
7
9
0
5

6
8
3
6
0
3
9
5
3
6
3
7
7
Difference £ of
Downwind
TSP

8.5
8.2
24.3
-7 .2
30.3
-119
39.7
-0. 3
47.2
29 .7
37.7
-] R6
-340
4 . 8
76 .2



R.5
8. 2
24. 3
-7.2
30.3
39 .7


24 . 3
-7.2
39.7



-------
                                                   TABLE  39




                        AMBIENT SULFUR DIOXIDE MEASUREMENTS UPWIND-DOWNWIND OF EMISSION SOURCE
vo
Da to
Wind
9-18
9-20
9-21
9-22
9-24
9-28
9-30
10-2
10-4
10-5
10-6
10-8
10-11
10-12
10-15
Mean
a
Wind
9-18
9-7.0
9-21
9-22
9-24
9-30
Mean
a
Wind
9-21
9-22
9-30
Mean
a
Downwind
Site Mrs. S
Directional
5
1
1
5
1
3
1
5
1
1
1
5
1
1
5


Directional
5
1
1
5
1
1


Directional
1
5
1


Tolerance
23
24
19
23
22
16
22
19
13
19
18
23
22
23
24
21
3
Tolerance
15
20
18
20
21
16
18
2
Tolerance
16
17
13
15
2
Upwind
ite Mrs.
=
1
5
b
1
5
6
5
1
5
5
5
1
5
5
1


=
1
5
5
1
5
5


=
5
1
5


45°
24
24
17
24
22
16
22
21
15
19
19
24
23
23
24
21
3
20°
19
18
17
21
17
16
18
2
10°
14
20
13
16
4
Downwind
so2
(lig/m3)

14
56
61
20
69
30
IS
25
39
21
44
00
26
70
1
33
22

14
56
61
26
69
15
40
24

61
26
15
34
24

.6
.5
.9
.1
.1
.6
.8
.0
.1
.5
. 3
.0
.5
.4
.1
.5
.8

.6
.5
.9
.1
.1
.8
.7
.6

.9
. 1
.8
.6
.2
Upwi nd
SO 2
(]ig/mj)

29
10
26
15
52
21
00
23
7
7
3
27
8
3
35
18
14

29
10
26
15
52
00
22
18

26
15
00
13
13

.2
. 3
.1
. 3
.1
.7
.0
.1
.6
.6
. 3
.1
.7
. 3
.1
.0
.4

.2
. 3
.1
.3
.1
.0
.2
.1

.1
. 3
.0
.8
. 1
Di r Cere nee
( DV; - uw )
(pg/m^)

-14
46
35
10
17
8
15
1
31
13
41
-27
17
67
34
20
23

-14
46
35
10
17
15
18
21

35
10
15
20
1 3

.6
.2
.8
.8
.0
.9
.8
.9
.5
.9
.0
.1
.8
.1
.0
.0
.8

.6
.2
.8
.8
.0
.8
.5
.1

.8
.8
. 8
.8
.2
Di Cfei r^ncv °- of
Downwi n
-------
                       TABLE   40
AMBIENT VANADIUM MEASUREMENTS UPWIND-DOWNWIND OF EMISSION SOURCE
Date
Wind
9-18
9-20
9-21
9-22
9-24
9-28
9-30
10-2
10-4
10-5
10-6
10-8
10-11
10-12
10-15
Mean
a
Wind
9-18
9-20
9-21
9-22
9-24
9-30
Moan
a
Downwind
Site Hrs.


Upwind
Site Hrs.

Directional Tolerance
5
1
1
5
1
3
1
5
1
1
1
5
1
]
5


23
24
19
23
22
16
22
19
13
19
18
23
22
23-
24
21
3
1
5
5
1
5
6
5
1
5
5
5
1
5
5
1


Directional Tolerance
5
1
1
5
1
1


15
20
18
20
21
16
10
2
1
5
5
1
5 '
5


Wind Directional Tolerance
9-21
9-22
9-30
Mean
o
1
5
1


16
17
13
15
2






= 45°
24
24
17
24
22
16
22
21
15
19
19
24
23
23
24
21
3
= 20°
19
18
17
21
17
16
18
2
= 10°
14
20
13
16
4
Downwind
Vanadium
(Vig/m3)

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0

0
0
0
0
0
0
0
0

0
0
0
0
0

.005
.063
.070
.01">
.061
.024
.058
.010
.041
.083
.029
.002
.071
.043
.004
.035
.028

.005
.063
.070
.017
.061
.058
.046
.027

.070
.017
.058
.048
.028
Upwind
Vanadium
(pg/m3)

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0

0
0
0
0
0
0
0
0

0
0
0
0
0

.033
.003
.008
.013
.003
.004
.008
.022
.012
.010
.008
.003
.004
.008
.005
.010
.008

.033
.003
.008
.013
.003
.008
.011
.011

.008
.013
.008
.010
.003
Difference
(DW - UW)
(pg/m3)

-0
0
0
0
0
0
0
-0
0
0
0
-0
0
0
-0
0
0

-0
0
0
0
0
0
0
0

0
0
0
0
0

.028
.060
.062
.004
.058
.020
.050
.012
.029
.073
.021
.001
.067
.035
.001
.029
.032

.028
.060
.062
.004
.058
. 050
.030
.036

.062
.004
.050
.038
.031
                                                            Difference * of
                                                               Downwind
                                                               Vanadium
                                                                 -505
                                                                   95.4
                                                                   88.5
                                                                   19 .7
                                                                   94 .9
                                                                   85.2
                                                                   86 .6
                                                                 -122
                                                                   70.5
                                                                   87.6
                                                                   72.4
                                                                  -50
                                                                   93.8
                                                                   81.1
                                                                  -31.6
                                                                  -505
                                                                   95.4
                                                                   88.5
                                                                   19 .7
                                                                   94 .9
                                                                   86.6
                                                                   88.5
                                                                   19. 7
                                                                   86.6

-------
Sulfur dioxide contribution was  45-60% and  vanadium  contribu-
tion was 65-80%, apparently independent  of  wind  variance
degree.  The summary of  upwind-downwind  measurements  is  shown
in Table 42.

Since the plant emission  rates of  total  sulfates and  particu-
lates were approximately  equal,  it  is  not  surprising  that  the
mean contributions  to  the ambient  levels were  also approxi-
mately equal.  Difference in TSP levels  (downwind minus  upwind)
was 5, 8, and 10 ug/m  when the  wind variance  was 45°,  20°,  and
10°, respectively.  Likewise, difference in total sulfate
levels were  1.4, 6, and  12 ug/m3 at  the  respective wind  vari-
ances.  Difference  in  vanadium concentration was 0.030  ug/m3,
or beween 0.3% and  0.6%  of the plant-contributed TSP.   This
fraction is  lower than the vanadium  fraction in  the  plant  par-
ticulate emissions  by  a  factor of  10,  possibly due to  rapid
deposition of metallic vanadium.   The  downwind minus  upwind
measurement  of sulfur  dioxide was  20 ug/m  • Neither  vanadium
nor sulfur dioxide  measurements  indicate a  susceptibility  to
increased ground-level concentrations  due  to low wind  direction
variance.

The first consideration  to these mean  values is  the  observation
that sulfate and total particulates  travel  a narrow  corridor
when wind direction is steady.   The  mean values  do not,  how-
ever, indicate the  extreme variability  in  plant  contribution
even with wind direction  tolerance  of  20°  (-64%  to +60% of
downwind sulfate levels).  Less  variability occurs at  a wind
variance of  10°  (34% to  60% of downwind  concentration),  but  in
this case only three values are  included.   Wind  tolerances of
45° show a negative plant sulfate  contribution on 40% of the
days observed.  Apparently upper winds  and  atmospheric stabil-
ity were important  factors on those  days.
                              195

-------
                                                         TABLE   41

                                 AMBIENT SULFATE  MEASUREMENTS  UPWIND-DOWNWIND OF EMISSION  SOURCE
CTi
Date
Wind
9-18
9-20
9-21
9-22
9-24
9-28
9-30
10-2
10-4
10-5
10-6
10-8
10-11
10-12
10-15
Hean
0
Wind
9-18
9-20
9-21
9-22
9-24
9-30
Mean
a
Wind
9-21
9-22
9-30
Mean
o
Downwind Upwind
Site Hrs. site Hrs .
Directional
5
1
1
5
1
3
1
5
1
1
1
5
1
1
5


Directional
5
1
1
5
1
1


Directional
1
5
1


Tolerance
23
24
19
23
22
16
22
19
13
19
18
23
22
23
24
21
3
Tolerance
15
20
18
20
21
16
18
2
Tolerance
16
17
13
15
2
=
1
5
5
1
5
6
5
1
5
5
5
1
5
5
1


=
1
1
5
1
1
5


=
5
1
5


45°
24
24
17
24
22
16
22
21
15
19
19
24
23
23
24
21
3
20°
19
18
17
21
17
16
18
2
10°
14
20
13
16
4
Downwind
so,-
(Vig/mJ)

5.
13.
43.
14.
11.
6.
8.
9 .
9.
13.
8.
2.
18.
18.
3.
12.
9.

5.
13.
43.
14 .
11.
8.
16 .
13.

43.
14.
8.
22.
18.

0
8
2
4
0
9
8
3
1
9
2
3
4
3
0
4
8

0
8
2
4
0
a
0
7

2
4
8
1
4
Upwind
(pg/m3)

8
12
17
7
8
7
5
8
8
11
8
3
25
25
4
10
6

8
12
17
7
8
5
10
4

17
7
5
10
6

.2
.0
. 3
.8
.8
.5
.8
.6
.0
.0
.9
. 3
.5
. 7
.4
.8
. 7

.2
.0
. 3
.8
.8
. 8
.0
.1

. 3
.8
.8
.3
.2
Difference P
(DW - IIW)
(Vig/m3)

-3.
1.
25.
6 .
2.
-0.
3.
0.
1.
2.
-0 .
-1.
-6.
-7.
-1.
1.
7.

-3.
1.
25.
6.
2.
3.
6.
10.

25.
6.
3.
11.
12.

2
8
9
6
2
G
0
7
1
9
7
0
1
4
4
/!
6

2
8
9
6
2
0
0
2

9
6
0
8
3
                                                                                                         Difference * o f
                                                                                                              Downwi nd
-63.6
 12 .6
 59.9
 46.1.
 1 9 .5
 -8.9
 33. 7
  7 . 5
 12. 7
 30 .0
  R. 5
-47.0
-33.0
-40 .2
-46.5
                                                                                                                -63. 6
                                                                                                                 12.6
                                                                                                                 59.9
                                                                                                                 46. 1
                                                                                                                 19 .5
                                                                                                                 33. 7
                                                                                                                 59 .9
                                                                                                                 46.1
                                                                                                                 33.7

-------
TSP
Vanadium
SO-
SO,
                                        TABLE  42




                        SUMMARY OF AMBIENT UPWIND-DOWNWIND MEASUREMENT;
Mean
X

X

X

X

X

X

X

X

X

X

X

X

0

X

X

X

X

X

X

X

X

X

X

X

X
Wind
Directional
Tolerance
45°
45°
20°
20°
10°
10°
45°
45°
20°
20°
10°
10°
45°
45°
20°
20°
10°
10°
45°
45°
20°
20°
10°
10°
Downwin
-------
These results reflect  the  concept  that  the  plant does in fact
contribute sulfate and other  materials  to the ambient air
levels, but because of high background  scatter and the use of
fixed monitoring sites, a  very  low  confidence is assigned to
the magnitude of the contribution.   In  fact the standard devi-
ations in many cases (all  cases  of  sulfate) exceed the mean.

STATISTICAL AMBIENT SULFATE PREDICTION  ESTIMATES

Regression analysis was used  to  develop a statistic prediction
model for ambient sulfate  concentrations.  This methodology has
several advantages in  that it allows available data to be used
to estimate ambient SO£ concentrations  in the study area.
While there is some advantages  that result  from this, there are
some points to be kept in  mind.  Any such prediction scheme
that results has a statistical,  not a physical basis.  Second,
the prediction scheme  may  not necessarily be equally applicable
at another location due to the  statistical  nature of the
scheme.

The statistical model  was  developed using stepwise multiple
regression.  This involved fitting  a set of independent vari-
ables to a single dependent variable.  That is;
/\            n
Y = b    +   .£,  b.  X.  +6           £   -\>   NID  (o.a )
     o      i=l   11                              e
In this case, the dependent  variable,  Y,  was the measured 24-
hour ambient sulfate  concentrations  downwind from the plant.
The following is a  list  of  independent variables, measured
hourly and converted  to  24-hour  averages:
                               198

-------
(1)  Portion of 24-hour  day  that  wind  blew  toward  downwind
     site, %
(2)  Wind speed, mph
(3)  Downwind SO2  concentration,  ppm
(4)  Downwind vanadium concentration,  ug/m3
(5)  Average temperature profile  (from tower  measurement),
     °F/ft.
(6)  Average wind  persistence
(7)  Average relative humidity
(8)  Average nephelometer  reading,  bscat  (10~4m~1)
(9)  Distance from plant to  downwind  site,  km
(10) Average mixing height,  m
(11) Total sulfate  emission, kg/day
(12) Particulate emission, kg/day
(13) S02 emission,  kg/day
(14) Background sulfate  concentration,  ug/m3

A site was considered to be  downwind  if  it  was  downwind  from
the plant during any portion of a day.  There could  be more
than one downwind  site during any day.  The  limits of  daily
wind direction variability,  designating a site  as  downwind,
were + 45° so that  an adequate number  of  data points were
available.  In this examination,  background  levels were  taken
from the upwind or  neutral site measurements.

The statistical model inserted the  variables  by priority,  using
the most significant variables first,  and so  on in order of  de-
creasing significance.   The  most  significant  variable  in the
analysis was background  sulfate;  obviously  the  downwind  sulfate
must be an incremental increase added  to  the  background  lev-
els.  The most significant variable after background  sulfate
was the percent of  time  the  wind  blew  towards the  downwind
site.  In order of  decreasing significance,  the following vari-
ables were inserted:  downwind SC^, downwind  vanadium,  nephelo-
meter reading, distance  downwind  from  plant,  and particulate
                              199

-------
           TABLE   43








RESULTS OF MULTIPLE REGRESSION ANALYSIS



 INDEPENDENT VARIABLE — DOWNWIND S0=.

Parameter



Y-Intercept
Downwind
Hours
Downwind
so2
Downwind
Vanadium
Nephelometer,
24 - hour
average
Downwind
Distance
from plant
Plant Emission,
P articulate
Background
so=4
Downwind
so"
Units Coefficient Value Nee- Mean Individual
ssary to al- Value Correlation
ter S0=4 Coefficient
*1. Oug/m3
19.9
% of +.02 50.0 57.4 .22
24 - ho ur
ppm -301.6 -003 .017 .32

jig/m3 +55.8 -018 .038 .40

b -6.9 -145 .664 .79
scat

km +2.2 -45 5.05 .04


kg/day +.001 1000 3997 .05

jig/m3 +2.9 -345 7.95 .89

>ag/m3 - - 11.82 1.00

                  20.0

-------
emission.  The remaining  variables  caused  an  increase of the
error term when  inserted,  therefore  they were  not  included in
the statistical  model.

The resulting regression  has  a  multiple  correlation  coefficient
of .96, adjusted R2  .89,  and  a  standard  error  of  estimates
2.43.  The regression  coefficients  are  shown  on Table 43,  and
are presented with mean values,  values  necessary  to  alter  down-
wind sulfate +1.0 ug/m3,  and the  individual  correlation coef-
ficients.  The inverse relationship  between  sulfate  and S02
reflects the instances where  high  background  sulfate levels
were observed with low SC>2 values.   Mean downwind  sulfate  con-
centration was 11.82 ug/m3; mean upwind  sulfate concentration
was 7.95 ug/m3.  Standard  deviation  of  the difference between
the predicted and actual  downwind  values was  2.43  ug/m3.

This statistical model uses the emission data  and  monitoring
sites designated in  this  experiment,  under those  meteorological
conditions that  prevailed  at  the time.   The  statistical equa-
tion is not a universal relationship and may  not  be  accurate
under any other  conditions or applications.   The  model is  an
accurate prediction  of ambient  sulfate  concentrations within
the limitations  imposed by the  data.
                               201

-------
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-------
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                             206

-------
                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
  REPORT NO.

    EPA-600/2-80-109
             3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
   IMPACT OF A PRIMARY SULFATE EMISSION SOURCE  ON
   AIR  QUALITY
                                                            5. REPORT DATE

                                                              May 1980
             6. PERFORMING ORGANIZATION CODE
 . AUTHOR(S)
    K.R.  Boldt, C.P. Chang,  E.J.  Kaplin, J.M.  Stansfield,
    B.R.  Wuebber
             8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
    York  Research Corporation
    Stamford, CT  06906
             10. PROGRAM ELEMENT NO.

               1AA603A  AA-91  (FY-79)
             11. CONTRACT/GRANT NO.
                                                              68-02-2965
12. SPONSORING AGENCY NAME AND ADDRESS
    Environmental Sciences  Research Laboratory  -  RTP, NC
    Office of Research and  Development
    U.S.  Environmental Protection Agency
    Research Triangle Park,  NC  27711
             13. TYPE OF REPORT AND PERIOD COVERED
               Final
             14. SPONSORING AGENCY CODE

               EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
         A one-month study  was carried out at  an  isolated oil-fired power  plant in
    New York State to assess  the impact of primary sulfate emissions on  air quality.
    Emissions of total  sulfate from the source varied from 22 kg/hr to 82  kg/hr
    per boiler with the sulfuric acid concentration averaging 74% of the total
    sulfate.  Particulate emissions ranged from 12 kg/hr to 70 kg/hr per boiler
    with between 32% and 67%  of the particle mass as water soluble sulfate.
    Vanadium was implicated as the driving force  in the magnitude of the primary
    sulfate emissions.   Measurements taken 5 km downwind of the plant indicated
    a  source sulfate contribution of from 30%  to  60% of the 24 hr average  ambient
    levels.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                               b.IDENTIFIERS/OPEN ENDED TERMS
                              COSATI E'ield/Group
    *Air pollution
    *Particles
    *SulI fates
    *Emission
     Electric power plants
                              13B
                              07B
                              10B
18. DISTRIBUTION STATEMENT
    RELEASE TO  PUBLIC
                                               19. SECURITY CLASS (This Report)
                                                 UNCLASSIFIED
                            21. NO. OF PAGES
                               227
20. SECURITY CLASS (This page)
  UNCLASSIFIED
                           22. PRICE
EPA Form 2220-1 (Rev. 4-77)   PREVIOUS EDITION is OBSOLETE
                                            207

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