United States Region 2 EPA/902/R-93-001d
Environmental Protection 902 January 1993
Agency
<&EPA Staten Island/New Jersey
Urban Air Toxics
Assessment Project
Report
Volume
Part B
Results and Discussion of the
Metals, Benzo[a]pyrene,
and Formaldehyde in Ambient Air
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ACKNOWLEDGEMENTS
This report is a collaborative effort of the staffs of the
Region II Office of the U.S. Environmental Protection Agency
(EPA), the New Jersey Department of Environmental Protection and
Energy, the New York State Department of Environmental
Conservation, the New York State Department of Health, the
University of Medicine and Dentistry of New Jersey and the
College of Staten Island. The project was undertaken at the
request of elected officials and other representatives of Staten
Island concerned that emissions from neighboring industrial
sources might be responsible for suspected excess cancer
incidences in the area.
Other EPA offices that provided assistance included the
Office of Air Quality Planning and Standards, which provided
contract support and advice; and particularly the Atmospheric
Research and Exposure Assessment Laboratory, which provided
contract support, quality assurance materials, and sampling and
analysis guidance, and participated in the quality assurance
testing that provided a common basis of comparison for the
volatile organic compound analyses. The Region II Office of
Policy and Management and its counterparts in the States of New
York and New Jersey processed the many grants and procurements,
and assisted in routing funding to the project where it was
needed.
The project was conceived and directed by Conrad Simon,
Director of the Air and Waste Management Division, who organized
and obtained the necessary federal funding.
Oversight of the overall project was provided by a
Management Steering Committee and oversight of specific
activities, by a Project Work Group. The members of these groups
are listed in Volume II of the report. The Project Coordinators
for EPA, Robert Kelly, Rudolph K. Kapichak, and Carol Bellizzi,
were responsible for,the final preparation of this document and
for editing the materials provided by the project subcommittee
chairs. William Baker facilitated the coordinators' work.
Drs. Edward Ferrand and, later, Dr. Theo. J. Kneip, working
under contract for EPA, wrote several sections, coordinated
others, and provided a technical review of the work.
The project was made possible by the strong commitment it
received from its inception by Christopher Daggett as Regional
Administrator (RA) for EPA Region II, and by the continuing
support it received from William Muszynski as Acting RA and as
Deputy RA, and from constantine Sidamon-Eristoff, the current RA.
The project has received considerable support from the other
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project organizations via the Management Steering Committee,
whose members are listed in Volume II.
11
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PREFACE - DESCRIPTION OP THE STATEN ISLAND/NEW JERSEY URBAN AIR
TOXICS ASSESSMENT PROJECT REPORT
This report describes a project undertaken by the States of
New York and New Jersey and the United States Environmental
Protection Agency with the assistance of the College of Staten
Island, the University of Medicine and Dentistry of New Jersey
and, as a contractor, the New Jersey Institute of Technology.
Volume I contains the historical basis for the project and a
summary of Volumes II, III, IV, and V of the project report.
Volume II of the report lists the objectives necessary for
achieving the overall purpose of the project, the organizational
structure of the project, and the tasks and responsibilities
assigned to the participants.
Volume III of the report presents the results and discussion
of each portion of the project for ambient air. It includes
monitoring data, the emission inventory, the results of the
source identification analyses, and comparisons of the monitoring
results with the results of other studies. Volume III is divided
into Part A for volatile organic compounds, and Part B for
metals, benzo[a]pyrene (BaP), and formaldehyde. Part B includes
the quality assurance (QA) reports for the metals, BaP, and
formaldehyde.
Volume IV presents the results and discussion for the indoor
air study performed in this project. It contains the QA reports
for the indoor air study, and a paper on the method for sampling
formaldehyde.
Volume V presents the results of the detailed statistical
analysis of the VOCs data, and the exposure and health risk
analyses for the project.
Volume VI, in two parts, consists of information on air
quality in the project area prior to the SI/NJ UATAP; quality
assurance (QA) reports that supplement the QA information in
Volume III, Parts A and B; the detailed workplans and QA plans of
each of the technical subcommittees; the QA reports prepared by
the organizations that analyzed the VOC samples; descriptions of
the sampling sites; assessment of the meteorological sites; and a
paper on emissions inventory development for publicly-owned
treatment works.
The AIRS database is the resource for recovery of the daily
data for the project. The quarterly summary reports from the
sampling organizations are available on a computer diskette from
the National Technical Information Service.
111
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8TATEN ISLAND/NEW JERSEY
URBAN AIR TOXICS ASSESSMENT PROJECT
VOLUME III, PART B.
RESULTS AND DISCUSSION OF THE METALS, BENZO[a]PYRENE, AND
FORMALDEHYDE IN AMBIENT AIR
EPA/902/R-93-001d
TABLE OF CONTENTS
1. INTRODUCTION 1
2. SAMPLING AND ANALYSIS 2
2.1 Particulates 2
2.2 Formaldehyde 3
3. RESULTS AND DISCUSSION 3
3.1 Concentration Data 3
3.2 Comparisons to Concentration Data from Other
Locations 3
3.3 Temporal Patterns 5
3.4 Spatial Patterns 6
3.4.2 Iron 6
3.4.3 Nickel 6
3.4.4 Cobalt 7
3.4.5 Vanadium and chromium 7
3.4.6 Lead 7
3.4.7 Copper and zinc 8
3.4.8 Cadmium 8
3.4.9 Mercury 8
3.4.10 BaP 8
4. CONCLUSIONS 9
5. ACKNOWLEDGEMENT 9
6. REFERENCES 10
TABLES IIIB-1 through 16 11
TABLES IIIB-17a through 18b 27
FIGURES IIIB-1 through 10 33
FIGURES IIIB-15 through 26 47
FIGURES IIIB-27 through 53 59
APPENDICES 88
APPENDIX A - QUALITY ASSURANCE SUMMARY A-l
APPENDIX B - DATA SUMMARIES BY QUARTERLY AVERAGE .... B-l
APPENDIX C - DATA SUMMARIES BY ANNUAL AVERAGE C-l
APPENDIX D - QUALITY ASSURANCE REPORT FROM NEW JERSEY
INSTITUTE OF TECHNOLOGY D-l
APPENDIX E - QUALITY ASSURANCE REPORT FROM NEW YORK STATE
DEPARTMENT OF HEALTH E-l
iv
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1. INTRODUCTION
The Staten Island/New Jersey Urban Air Toxics Assessment
Project (SI/NJ UATAP) included sampling for airborne particulate
matter and for formaldehyde at four sites, two in Staten Island
and two in New Jersey. The sampling period included October 6,
1988, through September 19, 1989. The work was intended to
provide data for use in estimating the health risks arising from
inhalation exposure to the toxic substances transported by the
particles, and to formaldehyde.
The particulate samples were prepared and analyzed at two of
the participating laboratories; and the formaldehyde samples, at
an EPA contract laboratory. The results were compiled, then
reviewed for validation.
The elements and compounds (analytes) selected for the
project were regarded as potentially hazardous materials likely
to be present at measurable concentrations in the samples, and
measurable with the methods available to the laboratories. The
potential sources of the materials include resuspended soils,
industrial emissions, incinerators, autos and trucks, power
plants, and home heating systems. While some of the analytes
selected may be characteristic of particular source categories,
it was not an objective of the project to fully characterize the
potential sources.
The data, summaries of which are available on computer
diskettes through the National Technical Information Service
(NTIS), are useful for (1) determining the average airborne
concentrations for various time periods, such as annual averages;
(2) seeking patterns in the concentrations versus time, space,
source emissions, or meteorological parameters; and (3)
estimating possible health risks resulting from inhalation
exposure.
This volume of the project report presents the
concentrations and patterns observed, and possible relations to
other variables. A risk assessment is presented in Volume V of
the project report.
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2. SAMPLING AND ANALYSIS
2.1 Particulates
The particulate samples were taken with Hi-Vol (high-volume)
samplers. These machines collect the particulate matter on
highly efficient filters and collect all particles up to about 50
microns (micrometers) in diameter. The respirable portion of the
samples is contained in particles with aerodynamic diameters of
about 10 microns or less; based on literature data1, the
respirable portion often constitutes approximately 30 to 60% of
the total sample concentration.
The initial stage in sample preparation was dissolution of
the analytes from the particulate matter on the filter in an acid
solution for metals analysis, or, for benzo[ot]pyrene (BaP) , in a
solvent. There were differences between the acid dissolution
methods of the two laboratories. The solutions obtained were
analyzed by either the atomic absorption or Inductively Coupled
Plasma-Optical Emission methods.
A summary of the results of the quality assurance (QA)
evaluation of the submitted data follows; it states whether the
data have been included in or excluded from the project data
base, and, if included, if there is an attending caveat on use of
the data. A more detailed QA discussion of the data is in an
appendix of this volume.
The NJIT and NYSDOH data for cadmium, copper, lead,
manganese, and zinc were accepted.
The NJIT data for chromium, iron, and nickel were accepted.
The NYSDOH data for arsenic and barium were accepted; NJIT
did not provide data for these.
The NJIT data for mercury were accepted; there is no
standard to assess accuracy, however. NYSDOH did not
provide mercury data.
The NYSDOH data for beryllium, cobalt, and molybdenum were
accepted, but there is no standard to assess their accuracy;
recoveries were good for solution spikes. Beryllium was
never detected by NYSDOH. NJIT did not provide data for
1 This assertion is based on information provided in an EPA
criteria document addressing the development of the PM-10
standard (for respirable-size particles) from the TSP standard
(for total suspended particulates) (U.S. EPA, 1986).
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beryllium or molybdenum; reported data for cobalt were
insufficient.
The NYSDOH data for chromium were rejected; recovery was
18%. The NYSDOH data for iron and nickel were accepted; but
with a caveat that they be regarded as minimum values since
recoveries were less than 80%.
NJIT data for BaP were accepted. NYSDOH data for BaP were
accepted but with a caveat, since recoveries averaged 49%.
2.2 Formaldehyde
The formaldehyde samples were collected by NJIT and NYSDEC
on 2,4-dinitophenylhydrazine-coated silica cartridges prepared
and analyzed by NSI, an EPA contract laboratory. Ozone
interferes with quantitation of formaldehyde by the method used;
no correction factor is available for use of the reported
concentrations as other than minimum values.
Formaldehyde data from the samples analyzed by NSI were
included in the project data base. Samples analyzed by NJIT were
not included due to the unavailability of QA information.
3. RESULTS AMD DISCUSSION
3.1 Concentration Data
Quarterly and annual average concentration data are
presented in Tables IIIB-1 through 16. Tables in the appendix of
this volume order the sites by annual average concentration and
by quarterly average concentration.
3.2 Comparisons to Concentration Data from Other Locations
Ranges and medians for annual average concentrations for
selected chemicals2 from the SI/NJ UATAP and the U.S. EPA Urban
Air Toxics Monitoring Project (UATMP) studies (U.S. EPA, 1989)
Generally, the metals selected for these comparisons were those
for which information for quantitative risk assessment was
available.
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are provided in Tables IIIB-17a and 18a. Minimum detection
limits (mdls) for the metals and BaP for the two studies are
listed in Table IIIB-17b. The annual average concentrations for
each compound at each of the 17 UATMP sites are listed in Tables
IIIB-17c and 18b, and compared graphically to the median annual
average concentration for the SI/NJ UATAP sites, or to
concentrations for individual SI/NJ UATAP sites, in Figures IIIB-
1 through 14. On the basis of these annual averages, the SI/NJ
UATAP data are comparable largely to the data for the UATMP
study. Interlaboratory comparisons with samples of known
composition would be necessary before any conclusions could be
drawn regarding possible differences in the data sets.
For copper, iron, lead, manganese, zinc, and BaP, the SI/NJ
UATAP annual average concentrations are at or below the median
concentration for the UATMP sites.
Cadmium concentrations at the SI/NJ UATAP sites are higher
than those at all but four of 17 UATMP sites. SI/NJ UATAP
chromium concentrations, available only for the three New Jersey
sites, were higher than those for all but three of 17 UATMP
sites.
The annual average concentrations of nickel and vanadium at
the SI/NJ UATAP sites data are, respectively, higher than those
at all but one of the UATMP sites, and higher than those at all
the UATMP sites. Vanadium and nickel are emitted by large oil-
burning sources in the northeastern United States, a region which
uses crude oils containing these elements.3
The graphs for cobalt and molybdenum show two unusual
characteristics. The SI/NJ UATAP data are unusually high
compared to the UATMP results; and identical concentrations are
reported for a number of the UATMP sites. These are likely to be
consequences of the differences in detection limits for the two
studies. The UATMP mdl for cobalt is 1.8 ng/m3; while the SI/NJ
UATAP mdl is 5 ng/m3. The UATMP mdl for molybdenum is 2.3 ng/m3;
while the SI/NJ UATAP mdl is 24 ng/m3. The reporting convention
for this project was that if the measured concentration was below
the mdl, the sample concentration was to be reported as half the
mdl. The combination of higher detection limits with readings
less than the mdl might account for the apparent higher
concentrations in the SI/NJ UATAP study area. In addition, the
chemical analyses for these two elements may be the cause for
apparent differences in concentrations at the SI/NJ UATAP sites
The airborne concentrations of nickel and vanadium decreased
markedly in New York City from the late 1960s to the mid-1970s as
the sulfur content of oils was reduced to meet S02 standards
(Kleinman et al., 1977).
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and the UATMP sites; cobalt and molybdenum are difficult to
dissolve and to analyze with accuracy. Thus, the reported
concentrations for these two elements should be given very
cautious consideration.
The data for arsenic appear to place the SI/NJ UATAP results
in the midrange of the UATMP data; again, however, a difference
in mdls might account for the apparent difference in
concentrations for the two studies. The mdls were 30, and later,
2 ng/m3 for the SI/NJ UATAP sites; and 5.5 ng/m3 for the UATMP
sites.
While the results for formaldehyde at two SI/NJ UATAP sites
are in the midrange of the annual average concentrations reported
for the UATMP sites, the consequence of the ozone interference
affecting both sets of data is that little information can be
derived regarding actual site-to-site differences in formaldehyde
concentration.11
3.3 Temporal Patterns
Concentration versus sampling date was plotted for multiple
analytes at single sites in a search for covariation of
particulate concentrations, and hence, suggestion of common
sources. The results are Figures IIIB-15 through 25.
Figures IIIB-15 to 18 for Carteret, NJ, exhibit the normal
variation in concentration with time found in data of this
nature. Variations in source emission rates and in
meteorological variables such as wind speed and direction affect
the airborne concentrations and cause the apparently irregular
variations in concentration. Visual comparisons of the results
for the ferrous metals in Figure IIIB-15 (nickel, chromium,
manganese, iron) with those for the non-ferrous metals in Figure
IIIB-16 (cadmium, copper, zinc, lead) indicate that they are not
closely related in their patterns. The dissimilarity of the
concentration patterns for lead and BaP (a polynuclear aromatic
hydrocarbon) in Figure IIIB-17 suggests that these two substances
are not from a common source.
Similar conclusions can be drawn from the results for the
Elizabeth site in Figures IIB-19 through 22, the Susan Wagner
Samplers in use for more recent years of the UATMP studies were
modified to reduce/remove the ozone interference regarded as not
amenable to use of a correction factor, and leading to an
underreporting of formaldehyde concentrations.
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site in Figures IIIB-23 and 25, and the PS-26 site in Figures
IIIB-26 through 28. In the latter two cases, some similarity in
patterns for some of the elements indicates that a complete
statistical analysis would be necessary to determine whether any
correlations did or did not exist in the results.
The complexity of the variables that create and disperse the
particles in the atmosphere has been known for many years.
Statistical methods can be applied to the data with the aid of a
computer to obtain an understanding of the impacts of
meteorological variables and source emissions on the airborne
concentration patterns of the particles. However, because of the
cost of the computer analyses, the statistical approaches are
usually reserved for cases where significant health risks or
potential regulatory violations must be addressed.
3.4 Spatial Patterns
Figures IIIB-29 through 42 provide a comparisons of
concentration patterns (concentration versus sampling date) for a
single analyte at multiple sites. The graphs have been sorted
into the order of barium, ferrous metals, non-ferrous metals, and
BaP. In cases for which two laboratories generated the reported
concentrations, graphs representing another level of sorting are
provided lest interlaboratory differences confound the
observation of similarity in patterns.
3.4.1 Barium
The data for barium at Susan Wagner and PS-26 in Figure
IIIB-29 suggest the likelihood of a relationship between
concentrations at these two sites.
3.4.2 Iron
Figures IIIB-30 through 32 for iron show that the patterns
for the four sites are similar and no major difference exists
between the data for the sites in the two states. The results
are the same for manganese (Figures IIIB-33 through 35); note
that the scales for the x- and y-axes in Figures 34 and 35 differ
by a factor of 2, resulting in an apparent visual difference that
does not appear in Figure IIIB-33.
3.4.3 Nickel
The results for nickel are different in that the two sites
in each state are similar, but the seasonal trends differ for the
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two sets of monitors. See Figures IIIB-36 through 38. Peak
concentrations in New Jersey occur in the period from April to
August 1989, while the peak concentrations in New York occur in
the period from January to February 1989. While insufficient
information is available to provide a definitive explanation of
these patterns, rationalization of the observations might involve
such variables as seasonal variations in wind direction or
velocity, number of sources and their locations relative to the
monitors, and interlaboratory differences.
3.4.4 Cobalt
No conclusions can be drawn for cobalt (New York sites
only), for which concentrations were less than the mdl of 5
ng/m3.
3.4.5 Vanadium and chromium
For vanadium and chromium there are data for only one state
in each case—vanadium for New York, and chromium for New Jersey.
For both cases, Figures IIIB-39 and 40, the pairs of sites appear
to show the same temporal variations. The period of higher
concentrations for chromium occurs from April to June of 1989;
source emissions, source versus sampler locations, and/or
meteorological variations are possible causes of the
concentration differences.
While average wind speeds are lower in the summer and higher
in the winter in the region, it is possible that the drying of
soils in the spring could permit resuspension of contaminated
soil with increased airborne concentrations of chromium as seen
in Figure IIIB-40. The concentrations would decrease when
vegetative cover grows over the soil, or when the soil is wet or
frozen and less easily resuspended. Resuspension occurs mostly
for the larger particles, with a relatively small fraction in the
respirable-size range which may reach the deep lung (alveoli).
3.4.6 Lead
The patterns for lead in Figures IIIB-42 through 44 show
distinct differences between the data for the two states. The
concentrations in New Jersey are about 40 ng/cu.m from October to
December of 1988, followed by a drop to about 20 ng/cu.m from
January to mid-March of 1989, and a return to about 40 to 50
ng/cu.m from late March to early June. The data for New York are
around 40 ng/cu.m from October 1988 to March of 1989, decreasing
to around 20 ng/cu.m from April to mid-June.
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Drops in average concentrations are often related to
seasonal shifts in average wind speeds; however, an average
windspeed variation would be regional in nature and affect all
stations in a similar manner. Thus the shifts in lead
concentrations in these data must be related to variables that
are not regional in nature, but more local to the sampling sites.
Such variables could be a combination of the geometry of source
and sampler locations with the average wind direction for the
various sites and time periods. Note also that the time period
of the higher chromium concentrations does not coincide with the
return of higher lead concentrations, nor do the other changes in
the concentrations of these two elements show any similarities.
3.4.7 Copper and zinc
The data for copper and zinc (Figures IIIB-44 through 49)
show little or no difference between the two states, and suggest
no apparent relationships to potential emission sources, sites,
or time periods.
3.4.8 Cadmium
For the New Jersey sites in Figure IIIB-50, there appears to
be a trend towards higher cadmium concentrations over the one-
year sampling period. The concentration increased from about 10
ng/m3 in October 1988, to about 50 ng/m3 in September 1989.
3.4.9 Mercury
Mercury data were available only at the New Jersey sites,
where there was an apparent decreasing trend in concentrations to
less than 0.5 ng/cu.m for the period from January to September
1989. See Figure IIIB-51.
3.4.10 BaP
BaP was measured at five sites including the background
site. The ranges of concentrations and temporal variations are
essentially the same for all five sites (Figures IIIB-52 through
55). This compound serves as an indicator compound for all of
the polynuclear aromatic hydrocarbons—a class of compounds
emitted by all fossil fuel burning sources, with auto and truck
traffic often the predominant factors. The similarity in the
data for all five sites indicates that the mobile sources
predominate in this area and reflects the regional influences of
traffic variation with season, as well as regional meteorological
effects.
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The lack of similarity of the patterns of lead and BaP
indicates that the mobile sources are no longer significant in
the overall lead emissions in the area.
4. CONCLUSIONS
The data sets for analytes found in the particulate matter
samples for the SI/NJ UATAP show that many of these toxic
substances are in the same concentration ranges as those found
for a number of sites in the EPA UATMP program during the same
time period. Where the SI/NJ UATAP data appear to be high, as is
the case for cadmium, vanadium (New York sites only, no valid
data for New Jersey sites), and nickel, there is an unfortunate
lack of certainty regarding accuracy of the reported SI/NJ UATAP
results. Vanadium and nickel concentrations have been higher in
the northeast than in other regions of the U.S. for many years.
There is little indication of unusual impacts from industrial
sources in the area, with only cadmium showing an increasing
concentration trend. Chromium concentrations were generally
higher at the New Jersey sites than at most of the UATMP sites;
no valid data were available for the New York sites.
There are a number of interesting and potentially useful
temporal and spatial patterns in the data, with some substances
showing differences between the sampling sites in the two states,
but not between sites within the states. Determination of the
likely causes of the patterns in the results would require a
major effort using multivariate statistical methods. Separating
source and meteorological effects might require concentration
data for additional chemical species, and meteorological data not
currently in the data base. Such a complex, costly program might
be justified in cases where the likelihood of a significant
health risk or of a regulatory violation has been demonstrated.
Since an ozone interference negatively biased the
formaldehyde results, little information is derived from the
apparent site-to-site differences for this compound.
5. ACKNOWLEDGEMENT
This volume was prepared by Dr. Theo. J, Kneip with support
from Karen Seet, Henry Feingersh, Avi Teitz, and Carol Bellizzi
of the U.S. Environmental Protection Agency Region II, and from
Olga Boyko of the New Jersey Department of Environmental
Protection and Energy.
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6. REFERENCES
Kleinman, M.T.; Pasternack, B.S.; Eisenbud, M; Kneip, T.J.
(1980) Identifying and estimating the relative importance of
the source of airborne particulates. Environ. Sci. &
Technology 14: 62-65.
U. S. Environmental Protection Agency. (1986) Procedures for
estimated probability of nonattainment of a PM10 NAAQS using
total suspended particulate or PM10 data. Research Triangle
Park, NC: Office of Air Quality Planning and Standards; EPA
report no. EPA-450/4-86-017.
U. S. Environmental Protection Agency (1989a). Nonmethane
organic compound monitoring program, final report, volume
II: urban air toxics monitoring program, April 1989.
Research Triangle Park, NC: Office of Air Quality Planning
and Standards; EPA report no. EPA-450/4-89-005.
10
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Table IIIB-1
ARSENIC
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
SITE * OF
* SAMPLES
B
A
E
1 11
2 13
ARITH. HEAN
(ng/m3)
1.9
2.7
* OF ARITH. HEAN * OF ARITH. MEAN it OF ARITH. MEAN * OF ARITH. MEAN
SAMPLES (ng/m3> SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/irtf)
14
K
2.6
3.5
U
U
9.5
11.1
10
11
12.9
11.6
49
52
6.5
7.1
ARSENIC
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
SITE * OF
* SAMPLES
B
A
E
1 9
2 10
ARITH. MEAN
(ng/m3)
K.5
* OF ARITH. MEAN * OF ARITH. MEAN lit OF ARITH. MEAN * OF ARITH. MEAN
SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3)
13
9
5.1
11
11
1.1
1.4
15
U
1.0
1.0
48
44
3.7
4.3
11
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Table IIIB-2
CADMIUM
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
SiTE c?M?,Fce ARI™- MEAN *°F ARI™- HEAN *°F AR'TH. MEAN *OF ARITH. MEAN * OF ARITH. MEAN
* SAMPLES SAMPLES
9.3
0.8
2.5
2.0
#OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN
SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/nij) SAMPLES (ng/m3)
15
15
15
13
9
1.8
1.5
2.3
2.3
2.0
15
13
15
11
12
1.9
1.8
1.7
2.5
2.5
15
11
12
15
15
4.1
2.7
2.2
2.5
3.0
60
54
42
48
46
4.3
1.6
2.1
2.4
2.5
12
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Table IIIB-3
CHROMIUM
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING FIRST YEAR
OCTOBER 1987 JANUARY 1988 APRIL 1988 JULY 1988 OCT 1987 - SEPT 1988
SITE * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN « OF ARITH. MEAN * OF ARITH. MEAN
SITE * SAMPLES (ng/mS) SAMPLES
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Table IIIB-4
COBALT
SITE
SUSAN WAGNER MS
PS 26
QUARTER BEGINNING
OCTOBER 1987
SITE « OF
* SAMPLES
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST TEAR
OCT 1987 - SEPT 1988
11
13
ARITH. MEAN
(ng/m3)
2.7
3.0
* OF ARITH. MEAN * OF ARITH. MEAN « OF ARITH. MEAN * OF ARITH. MEAN
SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3)
U
U
2.5
3.0
14
U
2.9
3.2
10
11
2.6
2.2
49
52
2.7
2.9
COBALT
SITE
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
SITE « OF
# SAMPLES
9
10
ARITH. MEAN
(ng/m3)
2.5
2.0
« OF ARITH. MEAN * OF ARITH. MEAN « OF ARITH. MEAN # OF ARITH. MEAN
SAMPLES
-------
Table IIIB-5
COPPER
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
*
B
A
E
1
2
* OF
SAMPLES
13
11
13
ARITH. MEAN
(ng/m3)
47.0
83.8
59.2
* OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN
SAMPLES (ng/m3) SAMPLES SAMPLES (ng/m3) SAMPLES (ng/m3)
47.0
83.8
59.2
15
14
U
78.4
90.7
45.9
10
3
14
14
113.5
76.4
121.1
50.5
14
13
10
11
105.4
22.9
95.3
75.4
52
16
49
52
84.6
32.9
98.8
56.7
COPPER
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
SITE * OF
* SAMPLES
15
9
10
ARITH. MEAN
(ng/n3)
26.6
79.4
39.6
* OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN # OF ARITH. MEAN
SAMPLES (ng/m3) SAMPLES (ng/m3> SAMPLES
-------
Table IIIB-6
IRON
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING FIRST YEAR
OCTOBER 1987 JANUARY 1988 APRIL 1988 JULY 1988 OCT 1987 - SEPT 1988
SITE * OF ARITH. KEAN « OF ARITH. MEAN * OF ARITH. NEAN * OF ARITH. NEAN * OF ARITH. MEAN
SITE * SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/mS) SAMPLES (ng/m3)
13
11
13
519.7
511.9
1168.0
15
14
14
752.6
522.8
875.7
10
3
14
14
805.4
661.0
807.8
1468.0
13
10
11
495.6
888.0
1433.0
38
16
49
52
686.8
526.6
676.3
1226.1
CARTERET B
ELIZABETH A
HIGHLAND PARK E
SUSAN WAGNER HS 1
PS 26 2
IRON
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING SECOND YEAR
OCTOBER 1988 JANUARY 1989 APRIL 1989 JULY 1989 OCT 1988 - SEPT 1989
SITE * OF ARITH. NEAN « OF ARITH. MEAN * OF ARITH. MEAN # OF ARITH. MEAN # OF ARITH. MEAN
SITE # SAMPLES (ng/«3> SAMPLES (ng/mJ) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3)
CARTERET B 15 426.0
ELIZABETH A 15 308.4
HIGHLAND PARK E
SUSAN WAGNER HS 1 9 537.3
PS 26 2 10 738.0
15
15
15
13
9
508.1
401.5
376.4
690.0
970.0
15
13
13
11
11
689.7
493.1
656.7
610.0
800.0
15
11
12
15
15
795.4
552.8
406.3
710.0
1110.0
60
54
40
48
45
604.8
428.5
476.5
649.3
923.6
16
-------
Table IIIB-7
LEAD
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT
1988
SITE * OF ARITH. NEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF AR1TH. NEAN
* SAMPLES (ng/m3) SAMPLES (ng/n3) SAMPLES (ng/n\3) SAMPLES (ng/m3) SAMPLES (ng/m3)
13
11
13
69.0
58.2
82.5
15
14
14
118.7
31.1
46.4
10
3
14
14
30.8
21.6
44.6
44.8
13
10
11
31.3
49.3
55.3
38
16
49
52
78.6
29.5
44.7
56.9
LEAD
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
SITE 0 OF ARITH. MEAN 0 OF ARITH. MEAN 0 OF ARITH. MEAN 0 OF ARITH. MEAN 0 OF ARITH. MEAN
0 SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES
-------
Table IIIB-8
MANGANESE
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN UAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
SITE * OF
# SAMPLES
13
11
13
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
ARITH. MEAN
-------
Table IIIB-9
MERCURY
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
SITE * OF
* SAMPLES
B
A
E
1
2
ARITH. MEAN
Cng/m3)
# OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN « OF ARITH. MEAN
SAMPLES (ng/mS) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3)
15
0.5
10
3
0.6
0.9
13
1.2
25
16
0.5
1.1
MERCURY
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
SITE * OF
* SAMPLES
15
15
ARITH. MEAN
(ng/m3)
0.8
0.7
# OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN # OF ARITH. MEAN
SAMPLES (ng/m5) SAMPLES (ng/m3) SAMPLES
-------
Table IIIB-10
MOLYBDENUM
SITE
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
SITE * OF
* SAMPLES
11
13
ARITH. MEAN
(ng/ffl3)
11.1
12.4
* OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN
SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3)
14
14
10.8
12.3
14
14
11.0
12.9
10
11
10.8
8.9
49
52
10.9
11.8
MOLYBDENUM
SITE
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1988
SITE * OF
* SAMPLES
QUARTER BEGINNING
JANUARY 1989
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
9
10
ARITH. MEAN
(ng/R)3)
10.7
7.9
* OF ARITH. MEAN 0 OF ARITH. MEAN # OF ARITH. MEAN * OF ARITH. MEAN
SAMPLES (ng/tn3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES
-------
Table IIIB-11
NICKEL
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
SITE * OF
* SAMPLES
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
13
11
13
ARITH. MEAN
-------
Table IIIB-12
VANADIUM
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING fIRST TEAR
OCTOBER 1987 JANUARY 1988 APRIL 1988 JULY 1988 OCT 1987 - SEPT 1988
SITE * OF ARITN. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN
SITE « SAMPLES (ng/«5) SAMPLES SAMPLES (ng/m3) SAMPLES (ng/nfl) SAMPLES (ng/m5)
SUSAN WAGNER HS 1 11 12.8 14 19.4 U It.6 10 9 5 49 13 6
PS 26 2 13 14.8 14 23.9 U 15.5 11 14.9 52 17.5
VANADIUM
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING SECOND YEAR
OCTOBER 1988 JANUARY 1989 APRIL 1989 JULY 1989 OCT 1988 - SEPT 1989
SITE * OF ARITH. MEAN # OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN
SITE # SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES Cng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3)
SUSAN WAGNER HS 1 9 9.3 13 22.5 11 10.1 15 16.2 48 15.2
PS 26 2 10 15.2 9 19.8 11 16.0 15 17.0 45 16.9
22
-------
182.0
112.4
145.5
15
U
14
89.8
89.5
107.8
10
3
14
14
90.3
78.4
95.1
106.8
13
10
11
83.8
176.1
160.8
38
16
49
52
121.5
62.8
113.9
128.2
Table IIIB-13
ZINC
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING FIRST VEAR
OCTOBER 1987 JANUARY 1988 APRIL 1988 JULY 1988 OCT 1987 - SEPT 1988
SITE IT OF ARJTN. MEAN * OF ARITH. MEAN * OF ARITK. MEAN * OF ARITH. HEAN OOF ARITH. MEAN
SITE « SAMPLES (ng/m3) SAMPLES
CARTERET B 13
ELIZABETH A
HIGHLAND PARK E
SUSAN WAGNER HS 1 11
PS 26 2 13
ZINC
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING SECOND YEAR
OCTOBER 1988 JANUARY 1989 APRIL 1989 JULY 1989 OCT 1988 - SEPT 19B9
SITE * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN
SITE * SAMPLES (ng/n3) SAMPLES (ng/m3) SAMPLES (ng/mS) SAMPLES (ng/m3) SAMPLES (r»g/m3)
CARTERET B 15 93.0
ELIZABETH A IS 117.9
HIGHLAND PARK E
SUSAN UAGNER HS 1 9 88.4
PS 26 2 10 83.8
15
15
IS
13
9
101.5
88.1
77.8
117.5
120.2
15
13
IS
11
11
93.2
105.9
134.9
54.2
70.4
15
11
12
10
15
173.1
131.3
76.5
194.7
109.3
60
54
42
43
45
115.2
109.5
97,8
113.2
96.3
23
-------
Table I1IB-14
BENZO
U
0.15
10
3
0.07
0.06
14
13
0.09
0.03
51
16
0.17
0.04
BENZO(A)PYRENE
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
SITE 0 OF
0 SAMPLES
B 15
A 15
E 10
ARITH. MEAN
(ng/m3)
0.24
0.22
0.31
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
0 OF ARITH. MEAN 0 OF ARITH. MEAN # OF ARITH. MEAN 0 OF ARITH. MEAN
SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/ro3)
15
15
15
0.35
0.29
0.15
15
14
15
0.07
0.11
0.06
15
11
13
0.15
0.12
0.07
60
55
53
0.20
0.19
O.U
-------
Table IIIB-15
FORMALDEHYDE - HCHO (METHANAL)
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1986
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
CARTERET
ELIZABETH
PISCATAWAY
SUSAN UAGNER HS
PORT RICHMOND PO
SITE * OF ARITH. MEAN * OF ARITH. MEAN # OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN
* SAMPLES (ppb) SAMPLES (ppb> SAMPLES (ppb) SAMPLES (ppb) SAMPLES
B
A
D
1
5
2.91
10
3.38
10
1
4.B1
3.30
4.05
25
10
1
3.63
3.30
4.05
FORMALDEHYDE - HCHO
SITE
CARTERET
ELIZABETH
PI SCATAIMY
SUSAN UAGNER HS
PORT RICHMOND PO
(METHANAL}
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
QUARTER BEGINNING
APRIL 1989
QUARTER BEGINNING
JULY 1989
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
*
8
A
D
1
5
* OF
SAMPLES
7
8
9
ARITH. MEAN
-------
Table IIIB-16
BARIUM
SITE
SUSAN WAGNER HS
PS 26
QUARTER BEGINNING
OCTOBER 1987
QUARTER BEGINNING
JANUARY 1988
QUARTER BEGINNING
APRIL 1988
QUARTER BEGINNING
JULY 1988
FIRST YEAR
OCT 1987 - SEPT 1988
SITE * OF ARITH. MEAN # OF ARITH. MEAN * OF ARITH. MEAN * OF ARITH. MEAN # OF ARITH. MEAN
* SAMPLES (ng/m5) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES (ng/m3) SAMPLES
-------
Table IHB-17a; Comparison of 1988 UATMP and 1989 SI/NJ UATAP metals and benzo[a] pyrene
Concentrations, ng/m3
Lead
Chromium
Nickel
Arsenic
Cadmiua
Mercury
Manganese
Cobalt
Copper
Iron
Molybdenum
Vanadium
Zinc
Benzo[a]pyrene
Range for SI/NJ UATAP annual avgs.,
10/88-10/89 (excluding Highland Park)
fRef: Data summaries of 1/90/92.)
min.
14.4*
31.3
15.6
19.1
3.7
1.8
0.5
14.8
2.5
36.0
445.6
9.6
15.2
96.3
0.15
max.
45.7*
37.2
26.8
28.2
4.3
4.2
0.5
21.6
2.5
83.3
923.6
9.7
16.9
116.1
0.21
median If of sites)
34.74
33.9
21.2
21.9
4.0
2.1
0.5
15.0
2.5
60.1
624.1
9.6
16.0
113.6
0.17
(4)
(2)**
(4)***
(2)
(4)
(2)
(4)
(2)
(4)
(4)
(2)
(2)
(4)
(4)
SI/NJ UATAP for
Highland Park,
1/89-10/89
annual avg.
min. 20.5/max. 91. U
47.8
12.3**
22.4
-
2.1
0.4
13.3
-
34.5
476.3
.
-
97.8
0.14
Range for 1988 UATMP
annual averages
for 17 urban areas
min.
10*
1.5
2.8
2.8
0.5
-
20.4
0.9
2.0
554.9
1.2
4.9
24.8
0.032
max.
440*
25.0
34.0
8.4
13.3
-
491.7
1.5
1913.0
9154.0
3.6
14.3
1084.0
5.212
median
40*
5.6
3.8
3.3
0.9
-
28.8
0.9
77.5
1182.0
1.2
5.2
89.1
0.183
* Quarterly averages, not annual averages.
* Not annual averages; based on 50 quarterly averages.
** Annual average uas computed without having data for 10/88 to 1/89.
*** The annual averages for two of the four sites were computed without having data for 10/88 to 1/89.
27
-------
Table IHB-17b; Detection limits for the metals and benzo[a]pyrene in the 1988 UATHP and the Sl/NJ UATAP
Chemical Minimum detection limit. ng/m3
1988 UATHP SI/MJ UATAP
MYSDOH NJIT
Lead
Chromium, total 10 - 10
Nickel 5.6 5 7.5
Arsenic 5.5 30. 2*
Cadmium 1.1 5 2.5
Mercury - - 0.01
Manganese 40.8 5 5
Cobalt 1.8 5*
Copper 3.2 5 7.5
Iron 20.3 11 10
Molybdenum 2.3 24
Vanadium 9.9 5
Zinc 13.3 10 3.5
Benzo[a]pyrene 0.2
- Not available.
* The minimum detection limit changed in mid-1988. Ref: Personal communication of S. Koblenz. NTSOOH to C. Bellizzi, U.S. EPA Region II, ca. February 1992.
* The minimum detection limit was not constant; sometimes it was lower than 5 ng/m3.
28
-------
Table HlB-17c: Metals and benzo[a]pyrene data from 1988 UATMP*
(18) (30) (20) (19) (20) (19) (9)
Cleveland, OH Sauget, IL Lansing, MI Midland, HI Port Huron, MI Detroit, MI Dearborn, MI
Lead, quarterly avgs.. ng/m3
1st qtr 150 100 30 20 40 60 70 (110)***
2nd qtr 410 270 20 10 30 70 80(110)***
3rd qtr 440 270 20 20 40 80 130 (100)***
4th qtr ... . . (90)***
Annual avg.**. ng/m3
Chroniun 25.0 9.8 5.2 (1.5)*** 5.2 5.2 7.7 23.9
Nickel 8.8 3.5 3.5 2.8 4.2 4.1 8.4
Arsenic 7.0 8.4 2.9 2.8 2.8 3.3 5.6
Cadmium 10.0 13.3 0.5 0.7 0.7 3.4 4.7
Mercury ... - - (0.3)***
Manganese 194.6 49.2 23.8 23.1 21.5 79.2 491.7
Cobalt 1.3 0.9 1.1 0.9 0.9 1.5 1.0
Copper 102.5 520.9 49.3 10.0 20.0 50.3 77.5
Iron 4279.0 1182.0 824.1 (431.8)*** 554.9 609.5 (343.7)*** 2047.0 9154.0
Molybdenum 3.6 1.6 1.2 1.2 1.2 1.3 3.1
Vanadium 7.0 4.9 5.2 4.9 10.8 5.2 9.5
Zinc 459.8 506.1 61.0 (81.4)*** 33.8 74.5 512.6 1084.0
Benzo[a]pyrene 5.212 0.183 0.434 0.171 0.100 0.319 0.374
* AIRS database print-out of 8/22/90. Data coded as 1988, organization code 800 (USEPA Monitoring Support Lab).
Hammond,IN, and Portland, OR. data were not available.
** Arithmetic mean
*** As measured by another organization.
Example of how to read this table:
(18) < Total number of valid samples
Cleveland. OH <—Monitor site name
Chromium 25.0 < Annual average concentration of chromium
Nickel 8.8
Arsenic 7.0
Cadmium 10.0
Mercury - <- Chemical was not included at this site.
29
-------
Table IIIB-17c. continued: Metals and benzo[a]pyrene data from 1988 UATMP*. continued
(16) (21)
Jacksonville. FL Miami, FL
(21)
Houston, TX
Lead, quarterly avgs., ng/m3
1st qtr
2nd qtr
3rd qtr
4th qtr
Annual avg.**, ng/m3
Chromium
Nickel
Arsenic
Cadmium
Mercury
Manganese
Cobalt
Copper
Iron
Molybdenum
Vanadium
Zinc
40
30
30
~
6.0
6.1
4.3
0.7
-
20.4
1.1
50.1
721.7
1.2
14.3
88.2
40
40
20
-
5.6
4.7
3.1
0.5
-
20.4
0.9
49.3
556.0
1.2
5.3
89.1
20 (40)***
20 (70)***
20 (30)***
(40)***
Benzo(a)pyrene
0.222
0.100
5.6
6.7
2.8
0.6
25.8
0.9
80.0
685.3
1.2
6.7
66.2
0.117
(22)
Dallas, TX
30
20
20
5.2
2.8
2.8
0.8
20.4
0.9
51.4
681.4
1.2
4.9
24.8
0.100
(23)
Atlanta, GA
50
50
30
5.5
2.8
3.5
1.4
28.8
0.9
65.0
1296.0
1.2
4.9
96.9
0.229
(23)
Burlington, VT
(11)
Chicago, IL
40
30
30
5.5
3.8
3.2
0.7
30.4
0.9
253.9
1285.0
1.2
6.7
73.1
0.147
80
40
12.6
2.8 (13.1)***
3.3
1.1
87.2
0.9
114.7
1588.0 (862.0)***
1.2
4.9
148.2
0.357
* AIRS database print-out of 8/22/90. Data coded as 1988.
Hammond,IN, and Portland, OR, data were not available.
** Arithmetic mean
*** As measured by another organization.
organization code 800 (USEPA Monitoring Support Lab).
30
-------
Table IllB-17c. continued: Metals and benzo[a]pyrene data from 1988 UATKP*, continued
(21)
(21) (22) Baton
Birmingham, AL Louisville, KY Rouge. LA
Lead, quarterly avgs., ng/mS
1st qtr 80 80 20
2nd qtr SO 90 20
3rd qtr 30 60 10
4th qtr
Annual avg.**, ng/m3
Chromium 6.1 9.8 5.2
Nickel 2.8 34.0 3.5
Arsenic 3.6 4.5 3.1
Cadmium 0.9 1.9 1.0
Mercury -
Manganese 34.2 64.5 21.4
Cobalt 0.9 1.5 0.9
Copper 1913.0 102.2 107.0
Iron 1078.0 1595.0 603.7
Molybdenum 1.5 2.4 1.2
Vanadium 4.9 4.9 8.8
Zinc 244.2 171.5 47.3
Benzotalpyrene 1.448 0.332 0.173
* AIRS database print-out of 8/22/90. Data coded as 1988, organization code 800 (USEPA Monitoring Support Lab).
Hammond,IN, and Portland, OR, data were not available.
** Arithmetic mean
*** As measured by another organization.
31
-------
Table HIB-18a; Comparison of 1989 UATHP and SI/MJ UATAP formaldehyde data*
Formaldehyde, ppbv
Range for SI/NJ UATAP annual avgs..
tO/88-10/89 (S.U. and Port Rich)
(Ref: Data summaries of 1/90/92.)
min. max. median (* of sites)
1.71 2.02 1.86 (2)
SI/NJ UATAP for
Pi scat away,
1/89-10/89
annual avg.
. **
Range for 1989 UATHP
annual averages
far 14 urban areas
min. max. median
1.41 3.81 2.04
Table IIlB-17b: Formaldehyde data from the 1989 UATMP*
(32)
Canden, NJ
(30)
Sauget. IL
(28) (30) (31) (7) (32)
Washington,D.C.-1 Washington,D.C.-2 St. Louis, MO Pensacola, FL Miami, FL
Formaldehyde, ppbv
2.419
1.45
3.768
3.148
2.465
1.674
1.763
(38)
Houston. TX
(29)
Dallas, TX
(32) (30) (30) (36)
Ft. Lauderdale, FL Chicago. IL Wichita. KS-1 Wichita. KS-2
(31)
Baton Rouge, LA
Formaldehyde, ppbv
2.319
2.010
2.243
2.073
1.471
1.409
1.525
* From EPA-450/4-91-006. January 1991, 1989 Urban Air Toxics Monitoring Program Aldehyde Results. U.S. EPA/Office of Air Quality Planning and Standards. Research
Triangle Park.
Both the UATMP and SI/MJ UATAP acknowledge an ozone interference with the sampling method.
The ozone interference results in the reporting of concentrations as lower than actual.
** Insufficient data; the average for seven samples during 10/88 to 1/89 was 1.78 ppbv.
32
-------
FIGURE IIIB-1
Comparison of SI/NJ UATAP Data (10/88-10/89)
with 1988 UATMP Data (10/87-10/88)
COPPER
E 2,000
1
8
o
o
0>
0)
CO
I
CO
c
1,000
500
\
\
V~/'~7\
^>$>v^>vv
Location
l Pvk NJ (SI/NJ UATAP background she)
• • Madum for Cartefet, Bizabeti, PS-26. and
Susan Wagner H.S.
33
-------
FIGURE IIIB-2
Comparison of SI/NJ UATAP Data (1 #88-10/89)
with 1988 UATMP Data (10/87-10/88)
IRON
10,000
8,000
o
to
~ 6,000
8
«
o
2
o
rv
c
c
4,000
2,000
V77X \
•^>V^W^
Location
* Hif^aid Park NJ (SI/NJ UATAP back^xxnd site)
"• M»cfiai for Cartarat, Bizabeti, PS-26, end
Susan Warper H.S.
-------
O
o
FIGURE IIIB-3
Comparison of SI/NJ UATAP Data (10/88 10/89)
with 1988 UATMP Data (10/87-10/88)
LEAD - Highest Quarterly Average
15 400
6
con
9
I
100
D
CT
CD
0
; -
«?
c^>:<^^
4*0
W
^s^
Location
SI/NJ UATAP site
3 5
-------
eoo
FIGURE IIIB-4
Comparison of SI/NJ UATAP Data (10/88-10/89)
with 1988 UATMP Data (10/87-10/88)
MANGANESE
13
.O
c
o
o
o
o
1
400
300
200
100
I o
v > s\ v / /\
FTTl VTA
17771
Location
• HigNaid PM( NJ (SI/NJ UATAP backyound site)
•• Median for Cartoret, Eirabeti, PS-26, and
Susan Waiter M.S.
36
-------
E 1,200
iHooo
cf
"•g 800
c
eoo
o
o
I «»
200
(0
FIGURE IIIB-5
Comparison of SI/?MJ UATAP Data (10/88-10/89)
with 1988 UATMP Data (10/87-10/88)
ZINC
I
IZZA
V7AWAV7A
I I I I \ l^ I I I I I I I I I I
Location
• H&*»id Pafc NJ (SI/NJ UATAP backgrowid site)
** Median for Cartorat Btzabeti, PS-26. and
Susan Warier H.S.
37
-------
FIGURE IIIB-6
Comparison of SI/NJ UATAP Data (10/88-10/89)
with 1988 UATMP Data (10/87-10/88)
BENZO(A)PYRENE
o
c
O
I4
"c
83
C «*
O
O
-------
14
FIGURE IIIB-7
Comparison of SI/NJ UATAP Data (10/88-10/89)
with 1988 UATMP Data (10/87-10/88)
CADMIUM
o 10
2
I 8
o «
o 6
>t>^^>^
39
-------
FIGURE IIIB-8
Comparison of SI/NJ UATAP Data (10/88-10/89)
with 1968 UATMP Data (10/87-10/88)
CHROMIUM
^ 30
c
I 20
§15
8
>^^>S>V^VV*
Location
* Highland Park NJ (SI/NJ UATAP background site)
** Median for Carteret and Elizabeth
40
-------
FIGURE IIIB-9
Comparison of SI/NJ UATAP Data (10/88-10/89)
with 1988 UATMP Data (10/87-10/88)
NICKEL
Location
Holland Pafc NJ (SI/NJ UATAP background site)
Median tor Carteret, Bizabetti, PS-26, and
Susan Wagner H.S.
41
-------
20
FIGURE IIIB-10
Comparison of SI/NJ UATAP Data (10/88^10/89)
With 1988 UATMP Data (10/87-10/88)
VANADIUM
g 10
8
7,
X^>^V^VVXV
Location
Metiai for Susai Wagnef H S. and P&26
42
-------
FIGURE IIIB-11
Comparison of SI/NJ UATAP Data (KV88-10/89)
with 1988 UATMP Data (10/87-10/88)
COBALT
2.5
I
o
§1.5
§
S 1
16 0.5
c
Ł / / /
/// 7/7 V
• Median for Susan Wagner M.S. and PS-26
*V **V _*&
>>^>^^<>^>d
yr
Location
-------
10
FIGURE IIIB-12
Comparison of SI/NJ UATAP Data (10/88-10/89)
with 1988 UATMP Data (10/87-1Q/88)
MOLYBDENUM
8
c
o
fi
C 6
0>
o
o
CD
0
L*X ^
^ .^& ,~** ^ ^* WV^ ^^
Locatbn
Metiwi for Susai Warier M.S. and PS-26
4 4
-------
10
FIGURE IIIB-13
Comparison of SI/NJ UATAP Data (10/88-10/89)
wrth 1988 UATMP Data (10/87-10/88)
ARSENIC
,o
ra
c
g
13
6
o
o
I
0
VI V^A lAjVI
/AV/AV/AV/A///,V/AV/AY//\
'-» 1 * •* « I t * ft lrgf*i \ A 4 *l l^f^Aiilrf^ri 1^4/1
A VSA
a>l^
\>K
^ A*"
Location
MMicn for Susan Wagrar H.S.
and PS-26
-------
FIGURE IIIB-14
Comparison of SI/NJ UATAP Data (KV88-10/89)
with 1989 UATMP Data for
FORMALDEHYDE
a
a.
I 3
8*
ID
a>
CO
1 1
Location
,a
^
Mecfan fcr Susan Wagrwr H.S. and Port Richnond
-------
200
co
O
150
100
LU
O
o
O
50
Figure IIIB-15
Nickel, Chromium, Manganese, and Iron
at Carteret, NJ
i I'nVi i i i i i i 11 i i i i i i i i i i i i i i i i i i i
I I I I I I
.f-CT-'-CVI .T-CSJf-OI .T-CJr-CM .r-Wt-CM .»~CVJ .OJ .t-OJ .*-
-O • • • -CO • • • -OC • ->->-Z • •—J
SIX DAY INTERVALS (i988-i989)
NICKEL
CHROMIUM
MANGANESE
IRON ( / 50 )
47
-------
Figure IIIB-16
Cadmium, Copper, Zinc, and Lead
at Carteret, NJ
400
x-. 300
CO
200
UJ
O
O
O
100
CADMIUM (X 10)
COPPER
ZINC
LEAD
/ \ , * \J I x / 1' '
\Xv-/' *.' V. t
i i 11 i i n 11 i 11 11 i i 11 i 11 i 11 111 i i i 111 i 11 i i 11 11 i i i i i 1111 i 11111 i i
.»-«OT-CNJ .T-CMr-CVI .-F-CM»-CVJ .T-W»-CM .t-W .CVJ .-»-CNJ .r-
t- • . • .Q • . • -co
SIX DAY INTERVALS (1988-89)
48
-------
1600
1400
^ 1200
CO
1000
800
O
O
O
600
400
200
Figure IIIB-17
Benzo[cr]pyrene and Lead
at Carteret, NJ
Q I I 1 I I I M I I I I I I 1 I I II Vl IVI I I I I I I I I I I I I I I II
BAP (X IOOO)
LEAD ( X 10 }
.T-CVJr-CVJ .^-CVJT-CM .*-CM»-CJ .i-CJ .CVJ .»-CM ,^-
-CO • • • -QC • ->->-2
SIX DAY INTERVALS (1988-89)
49
-------
^ 1.5
CO
HI
O
O
O
0.5
Figure I1IB-18
Mercury
at Carteret, NJ
MERCURY
SIX DAY INTERVALS (1988-89)
50
-------
100
80
CO
=- 60
<
*i n * "i '/*t / if-1 i » /
,' l vV V. AV'^M. '^A , VV'A ! '• ' x'Vv
V'\' , M'' i/'/»?;x'V*'''*^V/' ' 'V ^ (\
I I I I I i I II II I I I i I I I I M I I I I I I I I I I II I I I I II I I I I I I I I I | | | | | | | | | | | |
CDOOO^COWKaOCSICOinKt-CO^CDOOOCJCOlflKaT-PJ-^tOKO)
SIX DAY INTERVALS (1988-89)
NICKEL
CHROMIUM
IRON ( / 50 )
MANGANESE
51
-------
400
_ 300
CO
200
UJ
O
O
O
100
Figure IIIB-20
Cadmium, Copper, Zinc, and Lead
at Elizabeth, NJ
,^,^ v ,yr;^/y ', V-ft-/ '*'l/-\vr >fx ^ >
, v ' v ,,v, ' ' ^ s/ , , '\ i
KM I IT < I IN I I I I < I I I I I I II I I I If I I I I I I I I I I f I I I I I I I I I I I I I II I I I I I
CADMIUM ( X 10 )
COPPER
.T-CVJT-
-------
Figure IIIB-21
Benzo[cr]pyrene and Lead
at Elizabeth, NJ
o
o
LLI
O
70
60
50
40
30
8 *>
10
I I II I I I I I I I I I I I I I I I I I I I M I I I II M I I I I I I 1 II I I I I I I I I I I I I 1 I I
BAP { X 50 )
LEAD
Oi-rtinh»a)O
-------
Figure IIIB-22
Mercury
at Elizabeth, NJ
1.6
1.4
^ 1.2
CO
o
0.8
0.6
0.4
0.2
MERCURY
«i-CJ -C|CSI .CCVJ .*-Cg*-C\J .r-CM .CM .»-W .--
SIX DAY INTERVALS (1988-89)
-------
Figure IIIB-23
Molybdenum, Nickel, Cobalt, Iron, and Manganese
at Susan Wagner H.S.
120
100
CO
80
<
tr
UJ
O
O
O
60
40
20
SIX DAY INTERVALS (1988-89)
MOLYBDENUM
NICKEL
COBALT
IRON (/60 )
MANGANESE
55
-------
360
300
Ł2 250
Q
UJ
o
o
200
150
100
50
Figure IIIB-24
Arsenic, Cadmium, Copper, Zinc, and Lead
at Susan Wagner H.S.
l-H-U-M-l-H-M.I-U-I.H-M-l-l-H-M-l-H+H-H-t-H
ARSENIC (X 10)
CADMIUM
COPPER
ZINC
LEAD
SIX DAY INTERVALS (1988-89)
* 1800 graphed as 290 for better resolution of the various curves
56
-------
Figure IIIB-25
Benzo[o]pyrene, Vanadium, and Lead
at Susan Wagner H.S.
100
80
CO
=• 60
Q
LU
O
o
O
40
20
BAP
VANADIUM
LEAD
MI ......... M i
1 1 1 1 1 1
1 1 ......
.
LU
SIX DAY INTERVALS (1988-89)
57
-------
Figure IIIB-26
Molybdenum, Nickel, Copper, Iron, and Manganese
at PS-26
100
LLJ
20 -
SIX DAY INTERVALS (1988-89)
58
-------
Figure IIIB-27
Arsenic, Cadmium, Copper, Zinc, and Lead
at PS-26
250
200
CO
=- 150
|
<
H
Z 100
O
50
ARSENIC ( X 5 )
CADMIUM
COPPER
ZINC
LEAD
rvriTtrM-rivMTii-MTM-M VMTM-MTtiTt vr!VM-MTM-M-ri-i-n-r>r'n
<0 (DO ^~ CO lOK CD OCJ COlO K
SIX DAY INTERVALS (1988-89)
59
-------
100
80
CO
60
40
20
Figure IIIB-28
Benzo[a]pyrene, Vanadium, and Lead
at PS-26
co eo o •«-co 10 h» o) o eg
-------
FIGURE IIIB-29
BARIUM
TWO SITES
50
40
«• 30
1
O
20
10
PS 26
SWHS
J_L
SIX DAY INTERVALS (1988-89)
61
-------
FIGURE IIIB-30
2600
2000
1600
1000
500
IRON
4 SITES
(D CO O T-m lO N. O> O W CO »O K *~ O •*
.T-CO^-CVJ T-CSIT-CM ,i-cvit-oi .T-CVJ^-CM .T-CM .CM .T-CM ,^-
SIX DAY INTERVALS (1988-89)
ELIZABETH
CARTERET
PS 26
SWHS
62
-------
FIGURE IIIB-31
IRON
2 SITES (NJ)
1400
1200
1000
800
600
400
200
111. i t' i M 111 f 111111111111111111
ELIZABETH
CARTERET
QHi-»GjOOzzuJfnoa
OQQOOSoQ«cHJ^
^^\ ^^\ ^9^ ^9" ^i f^ ^^3 ^^J *^~ i^™
^^ ^^ *^ ^^»
SIX DAY INTERVALS (1988-89)
-------
FIGURE IIIB-32
IRON
2 SITES (NT)
zouu
^ 2000
•
2
•
O
(3 1500
2Ł
/•v
F
<
j]E 1000
z
I
z
O
500
r»
-
;
i
ii
'i
ii /i
'i / '
h / '
'i /i ,
h ; i ',
1 i / i ',
/ j . '
,' \ ' - v ' "
' •;•!,/ ' /' •!
i , i 'i i i • i i . i - i , \
J l " ' / i ' ' ' \ • » !
' ;, v." ' i, ( ' l' ' V i »
1 ( n • ' ' •' ' v i ' i , N
f H |.|| | | ,/< , ' J 1
\ ,S ' ' ' . ,' ' ' ' ' • ' '
V ^' * (,n " ' ' ' ' V
v i- ' ,^J • U< ui! ;' ; v
' Ii \ \fi -'i H 1
1 " i/ i *A' f/
>.i / r ,< ^ i/
'i /
\
i i i i i i i i M i i i i M i i i i i i M i i i i i i i i M i i i i i i i i MI i i i M i M i i M
PS 26
SWHS
(D CO O r-CO If) K O) O CM CO IO N r-CO-*
-------
FIGURE IIIB-33
120
100
g 80
O «>
LU
O
O
40
20
MANGANESE
4 SITES
V » I
» I
\i
v ~\' ;/- *
11111111111111111 11111 111111111111111111 ;
o
i-CJ .T-CVJf-OJ .T-CM^-CVJ .T-CJ .CVJ .'-CVJ .•«-
SIX DAY INTERVALS (1988-89)
EUZABETH
CARTERET
PS 26
SWHS
65
-------
FIGURE IIIB-34
MANGANESE
2 SITES (NJ)
120
100
o
3
O 60
40
O
O
20
EUZABETH
CARTERET
.*-rti-cvi .i-cvii-w .i-cvjT-evj .T-cMi-cvi .-»-cj .evj .^-cvj .T-
CO
SIX DAY INTERVALS (1988-89)
66
-------
FIGURE IIIB-35
MANGANESE
2 SITES (NY)
ou
50
^
•
5
3 *>
i
^
O 30
H^™
^
DC
Ł
LU 20
0
0
o
10
n
-
-
i
i
ii
i
i
; '
i, | n
'i »
, i , i n
ii i \ | M
• vi i ' Ml /, j;
' ; | : N : -' \ ii ;< ;
M I/ ^ ilf H '1 i \ji PV1
\ //v ! '/i 1* i ' ' J i i v r (i i
»' \ f/'^' > . • i | ,' 'i M 1M
\i i i?, i< i (1 r >i M i
- ' 1 i \ I » Mo , ' l| (
,i v > ' A ' ^ '
; » ' y i i f ^
' ' V :1
'
•< t
— II II 1 1 II 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 JJ
PS 26
SWHS
(OCOQT-(OlOKOJO->-z.
SIX DAY INTERVALS (1988-89)
67
-------
o
3
Q
LU
O
O
120
100
80
60
FIGURE IIIB-36
NICKEL
4 SITES
EUZABETH
CARTERET
PS 26
SWHS
SIX DAY INTERVALS (1988-89)
68
-------
80
60
O
Q
40
20
FIGURE IIIB-37
NICKEL
2 SITES (NJ)
0 i—1111111 11111111111111111111 111 11111 M i n 111 111 111
O CM CO IO h» T- CO •* CD 00 O CJ CO IO h«. O) r- OJ -* CD h* O)
•H •
ELIZABETH
CARTERET
SIX DAY INTERVALS (1988-89)
69
-------
FIGURE IIIB-38
NICKEL
2 SITES (NT)
\Ł\J
100
2
3 80
O 60
F
LU 40
O
8
20
o
•
i
- i i lii'i
'* -I / '\
- ; ' i; v;;^ ' >^ ~\
^ i ; ' / } ' \< -i \ A- N ; ', ' '
-r\ •> V, v -j . ' « v .' 7 / .;
i , />.; \/ r . \ /\x /s' ti i /^i
\ / > \ / !/ '
V \ 1
— 1 1 II 1 1 1 1 II 1 1 1 1 1 II 1 II 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
PS 26
SWHS
to co Q T-co in N o> o evi m in N i-m •* i-
.•'-OO-'-CM .i-CMf-CM t-CV4*-W ^-CN^CM ^04 CM i-
SIX DAY INTERVALS (1988-89)
-------
60
50
O
40
30
LU 20
o
8
10
*
*
1
rt
FIGURE IIIB-39
VANADIUM
2 SITES
•
i
, »
, t1
j»
• •
'
"
i »
1 '
1 l
i
,
",
"
i
•'
\. i
v
.T-CMf-CVJ ,^-CVJ»-M .'»-CM'»-O4 i-CVI CM ••-CM »-
SIX DAY INTERVALS (1988-89)
PS 26
SWHS
71
-------
FIGURE IIIB-40
CHROMIUM
2 SITES
200
150
o 100
50
ELIZABETH
CARTERET
.T-rt^-CVI T-CMT-CJ .i-
.T-CM't-CM .T-CJ .CVJ .1-CM .1-
§B5SS88853ffipp55iHlp55^1SSSg
OOZZ QQ-5-> C22 <<' ^ <
-------
O
140
120
100
80
< 60
40
20
FIGURE IIIB-41
LEAD
4 SITES
Mil
EUZABETH
CARTERET
PS 26
SWHS
SIX DAY INTERVALS (1988-89)
73
-------
FIGURE IIIB-42
LEAD
2 SITES
140
120
100
80
< 60
O
O
40
20
Q I 1 I I 1 I I I 1 I I I I I I I I I I I I I I I I I I I I I I II I I M I I | | | | | | | | | I I I I || I
EUZABETH
CARTERET
*-CVJ .i-OJT-OJ ,1-CVJ^M .i-OJ^-CM .-^CJ .CM ,^-CVJ .»-
2— J -g • -K^
SIX DAY INTERVALS (1988-89)
V)
74
-------
80
O
60
40
20 -
FIGURE IIIB-43
LEAD
2 SITES (NT)
•
1
1
1
- 1 1 It
' 1 |l ll
., ii! |
i ' !» ! ! i ! /'
1 ' r i 'v /'
* t ' {\ '
A i . ' i f i •
"" / 1- f : 1 1 1 1 | -1
1 ' 1 1 1 ! ' ' i PI
lij t i ll /' *f^
i ' . i ',' i! i il i ;" ' i ; i
i-ii •{ * i ' ' ' '
' i ; ; v '• * / i : '; ; ! l
i \! : ; ' ;Uv\ Vul
! u ! i .' \ •'-, ! !.'
j 1 \ • 1' i A i i
Ll 1 1 1 1 1 1 1 1 1 M 1 1 1 1 1 M 1 1 1 1 1 1 M 1 1 1 1 1 1 1 1 1
® COO'™ co 10 r^« o) o c\i co 10 s« ^PJ^CD oo o cvj to 10 f*» oi^ w ^
PS 26
SWHS
SIX DAY INTERVALS (1988-89)
75
-------
FIGURE IIIB-44
COPPER
4 SITES
300
250
3 20°
Q 160
100
50
co co Q T- co in N o> o evj co in K *- eo •* CD co o c>j eo 10 s.
-------
FIGURE IIIB-45
COPPER
2 SITES (NJ)
300
250
o
200
160
i
100
50
ELIZABETH
CARTERET
— .
OO^-CM .i-OJi-CM .T-OJT-CVJ .f-CVji-CM .T-CJ .CM ,*-CM .1-
•Q
•
8§§il
SIX DAY INTERVALS (1988-89)
77
-------
FIGURE IIIB-46
COPPER
2 SITES
250
PS 26
_ 200
O
(3 150
100
LU
ii i i
50
ri
ii
',
ii
ii
h
l
H
< i
11
i i
' i
' >
/
/I
l
M
\ 11
i i /
SWHS
o
m
SIX DAY INTERVALS (1988-89)
-------
FIGURE IIIB-47
400
300
200
100
ZINC
4 SITES
11
V)
SIX DAY INTERVALS (1988-89)
ELIZABETH
CARTERET
PS 26
SWHS
79
-------
FIGURE IIIB-48
ZINC
2 SITES (NJ)
400
300
200
100
ELIZABETH
CARTERET
to oo Q T-n m K a o cj co m K ^-co-^
.••-CO^-CM .^-CNi-CM .^-CM-r-CM .^-Ol-r-CVJ .^-OJ .CVJ .'-CM ,^-
SIX DAY INTERVALS (1988-89)
80
-------
FIGURE IIIB-49
ZINC
2 SITES (NT)
30U
300
***^
«
"* 250
5
Z 200
^
o
p
< 150
•Ł
UJ
i100
o
50
0
i
> }
i1
11
ii
!'. ' '
i' . 1 1
i' , i
" i
j '
i
, i
/» 'v '
i . d
< > =. i \ J '
«' « ! v '',
; \ ' * ' ' i
/ i 1 \\ ,\
' i i i i ' \
' ( 1 j* \ I 'J •/' ' ' \ t • !
> . (l '\ i it • , v is /, n
1 \ I < ' ' \ ' " ' N ' ' lj » M r% 1
" \ f |l \f ' ' ^ 1 l / ' 1 ^
! i; Vv i \ * « V V
II 1 ( \/\ ' U )
\\ • y v/x' u
ii V '
i(
i i i i i i i i i i i i i i i i i i | | | | || | | | | i i i i i i i i i i i
.f-cO'-cvj .^CMT-CVJ .^-CM'-CM .T-CJ^-CM .^cvj .CM .^-evj .*-
PS 26
SWHS
SIX DAY INTERVALS (1988-89)
81
-------
100
^ 80
FIGURE IIIB-50
CADMIUM
4 SITES
ELIZABETH (X10)
CARTERET (X10)
PS 26
SWHS
SIX DAY INTERVALS (1988-89)
82
-------
FIGURE IIIB-51
MERCURY
2 SITES
1.5
Q 1
S
LU
o
o
0,5 -
EUZABETH
CARTERET
1'— C>l .T-OJ^-CVJ .^"CJ .CVJ ,^'CVJ .T-
CO
SIX DAY INTERVALS (1988-89)
83
-------
1.6
1.4
1.2
0.8
0.6
8 °4
0.2
FIGURE IIIB-52
BAP
5 SITES
ELIZABETH
CARTERET
PS 26
SWHS
HIGHLAND PK
SIX DAY INTERVALS (1988-89)
84
-------
1.6
1.4
1.2 -
o
0.8
0,6 I-
0.4
0.2
FIGURE IIB-53
BAP
3 SITES (NJ)
ELIZABETH
CARTERET
HIGHLAND PK
Ms
SIX DAY INTERVALS (1988-89)
85
-------
FIGURE IIIB-54
BAP
HIGHLAND PARK
0.8
o.e -
O
0.4
0.2
LI 1 I I I I I M I I I I I I I I I M I I I I I L I I I I I I I I I I I I I I I
HIGHLAND PK
-
-------
FIGURE IIIB-55
BAP
3 SITES
0.8
0.6
o
0.4
O
0.2
PS 26
SWHS
HK3HLAND PK
I I I I I I I I I I I ..... I I I i ............... lYi i ii i i i ..... i
_1_L
.i-CMi-CI .T-CMi-CM .i-CVJ .CM .T^CVJ .*=
op.j-j-j-jo:-j_->->-z • -J -a • -H
^8lia§§ii^g|l
-------
APPENDICES
88
-------
APPENDIX A
QUALITY ASSURANCE SUMMARY FOR METALS, BENZO[a]PYRENE,
AND FORMALDEHYDE
1. INTRODUCTION
Each sampling organization was responsible for its own
Quality Assurance (QA). However, to ensure that appropriate
quality assurance methods were selected and followed, the QA
procedures of the organizations submitting monitoring data for
the project were reviewed by the QA Subcommittee.
2. METALS
Quality Assurance reports were received from both the New
Jersey Institute of Technology (NJIT) and the New York State
Department of Health (NYSDOH). NJIT's samples were collected by
its own staff, whereas the NYSDOH samples were collected by the
New York State Department of Environmental Conservation (NYSDEC).
2.1 Sample Collection
2.1.1 NYSDEC/NYSDOH
Sample collection and sampler calibration were conducted by
NYSDEC under the guidelines and procedures established in its
Ambient Air Quality Assurance Manual.
2.1.2 NJIT
NJIT's samplers were calibrated by the New Jersey Department
of Environmental Protection according to the methods outlined in
its Ambient Air Monitoring Quality Assurance Manual. Sample
collection was done by NJIT staff.
2.2 Analytical Results
Table IIIB-A1 provides a summary of the QA disposition of
the metals data from NYSDEC/NYSDOH and from NJIT.
A-l
-------
2.2.1 NYSDOH/NYSDEC
The analytical QA data provided by NYSDOH showed excellent
precision and recovery results for all compounds tested.
However, these data were generated using dilute solutions of
metals spiked onto filters. Field samples, however, consist of
particulates and not liquids, and the % recovery of metals from
particulates may be lower than % recoveries from liquid
standards.
To ascertain percent recoveries for particulate metals, an
urban dust Standard Reference Material (SRM) can be run. This
SRM, obtainable from the National Institute for Standards and
Technology (NIST), contains known trace amounts of many of the
metals monitored in the SI/NJ UATAP. However, NYSDOH did not run
these standards until recently.
NYSDOH results with the NIST urban dust SRM showed
recoveries of cadmium, copper, zinc, and lead to be 95% of the
SRM concentration. Barium and manganese recoveries were within
82% of the standard. Iron and nickel recoveries were within 75%
of the standard, and vanadium was within 63% of the NIST SRM.
Chromium recoveries were only 18% of the standard. Precision of
analysis for all compounds was uniformly excellent.
As a result of these findings, the data were treated as
follows:
1. All NYSDOH chromium data were rejected and removed from the
project data base.
2. The vanadium, iron, and nickel data were accepted, but were
caveated since their recoveries were below 80%. The values
reported for these compounds should be viewed as the minimum
values known to be present.
3. The cadmium, copper, zinc, barium, lead, and manganese data
were accepted. The results for arsenic, beryllium, cobalt,
mercury, and molybdenum were approved with the understanding
that their accuracy can not be verified with NIST
particulate SRMs because the SRMs do not exist.
The percent recovery data for NYSDOH results with SRMs are
presented in Table IIIB-A2, % Recovery From Urban Dust -
Ultrasonic Bath Digestion.
A-2
-------
2.2.2 NJIT
NJIT submitted QA data for 10 compounds: cadmium> chromium,
cobalt, copper, iron, lead, mercury, manganese, nickel, and zinc.
A serious concern with the NJIT report was the lack of specific
information pertaining to background contamination levels in
blank samples or the results of calibration checks. Also, data
to support estimates of precision were provided only for mercury.
Furthermore, NJIT asserted that absorbance vs. response curves
were generated for all compounds analyzed, but only provided
these curves for mercury and lead.
Mitigating these concerns, however, were NJIT's acceptable
analytical results for EPA particulate lead standards and the
HIST urban dust particulate SRMs. The NIST samples were analyzed
for 8 compounds: cadmium, chromium, copper, iron, lead, nickel,
manganese, and zinc. Recoveries using these standards were
typically in the range 85-100%. Therefore, NJIT's QA, though
somewhat lacking in documentation, was regarded as sufficient for
inclusion of data for the eight compounds named above into the
project data base.
Cobalt, although present in the NIST standard, was reported
by NJIT as below its detection limit. Since no other data,
including precision, calibration, and blank level data, were
included in the NJIT report, the cobalt data were excluded from
the project data base.
The submitted mercury data, although somewhat lacking in
detail, did include acceptable precision and calibration curve
data. Therefore, the mercury data were accepted for use in the
project data base. No standard was available from NIST or EPA
for mercury.
NJIT collected and reported data for vanadium, selenium, and
molybdenum during the course of the project. As stated in its QA
report, NJIT was unable to provide QA information for vanadium.
Selenium and molybdenum were not mentioned in NJIT's QA report at
all. Therefore monitoring data for these three compounds were
excluded from the project data base.
3. BENZO[ot]PYRENE
Benzo(a]pyrene (BaP) sampling in the project was conducted
by NJIT and NYSDEC. Sample analysis was done by NJIT and the
NYSDOH.
A-3
-------
3.1 Sample Collection
3.1.1. NYSDEC/NYSDOH
Calibration of BaP samplers was done by NYSDEC in accordance
with the NYSDEC guidance for flow calibration of high-volume
particulate samplers as outlined in its Ambient Air Monitoring
Quality Assurance Manual.
3.1.2 NJIT
Calibration of B(a)P samplers was done by the NJDEP
according to the procedures outlined in its Ambient Air
Monitoring Quality Assurance Manual.
3.2 Analytical Results
3.2.1 NYSDOH
Analysis of all NYSDEC BaP samples was done by NYSDOH. The
results of NYSDOH's analyses are summarized below.
1. Filters spiked with 100 ng of BaP had percent recoveries
averaging 49%, a sample standard deviation of 15.0, and a
coefficient of variation of 30.6.
2. Filters spiked with 200 ng of BaP had percent recoveries
averaging 84%, a standard deviation of 19.0, and a
coefficient of variation of 22.6.
3. The detection levels for BaP were not presented.
BaP concentrations for the summer months were reported by
NYSDOH to average 0.10 ng/m3. Assuming a 1600-m3 sample, typical
for a hi-vol sampler, there would be 160 ng of BaP collected on a
filter during an average summer day. In its procedure, NYSDOH
digests half of each filter; therefore, the total BaP extracted
from the half-filter would be 80 ng. Since NYSDOH's recoveries
at this level averaged 49%, it appears that NYSDOH's results are
negatively biased by at least 51% on average.
A-4
-------
Furthermore, NYSDOH's results are derived from liquid
standards spiked onto filters. The hi-vol/glass fiber filter
collection method used in the SI/NJ UATAP, however, gathers
particulate matter, where BaP recovery is often less than that
obtained when using liquid standards. Results with particulate
standards, such as the NIST Urban Dust Standard Reference
Material, were not provided by NYSDOH.
As a result of these findings, the NYSDOH BaP data is
included in the project data base with a caveat that the data
provided reflect the minimum concentration of BaP present.
3.2.2 NJIT
The QA data submitted by NJIT showed ±20% recoveries of BaP
from the Urban Dust Standard Reference Material (SRM's - obtained
from the National Institiute for Technology and Standards).
NJIT's detection limits were well into the sub-part per trillion
range. Recoveries at these low concentrations were >95% using
liquid SRM's. Simulated samples using liquids spiked onto
filters at concentrations of approximately 0.05 ppt yielded 87-
90% recovery.
Duplicate sample analyses showed standard deviations of
1.12%.
In view of these results, the NJIT BaP data were accepted
for inclusion in the project data base.
4. FORMALDEHYDE
Formaldehyde sampling in the project was conducted by the
New Jersey Institute of Technology (NJIT) and the New York State
Department of Environmental Conservation (NYSDEC). Sample
analysis was done by NSI, an EPA contractor, and by NJIT.
A-5
-------
4.1 Sample Collection
4.1.1 NYSDEC
Calibration of formaldehyde sample flow was done in
accordance with the NYSDEC procedures for flow calibration as
outlined in its Ambient Air Monitoring Quality Assurance Manual
4.1.2 NJIT
Calibration of NJIT formaldehyde samplers was done in
accordance with the same protocols used for its volatile organic
compound samplers.
4.2 Analytical Results
4.2.1 NYSDEC samples
Analysis of all NYSDEC formaldehyde samples was done by NSI
under contract with EPA at Research Triangle Park. Quality
Assurance data were provided by Dr. Silvestre Tejada at
EPA/AREAL, who had the oversight responsibility for formaldehyde
analysis conducted by NSI for EPA. NSI analyzed SI/NJ UATAP
samples concurrently with other samples as part of a national EPA
formaldehyde monitoring effort. The QA data presented by Dr.
Tejada did not come from SI/NJ UATAP samples directly, but rather
from NSI's results for the national studies that were done
concurrently with the SI/NJ UATAP.
Since the analytical protocols, personnel, instrumentation,
management, and EPA oversight were the same for these national
projects as for the SI/NJ UATAP, this QA information is
considered valid for assessing the quality of the analytical data
provided for the SI/NJ UATAP. Direct QA information for the
SI/NJ UATAP formaldehyde data is unavailable due to unresolved
sample log number difficulties.
The QA information provided by Dr. Tejada shows the
following:
1. Blank levels in formaldehyde tubes were always below 0.15
ppb.
A-6
-------
2. NSI analytical accuracy was assessed by EPA/AREAL in a cross
check with 2 other laboratories. Results of the study showed
a 2.1 % relative standard deviation among the laboratories.
3. Precision was estimated by evaluating collocated samples
from field studies. In most cases, the collocated samples
were within 10% of each other. In cases where this was not
the case, EPA concluded that the results were due to sampler
miscalibration or sample misidentification. The data
provided lends support to this view.
As a result of these findings, all of the NYSDEC-
collected/NSI-analyzed formaldehyde data were accepted for
inclusion in the project data base.
4.2.2 NJIT samples
Analyses of NJlT's formaldehyde samples were conducted
partly by NSI and partly in-house by NJIT. NSI's analytical QA
Was addressed in detail above; the same findings apply to the
NJIT-gathered/NSI-analyzed samples. However, no QA information
was provided for samples analyzed in-house by NJIT.
Therefore, (1) the NJIT-gathered/NSI-analyzed samples were
accepted for inclusion in the project data base; however, (2)
samples analyzed by NJIT were rejected from inclusion in the
project data base since appropriate QA information is not
available.
A-7
-------
Table IIIB-A1: SI/NJ UATAP Metals Data QA Status as of 12/4/91
Metal
Arsenic1
Barium
Beryllium1
Cadmium
Chromium
Cobalt1
Copper
Iron
Lead
Manganese
Mercury1
Molybdenum1
Nickel
Vanadium
Zinc
Benzo[a]pyrene
QA Status
NJIT
No analysis for
this compound
No analysis for
this compound
No analysis for
this compound
Approved
Approved
Insufficient data
Approved
Approved
Approved
Approved
Approved
Insufficient data
Approved
Insufficient data
Approved
Approved
NYSDOH/NYSDEC
Approved
Approved
Approved2
Approved
Rejected
Approved
Approved
Approved3
Approved
Approved
No analysis for
this compound
Approved
Approved3
Approved3
Approved
Approved*
No participate Standard Reference Material (SRM) was
available.
This compound was not detected in samples.
Recoveries of these compounds from the SRM were in the 63%-
76% range. They were acceptable for use in the project,
however they represent a minimum of the amount that may
actually have been present.
Recoveries of this compound from the SRM averaged 49%. They
reported concentrations are acceptable for use in the
project, however they represent a minimum of the amount that
may actually have been present.
A-8
-------
Table IIIB-A2
I
SAMPLE X
1
2
3
4
5
6
7
8
9
10
HEAN
STD. DEV.
U 95X CL
L 95X CL
SAMPLE X
1
S.
3
4
5
A
^
/
e
9
10
HEAh
STD. DEV.
U 95X CL
L 95$ CL
RECOVERY
CADKIUH
RECOVERY
96.9
95.1
91. S
95,0
109. S
96.9
9*. 5
97.1
96.3
97.2
97.0
4.40
99.7
94.2
NICKEL
RECOVERY
76.3
80.5
74.2
74.6
75.8
76.7
73.9
79.0
77.3
73.9
76.E
2.12
77.5
74.9
FROM URBAN DUST -
COPPER
I RECOVERY
94.5
97.0
94.7
96.1
95.7
95.0
96.6
97.1
96.6
94.9
95.B
0.94
96.4
95.2
VANADIUM
X RECOVERY
62.7
64.7
65.E
62.8
62.4
62.7
62.2
63.2
63.5
62.7
63.2
0.94
63.B
62.6
ULTRASONIC BATH DIGESTION
ZINC
X RECOVERY
97.1
98.4
96.6
98.3
98.0
97.1
97.3
97.9
98.2
100.5
97.9
1.03
98.6
97.3
LEAD
X RECOVERY
100.6
101.4
101.1
10S.4
102.4
100.6
101.6
(02.6
102.3
101.7
101.7
0.71
102.1
101.2
IRON
X RECOVERY
74.8
76.6
76.0
76.1
75.6
74.8
75.7
76.0
75.5
75.8
75.7
0.53
76.0
75.4
CHROMIUM
X RECOVERY
18.4
18.1
18.2
16.3
16.8
1B.4
18.2
18.1
18.8
18.2
18.4
0.25
18.5
18.2
BARIUM
X RECOVERY
82.6
83.8
82.2
81.7
83.5
81.7
81.9
82.3
82.9
81.8
82.4
0.71
82.9
82.0
HAN6ANE5E
X RECOVERY
86.6
87.4
84.8
86.3
87.2
85.6
86.4
86.9
87.1
87.0
86.5
0.76
87.0
86.1
A-9
-------
APPENDIX B
DATA SUMMARIES BY QUARTERLY AVERAGE
B-l
-------
ARSENIC
SITE
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
CARTERET
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
(ng/m3) SITE
2.7
1.9
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
CARTERET
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
g/m3) SITE
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
CARTERET
ELIZABETH
PORT RICHMOND PO
11.1
9.5
SUSAN WAGNER HS
PS 26
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARtTH. MEAN
(ng/m3>
12.9
11.6
QUARTER BEGINNING
OCTOBER 1988
QUARTER BEGINNING
JANUARY 1989
SITE
SUSAN WAGNER HS
PS 26
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
ARITH. MEAN
(ng/m3)
H.5
11.4
SITE
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
CARTERET
ELIZABETH
PORT RICHMOND PO
ARITH. MEAN
-------
Table IIIB-B2
CADMIUM
QUARTER BEGINNING
OCTOBER 1987
SITE
PS 26
SUSAN WAGNER HS
CARTERET
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
ARITH. MEAN
(ng/m3)
3.0
2.7
1.6
SITE
CARTERET
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
(ng/m3) SITE
12.6
3.0
2.5
CARTERET
PS 26
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1988
ARITH. MEAN
(ng/m3) SHE
4.5
3.2
2.9
1.6
SUSAN WAGNER HS
CARTERET
ELIZABETH
PS 26
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
(ng/nfl)
3.2
2.7
2.4
2.2
QUARTER BEGINNING
OCTOBER 1988
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
ARITH. MEAN
-------
Table
COBALT
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING
OCTOBER 1987 JANUARY 1988 APRIL 1988 JULY 1988
ARITH. MEAN ARITH. MEAN ARITH. MEAN ARITH. MEAN
SITE (ng/mJ) SITE (ng/n3) SITE {ng/n6) SITE (ng/m3)
PS 26 3.0 PS 26 3.0 PS 26 3.2 SUSAN WAGNER HS 2.6
SUSAN WAGNER HS 2.7 SUSAN WAGNER HS 2.5 SUSAN WAGNER HS 2.9 PS 26 2.2
PORT RICHMOND PO PORT RICHMOND PO PORT RICHMOND PO PORT RICHMOND PO
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING
OCTOBER 1988 JANUARY 1989 APRIL 1989 JULY 1989
ARITH. MEAN ARITH. MEAN ARITH. MEAN ARITH. MEAN
SITE (ng/m3) SITE (ng/m3) SITE (ng/m3) SITE
-------
Table IIIB-B4
COPPER
QUARTER BEGINNING
OCTOBER 1987
SITE
SUSAN WAGNER HS
PS 26
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
ARITH. MEAN
QUARTER BEGINNING
JANUARY 1989
SUSAN WAGNER HS 79.4
PS 26 39.6
ELIZABETH 26.6
CARTERET
HIGHLAND PARK
PORT RICHMOND PO
SITE
CARTERET
SUSAN WAGNER HS
PS 26
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
ARITH. MEAN
83.7
74.1
47.4
42.8
22.6
SITE
SUSAN WAGNER HS
CARTERET
PS 26
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1989
ARITH. MEAN
(ng/m3) SITE
86.3
69.1
38.9
32.2
25.0
SUSAN WAGNER HS
CARTERET
HIGHLAND PARK
ELIZABETH
PS 26
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1989
ARITH. MEAN
-------
IRON
QUARTER BEGINNING
OCTOBER 1987
SITE
PS 26
CARTERET
SUSAN UAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
ARETH. MEAN
(ng/*3)
1168.0
519.7
511.9
SITE
PS 26
CARTERET
SUSAN UAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
H33.0
888.0
495.6
QUARTER BEGINNING
OCTOBER 1988
SITE
PS 26
SUSAN UAGNER HS
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
ARITH. MEAN
-------
Table IIIB-B6
LEAD
SITE
PS 26
CARTERET
SUSAN WAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
(ng/m3)
82.5
69.0
58.2
SITE
CARTERET
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
(ng/*3) SITE
118.7
46.4
31.1
PS 26
SUSAN WAGNER HS
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1988
ARITH. MEAN
-------
MAMGAMESE
SITE
CARTERET
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
SITE
33.6
32.2
23.1
21.8
PS 26
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
CARTERET
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
22.3
20.3
18.6
15.6
12.4
SITE
CARTERET
HIGHLAND PARK
PS 26
ELIZABETH
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1989
ARITH. MEAN
(ng/m3)
25.7
15.6
15.5
15.0
12.2
SITE
CARTERET
PS 26
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1989
ARITH. MEAN
(ng/m3)
22.1
21.1
15.2
13.4
11.6
B-8
-------
Table IIIB-B8
MERCURY
SITE
CAfiTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 19B7
ARITH. MEAN
g/mS>
0.9
0.6
SITE
ELIZABETH
CARTERET
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
(ng/m3)
1.2
QUARTER BEGINNING
OCTOBER 1988
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN UAGNER HS
PS 26
PORT RICHMOND PO
ARITH. MEAN
(ng/«3)
0.8
0.7
SITE
HIGHLAND PARK
CARTERET
ELIZABETH
SUSAN UAGNER HS
PS 26
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1989
ARITH. MEAN
(ng/m3) SITE
0.5
0.4
0.3
HIGHLAND PARK
ELIZABETH
CARTERET
SUSAN UAGNER HS
PS 26
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1989
ARITH. MEAN
-------
la\>\e
MOLYBDENUM
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING
OCTOBER 1987 JANUARY 1988 APRIL 1988 JULY 1988
AR!™- f *" *"ITH- """ ARITH- MEAM *"'TH- MEAN
SITE (ng/m3) SITE (ng/«3) SITE (ng/m3) SITE (ng/nij}
P.* 26 , «•* PS 26 12.3 PS 26 12.9 SUSAN WAGNER HS 10.8
SUSAN WAGNER HS 11.1 SUSAN WAGNER HS 10.8 SUSAN WAGNER HS 11.0 PS 26 89
PORT RICHMOND PO PORT RICHMOND PO PORT RICHMOND PO PORT RICHMOND PO
QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING QUARTER BEGINNING
OCTOBER 1988 JANUARY 1989 APRIL 1989 JULY 1989
ARITH. MEAN ARITH. MEAN ARITH. MEAN ARITH. MEAN
SITE (ng/mJ) SITE (ng/m3) SITE (ng/m3) SITE (ng/m3)
SUSAN WAGNER HS 10.7 SUSAN WAGNER HS 9.2 PS 26 9.8 PS 26 12.1
PS 26 7.9 PS 26 7.7 SUSAN WAGNER HS 9.5 SUSAN WAGNER HS 9.5
PORT RICHMOND PO PORT RICHMOND PO PORT RICHMOND PO PORT RICHMOND PO
B-10
-------
Table IIIB-BIO
NICKEL
SITE
CARTERET
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
(ng/M3) SITE
30.6
29.4
15.6
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
CARTERET
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
76.3
27.7
26.4
SITE
CARTERET
PS 26
ELIZABETH
SUSAN WAGNER HS
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1988
ARITH. MEAN
(ng/m3)
29.3
16.6
13.6
13.6
SITE
ELIZABETH
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
CARTERET
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
(ng/m3)
44.5
16.6
14.7
SITE
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
CARTERET
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1988
ARITH. MEAN
(ng/m3) SITE
15.1
13.4
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
CARTERET
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1989
ARITH. MEAN
(ng/m3)
33.7
32.2
17.3
13.9
13.5
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1989
ARITH. MEAN
(ng/m3)
32.4
30.2
29.0
18.0
12.3
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1989
ARITH. MEAN
Cng/m3)
32.1
30.7
22.2
17.1
16.1
B-ll
-------
im-m
VANADIUM,
SITE
PS 26
SUSAN VAGUER HS
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
(ng/mS) SITE
14.8
12.8
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
(ng/m3) SITE
23.9
19.4
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1988
ARITH. MEAN
(ng/m3) SITE
15.5
11.6
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
(ng/m3)
14.9
9.3
QUARTER BEGINNING
OCTOBER 1988
ARITH. MEAN
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
15.2
9.3
SITE
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1989
ARITH. MEAN
-------
Table IIIB-B12
ZINC
SITE
CARTERET
PS 26
SUSAN WAGNER NS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
(ng/mJ) SITE
182.0 PS 26
145.5 CARTERET
112.4 SUSAN VAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
(ng/m3) SITE
107.8
89.8
89.5
PS 26
SUSAN WAGNER HS
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1988
ARITH. MEAN
SITE
106.8
95.1
90.3
78.4
PS 26
CARTERET
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
(ng/m3)
128.2
121.5
115.9
82.8
SITE
CARTERET 117.9
ELIZABETH 93.0
SUSAN WAGNER HS 88.4
PS 26 83.8
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1988
ARITH. HEAN
-------
Ta\>U
CHROMIUM
SITE
CARTERET
HIGHLAND PARK
ELIZABETH
QUARTER BEGIHMING
OCTOBER 1987
ARITH. NEAN
16.5
8.4
5.2
B-14
-------
Table IIIB-B14
BENZO(A)PYRENE
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
(ng/m3)
0.36
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
-------
TORMALOEHYDE - HCHO
SITE
CARTERET
ELIZABETH
PISCATAWAY
SUSAN UAGNER MS
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1987
ARITH. MEAN
(ppb) SITE
2.91
CARTERET
ELIZABETH
PISCATAUAf
SUSAN UAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
3.38
QUARTER BEGINNING
APRIL 1988
ARITH. MEAN
SITE
CARTERET
ELIZABETH
PI SCATAWAY
SUSAN UAGNER HS
PORT RICHMOND PO
SITE
CARTERET
SUSAM UAGNER HS
P1SCATAWAY
ELIZABETH
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
-------
Table IIIB-B16
BARIUM
QUARTER BEGINNING
OCTOBER 1987
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
ARITH. HE AN
(ng/ra3)
28.4
15.8
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1988
ARITH. MEAN
(ng/m3)
21.7
14.4
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1988
ARITH. MEAN
(ng/mS)
24.2
13.2
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1988
ARITH. MEAN
(ng/m3)
27.5
17.8
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
OCTOBER 1988
ARITH. MEAN
(ng/m3)
22.2
U.5
SITE
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
QUARTER BEGINNING
JANUARY 1989
ARITH. MEAN
(ng/m3)
25.8
22.5
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
APRIL 1989
ARITH. MEAN
(ng/m3)
16.8
13.4
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
QUARTER BEGINNING
JULY 1989
ARITH. MEAN
(ng/nx3)
27.8
4.9
B-17
-------
APPENDIX C
DATA SUMMARIES BY ANNUAL AVERAGE
C-l
-------
Table IIIB-C1
ARSENIC
SITE
PS 26
SUSAN WAGNER HS
ELIZABETH
CARTERET
HIGHLAND PARK
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
2
1
A
B
E
5
# OF
SAMPLES
52
49
ARITH. MEAN
(ng/m3)
7.1
6.5
SITE
PS 26
SUSAN WAGNER HS
ELIZABETH
CARTERET
HIGHLAND PARK
PORT RICHMOND PO
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
2
1
A
B
E
5
# OF
SAMPLES
44
48
ARITH. MEAN
(ng/m3)
4.3
3.7
C-2
-------
Table IIIB-C2
CADMIUM
SITE
CARTERET
PS 26
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
B
2
1
A
E
5
* OF
SAMPLES
52
52
49
16
ARITH. MEAN
(ng/m3)
5.6
2.9
2.8
2.3
SITE
CARTERET
PS 26
SUSAN WAGNER HS
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
B
2
1
E
A
5
# OF
SAMPLES
60
46
48
42
54
ARITH. MEAN
(ng/ra3)
4.3
2.5
2.5
2.1
1.6
C-3
-------
Table IIIB-C3
CHROMIUM
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SITE
#
B
A
E
# OF
SAMPLES
52
16
ARITH. MEAN
(ng/m3)
22.2
8.2
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
B
A
E
# OF
SAMPLES
46
56
42
ARITH. MEAN
(ng/m3)
26.8
15.6
12.3
C-4
-------
Table IIIB-C4
COBALT
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
SITE
#
2
1
5
# OF
SAMPLES
52
49
ARITH. MEAN
(ng/m3)
2.9
2.7
SITE
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
1
2
5
# OF
SAMPLES
48
45
ARITH. MEAN
(ng/m3)
2.5
2.5
C-5
-------
Table IIIB-C5
COPPER
SITE
SUSAN WAGNER HS
CARTERET
PS 26
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
1
B
2
A
E
5
# OF
SAMPLES
49
52
52
16
ARITH. MEAN
(ng/m3)
98.8
84.6
56.7
32.9
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
SUSAN WAGNER HS
CARTERET
PS 26
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
SITE
#
1
B
2
A
E
5
# OF
SAMPLES
48
45
45
54
42
ARITH. MEAN
(ng/m3)
83.3
80.3
40.9
34.5
33.8
C-6
-------
Table IIIB-C6
IRON
SITE
PS 26
CARTERET
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
2
B
1
A
E
5
I OF
SAMPLES
52
38
49
16
ARITH. MEAN
(ng/m3)
1226.1
686.8
676.3
526.6
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
PS 26
SUSAN WAGNER HS
CARTERET
HIGHLAND PARK
ELIZABETH
PORT RICHMOND PO
SITE
#
2
1
B
E
A
5
# OF
SAMPLES
45
48
60
40
54
ARITH. MEAN
(ng/m3)
923.6
649.3
604.8
476.5
428.5
C-7
-------
Table IIIB-C7
LEAD
FIRST YEAR
OCT 1987 - SEPT 1988
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/m3)
CARTERET B 38 78.6
PS 26 2 52 56.9
SUSAN WAGNER HS 1 49 44.7
ELIZABETH A 16 29.5
HIGHLAND PARK E
PORT RICHMOND PO 5
SECOND YEAR
OCT 1988 - SEPT 1989
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/m3)
HIGHLAND PARK E 40 49.0
PS 26 2 44 39.2
CARTERET B 60 36.4
ELIZABETH A 54 30.8
SUSAN WAGNER HS 1 48 31.3
PORT RICHMOND PO 5
C-8
-------
Table IIIB-C8
MANGANESE
SITE
CARTERET
PS 26
ELIZABETH
SUSAN WAGNER HS
HIGHLAND PARK
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
B
2
A
1
E
5
# OF
SAMPLES
38
52
16
49
ARITH. MEAN
(ng/m3)
29.2
28.7
18.9
18.5
SITE
CARTERET
PS 26
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
B
2
1
A
E
5
# OF
SAMPLES
60
45
48
54
42
ARITH. MEAN
(ng/m3)
21.8
18.8
15.2
14.8
13.5
C-9
-------
Table IIIB-C9
MERCURY
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
B
A
E
1
2
5
# OF
SAMPLES
25
16
ARITH. MEAN
(ng/m3)
5.4
2.7
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
SUSAN WAGNER HS
PS 26
PORT RICHMOND PO
SITE
#
B
A
E
1
2
5
# OF
SAMPLES
60
57
45
ARITH. MEAN
(ng/m3)
0.5
0.5
0.4
C-10
-------
Table IIIB-C10
MOLYBDENUM
FIRST YEAR
OCT 1987 - SEPT 1988
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/m3)
PS 26 2 52 11.8
SUSAN WAGNER HS 1 49 10.9
PORT RICHMOND PO 5
SECOND YEAR
OCT 1988 - SEPT 1989
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/ro3)
PS 26 2 45 9.7
SUSAN WAGNER HS 1 48 9.6
PORT RICHMOND PO 5
C-ll
-------
Table IIIB-C11
NICKEL
FIRST YEAR
OCT 1987 - SEPT 1988
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/m3)
CARTERET B 38 48.3
ELIZABETH A 16 38.7
PS 26 2 52 22.8
SUSAN WAGNER HS 1 49 17.9
HIGHLAND PARK E
PORT RICHMOND PO 5
SECOND YEAR
OCT 1988 - SEPT 1989
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/m3)
CARTERET B 45 26.1
ELIZABETH A 39 23.9
HIGHLAND PARK E 40 22.6
PS 26 2 45 20.2
SUSAN WAGNER HS 1 48 19.1
PORT RICHMOND PO 5
C-12
-------
Table IIIB-C12
VANADIUM
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
2
1
5
# OF
SAMPLES
52
49
ARITH. MEAN
(ng/m3)
17.5
13.6
SITE
PS 26
SUSAN WAGNER HS
PORT RICHMOND PO
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
2
1
5
# OF
SAMPLES
45
48
ARITH. MEAN
(ng/m3)
16.9
15.2
C-13
-------
Table IIIB-C13
ZINC
SITE
PS 26
CARTERET
SUSAN WAGNER HS
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
2
B
1
A
E
5
# OF
SAMPLES
52
38
49
16
ARITH. MEAN
(ng/m3)
128.2
121.5
113.9
82.8
SITE
CARTERET
ELIZABETH
SUSAN WAGNER HS
HIGHLAND PARK
PS 26
PORT RICHMOND PO
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
B
A
1
E
2
5
# OF
SAMPLES
60
54
43
42
45
ARITH. MEAN
(ng/m3)
115.2
109.5
113.2
97.8
96.3
C-14
-------
Table IIIB-C14
BENZO(A)PYRENE
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
B
A
E
5
# OF
SAMPLES
51
16
ARITH. MEAN
(ng/m3)
0.17
0.04
SITE
CARTERET
ELIZABETH
HIGHLAND PARK
PORT RICHMOND PO
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
B
A
E
5
# OF
SAMPLES
60
55
53
ARITH. MEAN
(ng/m3)
0.20
0.19
0.14
C-15
-------
Table IIIB-C15
FORMALDEHYDE - HCHO (METHANAL)
SITE
SUSAN WAGNER HS
CARTERET
PISCATAWAY
ELIZABETH
PORT RICHMOND PO
FIRST YEAR
OCT 1987 - SEPT 1988
SITE
#
1
B
D
A
5
# OF
SAMPLES
1
25
10
ARITH. MEAN
(PPb)
4.05
3.63
3.30
SITE
ELIZABETH
SUSAN WAGNER HS
PISCATAWAY
PORT RICHMOND PO
CARTERET
SECOND YEAR
OCT 1988 - SEPT 1989
SITE
#
A
1
D
5
B
# OF
SAMPLES
6
44
7
35
ARITH. MEAN
(PPb)
2.89
2.02
1.78
1.71
C-16
-------
Table IIIB-C16
BARIUM
FIRST YEAR
OCT 1987 - SEPT 1988
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/m3)
PS 26 2 52 25.3
SUSAN WAGNER HS 1 49 15.1
PORT RICHMOND PO 5
SECOND YEAR
OCT 1988 - SEPT 1989
SITE # OF ARITH. MEAN
SITE # SAMPLES (ng/m3)
PS 26 2 55 19.2
SUSAN WAGNER HS 1 51 12.9
PORT RICHMOND PO 5
C-17
-------
APPENDIX D
QUALITY ASSURANCE REPORT FROM NEW JERSEY INSTITUTE OF TECHNOLOGY
METALS IN AIRBORNE PARTICULATE
Joseph W. Bozzelli, Dept. of Chemistry and Chemical Engineering
New Jersey Institute of Technology, Newark, NJ 07102.
Quality Assurance Report
Submitted to
Steven Quan
Air Quality Division
New Jersey Department of Environmental Protection
State St
Trenton, NJ 08625
609 633 1110
Submitted by:
Joseph W. Bozzelli,
Dept. of Chemistry and Chemical Engineering
New Jersey Institute of Technology,
Newark, NJ 07102.
201 596 3459
D-l
-------
METALS IN AIRBORNE PARTICULATE
Joseph W. Bozzelli, Dept. of Chemistry and Chemical Engineering
New Jersey Institute of Technology, Newark, NJ 07102.
The sample preparation and analysis procedures are designed
to provide optimum collection efficiency and accuracy in deter-
mining levels of toxic metals in the ambient airborne particulate
sampled. Atomic Absorption spectrometry utilizing air acetylene
flame was used for all metals except Mercury, where Cold Vapor AA
was used.
ANALYTICAL PROCEDURES
The analysis of the airborne particulate sample was per-
formed by dissolving (digesting) the particulate from the filter
paper in an acid solution1, quantitatively transferring the solu-
tion into a volumetric flask, and diluting it to exactly 50 ml
volume. The analysis was then performed by atomic absorption
spectroscopy. The spectrometer was set to the optimum operating
parameters for the analysis of each specific metal before analy-
sis of that metal was performed.
A group of samples (usually 6 plus 1 blank filter for filter
and acid background correction) were all digested during the
same time period. Analyses for the metals in this digestion batch
were then done within three days after digestion. The analytical
techniques used in these determinations are similar to those
described in references 13.
D-2
-------
The analysis of metals from airborne particulate consists of
several steps. These include:
1 - Preparation - Mounting of the Filter
2 - Particulate collection
3 - Digestion of the particulate to dissolve metals of interest
4 - Calibration of the AA instrument using standards
5 - Analysis of Metal
1 - Preparation - Mounting of the Filter
Filters were supplied by NJDEP. They were kept in a desic-
cator prior to weighing on an analytical balance capable of 100
micrograra measurements. The balance was serviced once per year
and calibrated with weights traceable to the National Bureau of
Standards. The weighing was only useful for total particulate
measurement.
The filters were placed in the desiccator for a minimum of
3 days prior to weighing after sample collection to eliminate
errors in particulate weights from moisture.
The desiccant was monitored with color indicating silica gel
and was regenerated when required via heating to 200 C in a
vacuum oven.
D-3
-------
2 - Particulate Collection
The 8 x 10 inch glass fiber filter (Whatman) was placed
into a sampler filter holder assembly and mounted onto the sam-
pling blower motor assembly at 0900 five days prior to automatic
sampler turn on. The sampler was manually checked at 0900 hours
on the day of sampling (midnight to midnight sampling) for flow
calibration. The manual check verified and served to calibrate
the continuous flow (pressure monitor) recorder measurements.
The sampler / filter holder assembly was removed from the Hi
Vol blower motor assembly at 0900 hours on the day after the
sampling midnight turn-off. The total time (hours, minutes) of
sample collection was recorded by NJIT and reported to NJDEP.
The filter holder assembly was then returned to the labora-
tory. The filter was removed from the filter holder and placed
into the desiccator prior to weighing.
NJDEP calibrated the Hi Vol samplers versus Flow monitor
(pressure) and provided the total flow to NJIT, after total time
of operation were reported to NJDEP by NJIT.
3 - Digestion of the Particulate to Dissolve (DIGEST) the Metals
The analysis of the metals in the particulate consists of
the digestion and the second stage, which is the quantitative
analysis of the specific metals in the solution.
D-4
-------
A section which represents 50 percent of the 8 x 10 inch
filter paper was digested, 8 by 5 inch piece. This piece was cut
up into small (less than 2 cm x 2 cm) pieces and placed into a
250 ml round bottom flask for digestion.
Six sample filters and 1 blank filter were digested during
the same time period. Analysis for metals in the digestion batch
was always performed within 3 days of the digestion to minimize
sample loss of the analyte on the container walls.
The digestion acid, 50 ml per filter sample, consists of 50%
nitric, 10% hydrochloric acids and 40% high purity super water
(deionized and then doubly distilled) , plus 3 ml of 30% hydrogen
peroxide. The hydrogen peroxide volume was adjusted to eliminate
(oxidize) carbon solids so that no metals remained adsorbed
within the carbon particulate. The Peroxide was added dropwise
after the solution was boiling and then allowed to cool to just
below boiling. Boiling was then continued after completion of
the clarification of the carbon soot.
The solution was held at or near boiling in round bottom
flasks with water cooled condensers for approximately 8 hours.
Some filters were digested for 16 hours, but it was discerned
that the longer digestion time did not improve the analysis. All
quality assurance data on the EPA and NBS (NIST) standard fil-
ters and urban dust particulate materials respectively, were
performed using the 8 hour digestion time period.
D-5
-------
Upon completion of the heating digestion period the solution
was removed from the digestion flasks and diluted to 50 ml vol-
ume. It was poured into a volumetric flask through a filter paper
- funnel assembly to remove glass fibers from the solution, which
would serve to block or partially obstruct the liquid flow into
the aspirator of the AA, if not removed. The 50 ml volume was
made up with rinse from the digestion flasks and condensers and
then from distilled water.
Commercial standards for each metal were purchased (Baxter
Health Care Inc.) either in 1000 ppro concentration or in high
purity solid form and then dissolved in acid solution to a known
concentration. The standards were diluted with doubly distilled
deionized water using calibrated pipets and volumetric flasks.
Typical levels of standard solution were between 0.1 and 10
mg/ml. A least squares fit to absorbance vs. concentration line
was calculated using the standards data and the point (0,0) The
slope from this least squares calculation was then used to deter-
mine the concentration (mg/ml) from the sample absorbance read-
ings. A typical plot for Lead standards is shown in Figure 1.
Minimum Detection Limits (MDL's) were determined by two
methods. One method was that used at NJIT routinely, the second
was a method provided by the USEPA Region II. The NJIT method was
simply a signal required to provide 4 times the Signal to noise
of the AA instruement absorbance reading for standard solutions.
The EPA provided method yielded somewhat lower MDL's and the
D-6
-------
25
Calibration Curve for the Lead
0
C
rrj
20
15
10
-------
reader should be referred to MDL reporting requirements for this
Project, supplied by the USEPA Region II for further specific
information on this method.
These EPA - MDL values are determined from the Standard
Curve run on each day of analysis — each metal. They provide,
quality assurance data as per EPA requirement. this includes
quality assurance to specific evaluation on each set of values
supplied to EPA in the data report. These MDL's incorporate
values of the absolute values (responses), of the standards for
each metal for each set of analysis (standards run before and
after each set of analysis for each metal on the AA instruments -
Each batch of 6 runs plus blank). The MDL's are therefore calcu-
lated and reported separately for each batch of analysis and
incorporated into the data sheets and data format disks provided
to USEPA as required part of the EPA data reporting format. Since
this method was developed reviewed and recommended by EPA it is
not further discussed here.
D-7
-------
nni
AIR
SUPPIY
Q.N
Off
-rfcw
CONTROL
ORIFICE
_ O
(20%)
IMPINGER
(00%)
EXHAUST
ADSORPTION
CELL
-------
TABLE I
METAL
Pb
Mn
Ni
Cd
Hg
Co
Zn
Cr
Fe
Cu
Concentration
(ug/ml)
0.2
0.1
0.15
0.05
MINIMUM DETECTABLE QUANTITIES
**
EPA
(ug/ml)
0.042
0.017
0.027
0.0035
0.05(ng/ul) 0.057 (ng/ul)
0.2
0.07
0.2
0.2
0.15
0.48
0.26
0.13
0.14
0.28
Air L
(Ng/M
eve Is
3)*
10.
5.
7.5
2.5
0.01#
10.
3.5
10.0
10.
7.5
* Assuming a 2000 m3 sample volume collected, with half (1000
m3) being analyzed and the NJIT detection limits. (Nanogram/nr)
/ Cold Vapor Technique (all units - nanograms)
** Determined by methods provided by USEPA (Region II). These
lover MD1 values are determined from the Standard Curve run on
each day of analysis of each metal. They provide, as per EPA
requirement, quality assurance data - specific evaluation on each
set of values supplied to EPA in the data report. These MDL's
incorporate values of the absolute values - responses, of the
standards run before and after each set of analysis for each
metal on the AA instruments. Each batch of 6 runs plus blank.
NJIT - The total amount (concentration in ug/ml) of each
metal is required to give a signal of 4 times the noise level for
a 50 ml volume of analyte solution. Occasionally, a value less
than this minimum is reported. These low values, due to spec-
trometer readings of less than 4 x noise or due to subtraction of
a large blank, have a larger margin of error than discussed (see
later).
This table only represents minimum detection limits as
evaluated by NJIT. The separate Quality assurance minimum detec-
tion limits as determined using the USEPA supplied formula were
rigorously reported with all of the sample data supplied to NJDEP
and to the USEPA.
D-a
-------
Mercury Analysis by Cold Vapor Atomic Analysis
The Hatch and Ott Cold Vapor technique used for mercury
analysis on an AA has been modified in order to improve both
precision and accuracy. The drying filter for elimination of
water vapor has been removed from the Hg vapor inlet line absorp-
tion cell and the activated charcoal mercury removal trap has
been eliminated. A diagram of the present mercury cold vapor
apparatus is shown in Figure 2. It consists of an air supply pump
an impinger and an impinger pass line, an inlet to the absorption
cell and exhaust from the cell directly to a fume hood.
A constant fraction, 20 percent, of the air flow from the
pump by-passes the impinger assembly and flows directly into the
absorption cell. This is a sufficient flow of dry air to prevent
water vapor from condensing on the cell windows, body, or tubing
lines.
The digestion of the filter containing the particulate,
storage under acidified conditions, and treatment of the diges-
tion solution with stannous chloride just prior to analyses,
remain identical to the previous method. Using this method the
absorbance reading peaks about ten seconds after the air supply
pump is turned on, and the peak width is approximately 15 sec-
onds. The sample flows through the absorption cell and is ex-
hausted into a fume hood. An illustration of the reproducibility
of the method is shown in Figure 3, where replicate samples gave
a standard deviation of 0.5%. The volume of the sample used in
D-9
-------
the impinger, 5ml, permits up to 8 analyses on the same air sam-
ple, if required. All absorbance readings are output on a record-
er for display and data measurement.
A typical plot of absorbance versus micrograms of Hg per ml
using a 5ml volume of standard solution is shown in Fig 4. The
minimum detectable amount is 0.05 ng of Hg per ul, using a 5ml
sample into the saturator. Using a 50 ml volume of solution from
digestion this corresponds to 10 ng of Hg per filter, minimum
detectable limit — O.Olng.m3 for 1000 m3 sample.
The analyte solution was made by taking a 20 ml portion of
the digested solution and 2 ml of concentrated nitric acid in a
capped plastic vial. The nitric acid was added in order to
stabilize the Mercury as the HgO. 10 ml of this solution was
placed in a 50 ml aerator tube just before the analysis. 1 ml of
10% (saturated) stannous chloride solution was then added to the
liquid in the aerator tube and standard cold vapor ana-lysis
performed. The Stannous chloride converted the HgO into Hg
vapor, which was circulated into the path of the AA lamp (light
source).
A separate AA instrument was set up for the Hg analysis and
dedicated to this analysis. This instrument was not used for any
other analysis.
D-10
-------
PRECISION OF fCKCtJRY ANALYSIS
MrANIVUJD niEVJATlON - fl,5Z
5,0 n.. or D.O't ijii./ru., He, SI/MIIWRI)
1 MINUTt
UJ
o
o
to
V
V
/RfPLlCATU rk.KCiJK
-------
FIGURE - iv
HEIICIIItY ATOMIC AIISOKI'T.ION CALIBRATION CURVE
AQSORUANCE READINGS VERSUS CONCENTRATION OF Kg STANDARDS
.bOO —
RUN NO. 12
CORRELATION COEF. .99982
STD. HEV. 4 .00153
b 10
50
HG/HL
MERCURY COHCENtllMlON
100
-------
Quality Assurance
Analysis of USEPA Lead Standards
Glass fiber filter strips impregnated with known amounts of
lead material were obtained from the United States Environmental
Protection Agency, Quality Assurance Branch, Research Triangle
Park, North Carolina. These filter strips were analyzed with
identical procedures to those used in determinations in this
project on airborne particulate. A comparison of the EPA sup-
plied values with the results obtained in this laboratory showed
our analysis was routinely within 95% of the known standards.
Table II illustrates the agreement for lead.
Table II
ANALYSIS OF USEPA LEAD STANDARDS
USEPA ID. f LEAD(EPA) LEAD (NJIT) %NJIT/EPA
Pb 831-4135
Pb 831-5145
Pb 831-6024
Pb 831-7150
Pb 831-8153
900
1300
1100
2000
1800
910
1239
1055
1841
1682
.9
.4
.2
.6
.3
101.2
95.3
95.9
92.1
93.5
Pb 831-9148
1600
1473.3
92.8
D-ll
-------
Analysis of National Bureau of Standards Urban Particulate
The National Bureau of Standards (NBS) urban particulate
standard, No. 1648, was purchased and analyzed in these laborato-
ries for quality assurance determinations. The standard was
analyzed for lead and cadmium nickel and manganese in the initial
determinations and for chromium, iron, copper and zinc in the
last four determinations. The results are listed in Table III.
This particulate required extensive drying in an oven before a
sample of it could be accurately weighed and analysis performed.
The drying step was done in an oven at 150°C for a period of 16
hours or longer. The drying is necessary to remove water vapor
which had adsorbed on the standards and is part of the NBS recom-
mended procedure.
D-12
-------
Table III
COMPARISON OF NJIT METALS ANALYSIS WITH
NATIONAL BUREAU OF STANDARDS
PARTICULATE STANDARD NO. 1648
Analysis NBS - 3
Metal NJIT NBS % (NJIT/NBS)
Cadmium 56.9 75 ±7 76
Lead 6,024 6,550 ±8 92
NBS , - 4
Cadmium
Lead
Nickel
NBS - 5
Cadmium
Lead
Nickel
Manganese
NBS - 6
Cadmium
Lead
Nickel
Manganese
65
5,546
90
78.8
5,654
72.4
562
76
6,244
152
603
75 ±7
6,550 ±8
82 ±3
75
6,550
82
800a
75
6,550
82
800a
87
85
110
105
86.3
88.3
71
101
95.3
185**
75.4
* Concentrations in ug metal per gram of dry particulate.
** Possible contamination of sample.
D-13
-------
TABLE III (Con't)
NBS - 7D
Metal
Cadmium
Lead
Nickel
Manganese
Chromium
Iron - Fe
Copper
Zinc
NBS -
Cadmium
Lead
Nickel
Manganese
Chromium
Iron - Fe
Copper
Zinc
NJIT
69.4
7,310
74.4
695
348
38,23
523
4,49
8D
77.6
6,589
88.8
717
371
37,47
567
4,59
NBS
75
6,550
82
800a
403
39,100
609
4,760
75
6,550
82
800a
403
39,100
609
4,760
% (NJIT/NBS)
92.5
111.6
90.7
86.9
86.4
97.8
85.9
94.3
103.4
100.6
108.3
89.6
92.1
95.8
93.1
96.4
* Concentrations in ug metal per gram of dry particulate.
D-14
-------
Table III (con't)
NBS - 9D
Cadmium
Lead
Nickel
Manganese
Chromium
Iron - Fe
Copper
Zinc
NBS -
Cadmium
Lead
Nickel
Manganese
Chromium
Iron - Fe
Copper
Zinc
68.6
6,930
75.6
703
339
37,6
541
4,87
10D
68.3
6,380
84.9
686
377
36,3
555
4,17
75
6,550
82
B00a
403
39,100
609
4,760
75
6,550
82
800a
403
39,100
609
4,760
91.5
105.8
92.2
87.9
84.1
96.2
88.8
102.1
91.0
97.4
103.5
85.8
93.5
92.8
91.1
87.6
a - Not a NBS certified value.
- Cobalt levels too low to quantitize with size of our samples.
- Mercury is not reported in the NIST Standard.
* Concentrations in ug metal per gram of dry particulate.
D-15
-------
Quality Assurance in Analysis
Metals Except Mercury, i.e. Pb, Cd, Mn, ... etc.
The digested samples are kept in polyethylene volumetric
flasks or vials until they were analyzed by atomic absorption
spectroscopy. . The solutions are thoroughly mixed to assure
uniform concentration before the analyses are performed. The
digested sample is then aspirated into the air-acetylene flame of
the atomic absorption instrument and the absorbance monitored.
The atomic absorption spectrometer is tuned each day before
analyses are run (burner alignment, optimization of lamp align-
ment and frequency). Calibration absorbance curves are prepared
each day from standard metal solutions. When samples are run,
the standards are checked at the beginning and end of the analy-
sis of each metal. In the analysis of a group of samples for one
metal, all the spectrometer conditions are first optimized, the
standards run, and a graph of absorbance versus concentration
(ug/ml) is plotted to verify the linear relationship. This is
done for each metal in the group of six samples plus blank. The
samples are then analyzed for the metal, 3 readings are taken in
a time frame of 5 to 10 seconds per reading. It should be noted
that usual Flame AA analysis takes readings in time frames of 1 -
2 seconds per reading. The zero reading is checked after each
absorbance measurement, and standards are rerun to check instru-
ment drift after approximately every seven samples.
Commercial standards for each metal are purchased either in
D-16
-------
1000 ppm concentrations or in high purity solid form and then
prepared in acid solution to a known concentration. The stand-
ards are diluted with the "super water" using calibrated pipets
and volumetric flasks. Typical levels are between 0.1 and 10
ug/ml. An example of the procedures and calculations for making
a known lead standard from a solid aliquot of PbCl2 is illustrat-
ed in the attachemnt following this section of the report.
The absorbance is directly proportional to the standard,
showing a linear relationship in accordance with Beers Law. A
least squares fit to this line is calculated using the standards
data and the point (0,0) which is valid for these AA plots. The
slope from this least squares calculation is then used to deter-
mine the concentration (ug/m) from the sample absorbance read-
ings. Figure 1, as mentioned previously, shows a typical absorp-
tion curve for lead standards. Samples found at higher concentra-
tions than these values are diluted and rerun in order to locate
the concentration within the linear portion of the curve. The
spectrometer conditions for each metal and lamp are listed in
Table IV and are for the wavelength at which the AA is most
sensitive to the metal under analysis.
Vanadium was initially analyzed using a nitrous oxide -
acetylene flame. After two blowouts of the flame it was deter-
mined that continued use of our AA with this method was unsafe.
Vanadium analysis was discontinued. While it is felt that the
Vanadium results reported are of reasonable accuracy and qualil-
ty, proper quality assurance procedures and calibrations can not
be reported.
D-i?
-------
Table IV
Operating Parameters for Atomic Absorption Analysis
Metals Air-Acetylene Flame.
Spectral Lamp
Element Wavelength (nm) Band Pass (nm) Current ma
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
Lead
Nickel
Copper
Cobalt
Iron
Zinc
Chromium
Mercury*
Manganese
Cadmium
217.0
232.0
324.8
240.7
248.3
213.9
357.9
253.7
279.5
228.8
1
1
2
1
2
1
2
1
2
1
4
5
4
6
6
5
6
3
5
3
* Cold Vapor Method
Spectro photometric Conditions for Each Metal
Vanadium was initially analyzed using a nitrous oxide -
acetylene flame. After two blowouts of the flame it was deter-
mined that continued use of our AA with this method was unsafe.
Vanadium analysis was discontinued. While it is felt that the
Vanadium results reported are of reasonable accuracy and qualil-
ty, proper quality assurance procedures and calibrations can not
be reported.
D-18
-------
ANALYSIS OF PRECISION AND ACCURACY
1. Error Analysis
The relative errors associated with each of the steps in the
collection and analysis of airborne particulate for metals are
presented below.
Standard Solutions
Standard solutions of 1000 ppm (1000 ug/ml) were purchased
from Baxter Health Care, Edison, NJ. The accuracy of these atomic
absorption reagents was National Bureau of Standards certified
(±0.2% of the reported concentration). The standards are diluted
using precision pipets, burettes and volumetric flasks. Slated
errors from reading volume levels in volumetric flasks and pipets
is less then 1%, while error for reading a small difference from
a burette may be as high as 2 percent. On the basis of the
burette error the accuracy of the standard solution is placed
within 2.0 percent of the nominal value. The burets are not used
frequently and most of the standard solutions are therefore
considered to have an even smaller error limit.
It is valuable to note that agreement with the USEPA lead
standards - filter strips provides reinforcement of the accuracy
in the standard make up. This is because there is no digestion
or extraction problem here, i.e. all the metal is easily extract-
ed from the filter. It is then, primarily, lab techniques and
standard accuracy which dictate whether one achieves agreement
with the EPA standard filter values.
D-ig
-------
Standard Solutions - Storage
Standard solutions are stored in polyethylene bottles and
are routinely checked for stability. New standard solutions are
made up for these studies approximately once every four weeks. A
comparison of the AA signals from the old and new standards
provides information on stability of the standard solutions.
This corresponds, in this study, to once every two times samples
are analyzed. New solutions are always stored in the bottles
which had previously contained the same concentrations of the
same metal. This eliminates adsorption effects on the walls of
the plastic containers. Errors which arose from slight changes
in standard concentrations due to storage are Further monitored
by observing the behavior of the standard curves. The loss of a
metal to the vessel surfaces is amplified greatly on the very low
concentration standards. This results in a low value for the
lower concentration standard absorbance readings, and a corre-
sponding higher value for the higher concentration standards.
Average standard deviations from standard curves correspond to
less than 5%, thus we estimate this error at 5%.
AA Analysis:
The Absolute accuracy of the atomic absorption analysis
results from sensitivity specific to each element being analyzed.
Please see table I.
D-20
-------
Digestion
The digestion step used is a standard method accepted by the
United States Environmental Protection Agency and a thorough
study of its effectiveness is not undertaken. The results from
digestion and analysis of the NIST Standard Particulate (road
Dust) sample provides a good indication of the accuracy of our
digestion, with the exception of tests NBS 1-3 which were not
performed on thoroughly dried material our average error is
within 10% for the three metals (Cd, Pb, Ni, Fe, Zn) tested rou-
tinely and within 23 % for Manganese. The error for Manganese
improved to within 20 percent on the last 4 particulate analy-
sis. An approximately error limit of 10% is assigned to this step
by assuming that it contributes half of the total error (±20%)
accepted by the U.S. EPA> This estimate correlates well with the
data obtained in these labs on metal standards, supplied by the
USEPA and the National Bureau of Standards described earlier.
Chromium and Copper analysis were with in 15%.
Collection
The collection efficiency of the glass fiber filters is
99.9% for 0.3 micron particles and greater than 99.9% for larger
particles, as reported by the manufacturer, Whatman in this
study.
Volume of Air Samples
A detailed discussion of the volume flow calibration of the
sampling pumps is included in a separate section supplied by
D-21
-------
A summary of these errors is illustrated in Table V
Table V
Summary of Error Analysis for Collection and Measurement
Airborne Particulate for Toxic Metals.
ERROR LEVELS
PROCEDURE ACCURACY(%) ERROR LEVEL (%)
1. Standards 98. ±2.0
2. Standard Storage 95. ±5.0
3. Digestion completeness 90. ±10.0
4. Collection Efficiency0 99. ±1.0
5. Volume of air sample 90. ±10.0
Overall (Root mean square) ±17
c. Within the size range 0.3 - 30 urn (micro meters).
The estimate of error associated with AA instrument insta-
bility is determined by the average instability observed for a
series of readings near blank level. This is dependent on the
specific metal being evaluated and on te condition of the emis-
sion lamp of that metal. It corresponds to 0.2 micrograms per
milliliter for the metal (Pb), which we determine to exhibit this
problem to the largest extent. This is equivalent to 10.0
micrograms total in the 50 ml volume of analyte solution and
equates to ± 10. ng/m3 air sample - 1000 m3 volume. The percent
error is difficult to fully evaluate because different metals
have different concentrations and thus different % error for each
case. The EPA has indicated to NJIT that the best way to evalu-
ate this is to utilize the USEPA Minimum Detection Limit Value
(MDL) as we report in Table I for a select set of studies. These
values have been reported to the USEPA for each metal, each set
of analysis.
D-22
-------
The EPA - MDL values are determined from the Standard Curve
run on each day of analysis — each metal. They provide, quali-
ty assurance data as per EPA requirement. this includes quality
assurance to specific evaluation on each set of values supplied
to EPA in the data report. These MDL's incorporate values of the
absolute values (responses), of the standards for each metal for
each set of analysis (standards run before and after each set of
analysis for each metal on the AA instruments - Each batch of 6
runs plus blank). The MDL's are therefore calculated and report-
ed separately for each batch of analysis and incorporated into
the data sheets and data format disks provided to USEPA as re-
quired part of the EPA data reporting format. Since this method
was developed reviewed and recommended by EPA it is not further
discussed here.
-------
Atomic Absorption Analysis
Introduction
Since determination of metallic elements in a sample matrix
is a complex process, a sensitive and selective method of analy-
sis was desirable. The steadily growing list of atomic absorp-
tion analytical applications now covers almost all of the ele-
ments. The major breakthrough in the development of the use of
measurement of atomic absorbance as an analytical technique came
in the 1950s when Sir Alan Walsh realized that it was possible to
use a line source which emitted very narrow lines at the same
wave length in place of a continuum source.
Operating Principles
As the instrument is turned on and the necessary lamp cur-
rents, wavelength, slit widths and PMT voltages are set to the
required levels, a light source (hollow cathode lamp) emits the
spectrum of the metal selected for analysis. A specific line of
the target metal spectrum is capable of being absorbed by atoms
of the same metal if they are present in the sample. The liquid
sample is converted to a fine aerosol by a nebulizer and the
aerosol is then reduced to the constituent atoms in a flame. The
flame lies in the light path between the lamp and the line detec-
tor (monochromator and photomultiplier tube). If any of the
metal is present in the sample, absorption of the characteristic
line will provide an accurate measure of the concentration of the
metal. The analytical precision is typically around 1% relative.
-------
Principle of the method — Atomic Absorption
In atomic absorption, the element of interest in the sample
is not present in an excited state. Rather, it is in an elemen-
tal form dissociated from its chemical bonds and placed into an
unexcited, un-ionized "ground" state. This dissociation is most
commonly achieved by placing the sample into a high temperature
flame. The element is then capable of absorbing radiation at
discrete lines of narrow bandwidth.
A hollow cathode lamp usually provides the narrow emission
lines which are to be absorbed by the same element. The lamp
contains a cathode made of the same element being determined and
is filled with an inert atmosphere at low pressure. Such a lamp
emits the spectrum of the desired target element.
The atomic absorption spectrophotometer was tuned each day
before the analysis was carried out. The tuning process involves
burner alignment, optimization of lamp alignment and wavelength.
A Varian atomic absorption spectrophotometer, model 12 was used.
The calibration absorbance curve for each metal was pre-
pared from standard metal solutions each time the analysis was
carried out. When samples were run, the standards were checked at
the beginning and end of each set of metal analyses. In an
analysis of a group of samples for a metal, all the spectro-
photometric conditions, wavelength, alignment, lamp current and
zero reading were first optimized. The standards were then run
D-25
-------
and a graph of absorbance versus concentration is plotted to
verify the linear relationship. The zero reading was checked for
instrumental drift. Figure 1 shows a typical absorption curve
for the lead standard. The spectro-photometric conditions for
each metal and lamp are listed in Table IV. The line source com-
monly used is a hollow-cathode lamp and the flame is air-acety-
lene.
D-26
-------
Standard Solution Concentration Example Calculation
Lead chloride Pb C12 Molecular Weight PbCl2 = 278
Atomic Weights Pb = 207 C12 = 71
Wt of Pb in PbCl2 = 207/278 x Grams PbCl2 weighed out
Definition 1000 PPM Pb = Igm/lOOOg = Igm/liter = 0.1 gro/lOOml
Assume Weighed 0.1300 Cms PbCl2 on analytical balance
Dissolve 0.13 gms PbC12 x 207/278 » 0.0975 gms Pb
Solution made by heating Sample PbCl2 in 10 % nitric acid solu-
tion in super water.
0.0975 gms Pb in 100ml = 975. PPM,, Mix Well Before Use
Lower concentrations of lead standard are made by serial dilution
of this 975 ppm solution.
the formula to use for determining quantities of this 975 ppm
standard and the distilled water diluent is:
Vi x Ci * Vf x Cf
where V is volume C is concentration in ppm
i stands for initial f stands for final
Choose Vf to be a convenient volume, where there is a volumetric
flask available, typically 250 to 500 ml is utilized. Pick 500.
Ci is fixed at 975 ppm in this example until a lower concentra-
tion is made up.
Cf should be an intermediate concentration, that requires a
volume of Ci, which can be measured accurately. (0.01 micro
liters is, for example, difficult to measure quantitatively using
a pipette. Typically one might choose 50 or 100 ppm for Cf.
Choosing 50 ppm for Cf, one calculates Vi should be 25.6 ml;
that is 25.6 milliliters of 975 ppm standard needs to be added to
the 500 ml volumetric and then the volumetric filled to the 500
ml mark with distilled or super water to make up a 50 ppm stand-
ard.
This solution also needs to be very well mixed before using for a
standard or an initial concentration to make up a lower concen-
tration solution.
D-27
-------
REFERENCES
1. High volume sampling, General Metal Work Inc., 8369 Bridge-
town Road, Village of Cleves, Ohio 45002
2. Harrison, R.M.; Williams C.R. "Airborne Cadmium, Lead and
Zinc at Rural and Urban Sites in North West England" Atmospheric
Environment Vol. 16 No. 11-2669-2681 1982.
3. Wagner, R. "Environment and Man" Third Edition, w.w. Norton
Co, New York 1978 pp. 136-155.
4. Kneip T.j: Lloyd P.J.: Wolf G., "Toxic Airborne Elements in
the New York Metropolotan Area," Journal Air Pollution Control
Association, 510-512 1978.
5. U.S. Environmental Protection Agency National Ambient Air
Quality Stanard for Lead, Federal Register 43 No 194, p. 46246,
1978.
6. Provenzano, G.R. "Motor Vehicle Lead Emission in United
States: An Analysis of Important Determinents, Geographic
Patterns and Future Trends,"
Jounral Air Pollution Control Association: 28, 1193-1199 (1978)
7. Monahan, S. "Environmental Chemistry", Willard Grant Press,
Boston Massachusetts, 1975, p. 416.
8. Margler, L.W. ; Rogozen, M.B.; Ziskind, R.A. ; and Reynolds
R. " Rapid Screening and Identification of Airborne Carcinogens
of Greatest Concern in California" APCA Journal, Vol 29, No. 11,
November 1979.
9. High Volume Samplers, The Staplex Co. 777 Fifth Avenue,
Brooklyn, New York 11232
10. Size Fraction High Volume Samplers, Anderson 2000 Inc.,
P.O. Box 20769, 1000 Sullivan Road, Atlanta, georgia 30320.
11. Quartz Fiber and Glass Fiber Filters, Gelman Instrument
Company, 600 South Wagner Road, Ann Arbor, Michigan 488106.
12. Mitchel, W.J.; Midgett, M.R.; Measuring Inorganic and
Alkyl Lead Emission form stationary sources", Journal Air
Pollution Control Association.
13. "Tentative Method of Analysis for lead content atmospheric
particulate matter using atomic absorption spectroscopy", ASTM
Method No. 315 Standard Method No. 315 Standard Method of
Analysis, ASTM 1978.
14. Bozzelli, J.W.; Kebbekus B.B., "Lead and Toxic Metals in
airbornes particule" New Jersey Department of Environmental
Protection, Toxic Substances Division, Trenton, New Jersey Feb.
1980.
D-28
-------
B-2
Appendix B
Quality Assurance
Class fiber filters from E.F.A. (calendar years 1989 and 1990).
manufactured by Whatman, were used at all sites.
Metals by Inductively Coupled Plasma (ICP^
Twenty sample filters, one acid blank, one filter blank, one *plke, and
one duplicate filter aliquot were analyzed per batch.
Arsenic by Graphite Furnace
Twenty sample filters, one filter blank, and one N.B.S. Urban Dust
aliquot were analyzed per batch.
Mercury by Cold Vapor Atomic Absorption
Twenty sample filters, one filter blank, and two Icirown mercury reference
solutions were analyzed per batch.
Average acid blanks, filter blanks, kocvn Q.C. recoveries, spike
recoveries, and duplicate precision are presented in the following tables.
E-l
-------
B-3
Table B-I Average Acid Blanks
Metals ng/ml Extract
Barium <20
Beryllium < A
Cadmium <20
Chromium <20
Cobalt <20
Copper <20
Iron <40
Lead <80
Manganese <20
Molybdenum
-------
B-A
Tables B-II Averae* Pilfer Blanks
Metal
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Molybdenum
Nickel
Vanadium
Zinc
ng/ml extract
<10
36
92
< 4
<20
<20
<20
<20
117
<80
<20
<0.2
<80
<20
<20
59
ng/filter
< 3000
17000 (CV 1989)
44000 (CY 1990)
< 2000
<10000
<10000
<10000
<10000
56200
<40000
<10000
< 60
<40000
<10000
<10000
28000
E-3
-------
B-5
Computer Printouts
B-III Known QC Recoveries (Urban Dust. Hg Solutions)
B-IV Spike Recoveries
B-V Duplicate Precision
E-4
-------
NEW YORK STATE DEPARTMENT OF HEALTH
UadtMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Ceaistry
QUALITY CONTROL SUMMARY SHEET ARSENIC (URBAN DUST)
TARGET 100 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
UPPER 991 CL 1107.7520
UPPER 951 CL 1103.3397
KAN 19.3909
lOUCfi 951 CL 75.U22
LOWER 991 CL 71.0896
Batch Number l 20 25
HAS * I-10.409I
991 CONFIDENCE LEVEL '! 20.54026 1
951 COKHDENCE LEVEL *! 15.10*23 I
Batch
Number
l
e
I?
IB
19
20
11
cc
23
;t
;r
OPERATOR
23
23
23
23
2:
Ł2
23
it
22
§Ł
22
QUALITY CONTROL
X Recovery
DATA
88.7
Vt.S
102.0
86:6
84.0
79.1
K.t
't.7
5ŁA
9<,.9
Si. 6
DATA UHICH EICEŁ0 95*. CONFIDENCE LEVEL HARKED BY («)| 991 CDNFIDCKE LEVEL (•«>
9!'. CONFIDENCE LEVEL ' Mti 991 CONFIDENCE LEVEL « 2.58r
E-5
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Uadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
TARGET 0.830
QUALITY CONTROL SUMMARY SHEET
MEAN COMPUTED FROM 1 TO 25
MERCURY (REFERENCE SOL.)
RANGE MEAN *- 12.5 */.
UPPER 99X CL
UPPER 951 CL
0.9311
0.9107
ill!
I I I I
MEAN
i i
LOWER 931 CL 0.7820
LOVER 991 CL 0.7417
Batch Number]
BIAS * «1.9?2I
991 CONFIDENCE LEVEL 'i lO.OGtfc S
951 COKFIDENCE LEVEL <: 7.401704 1
i i i i i
20
Batch OPERATOR
Number
i
2
i?
;Ł
« 5
tv
2!
cc
ji
••
23
23
23
23
23
23
23
23
• *
c3
8UAL1TY CONTROL
ng/mi
DATA
O.BOS
c.sos
0.847
ti.822
0.837
0.874
0.631
P.E57
o!e*:
C-.822
C.B24
C.E'i
C.S3:
i* 5*7
C.
(.
.;.
'^ •
v
•?
s?»
t™
iS
ss
'.'. :;
A WHICH E:CEED 9!: CCNTIDEXC: LEVEL HARKQ BY ID; 991 CONFIDENCE LEVEL <•*>
CONFIDENCE LEVE. * 1.94; «"S CONFIDENCE LEVEL * 2.5Br
E-6
-------
NEW YORK STATE DEPARTMENT OF HEALTH
UadSMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
TARGET 1.33
QUALITY CONTROL SUMMARY SHEET
MEAN COMPUTED FROM 1 TO 25
MERCURY (REFERENCE SOL.)
RANGE MEAN +- 10 '/.
UFFER 9?J CL
UFFER 95i CL
i 1 1 I I : i i I i
l.Se?!
LCKR «: CL Lett'!
. l.c!';
Batch Number ;
I'.-: * -O.J3i»
?V. CS^'t-^t LEVEL *i B.ii?:?
?:•. ;:•!.-• ID-sit LEVEL «: 6.55«c
Batch OPEwTW BJftllT"
Number ng/
*-.
I
«<
-
•
r
• *S U-.ICK E
:. ::-Kri:e!i
i
i
EES TO
LEVEL
•
t
•
"ITD**
kMKu.
nl
A
«
-
i
:Kn:i:;:: LEV& ns^ra EY «); m CONFIDENCE LEVEL uo
« Mti «: :O»,TIDENCE LEVEL « Z.SBJ
E-7
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Uadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical C«mi»try
QUALITY CONTROL SUMMARY SHEET BARIUM (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
UPPER 991 CL 1133.2371 ||||||||[||
UPPER 951 CL 1125.9073 —*
HEAN 1102.736* —
LOUER 951 CL 79.5653
LO«R 991 CL 78.2354 TTTTTTTTTTT
Batch Number I 20 25
HAS > +2.736X
991 CONFIDENCE LEVEL *i 29.4883* I
951 CONFIDENCE LEVEL *! 22.55394 1
Batch
Number
1
2
17
IB
19
20
21
22
23
2
9H CONFIDENCE LEVEL • 1.94i 991 CONFIDENCE LEVEL * Z.SBi
E-8
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Uadaworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemivtry
QUALITY CONTROL SUMMARY SHEET BERYLIUM ! 7.!5»395 I
Batch
Number
l
I
n
IB
19
20
si
22
23
24
21
OPERATOR
23
23
23
23
23
23
23
23
23
23
23
QUALITY CONTROL
X recovery
DATA
93.6
92.0
90. ii
100.0
101.6
96.0
92.0
92.6
9E.B
93.6
98.4
DATA WHICH EICEU 951 CONFIDENCE LEVEL MRKEI BY til; 99! CONFIDENCE LCVEl (»«)
9SI CONFIDENCE LEVEL * 1.96f 991 CONFIDENCE LEVEL * 2.58r
E-9
-------
NEW YORK STATE DEPARTMENT OF HEALTH
WadSMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cenistry
QUALITY CONTROL SUMMARY SHEET CADMIUM (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 23 SCALED BY OUTLIER
UPfER 991 CL 1121.7542 uillllll
UPPER 951 CL 1115.4UI
KEAN 94.3111
LOWER 951 CL 74.9807
LOiER 991 CL 70.8440 TTTTTTT»T
Batch Number t ^
BIAS « -3.4891
991 CONFIDENCE LEVEL *! 24.41947 1
T5S CONFIDENCE LEVEL '! 20.07074 I
Batch
Number
i
E
17
18
19
20
Ł3
24
25
OPERATOR
23
E3
23
23
23
23
23
23
23
BUALITY CONTROL
% recovery
1 DATA
87. 1
W.t
103.7
fl.3
87.1
103.7
95.*
114.01
87.1
MTA WHICH EICEED 951 CONFIDENCE LEVEL KMKE1 IT (•)? MS CONFIDENCE LEVEL <•«>
951 CONFIDENCE LEVEL * l.94r 991 CONFIDENCE LEVEL • 2.58r
E-10
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Uadsworth C»nt»r for Laboratories And R«»«arch
Laboratory of Inorganic Analytical C«mi«try
QUALITY CONTROL SUMMARY SHEET CHROMIUM (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
UPPER 991 CL IW.8105 Ml|lllllll
UPPER 951 CL 1133.1175
REAM 1105.434*.
LOKF 95; CL 78.1532
LOWER 991 CL 49.*422 TTTTTTTTTTT
Batch Number i 20 25
BIAS ' '5.436S
991 CONFIDENCE LEVEL *t 34.2MW S
93S CONFIDENCE LEVEL '! 24.01*84 1
Batch
Number
i
2
17
18
19
20
21
22
23
2
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
QUALITY CONTROL SUMMARY SHEET COBALT (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 23 RANGE MEAN *- 1*7.5 7.
UPPER 991 CL 1128.3585
UPPER 951 a II2*.1*78
MEAN 1110.83*4 —
LOUER 951 CL 97.5250
LOUER 99X CL 93.31*2
ii111111111
Batch Number 1 » 83
BIAS * I+IO,!3U
991 CONFIDENCE LEVEL «! 15,80904 J
951 CONFIDENCE LEVEL '! 12.00997 I
Batch
Number
1
2
17
11
19
20
21
22
23
24
25
OPERATOR
23
23
23
23
23
23
23
23
23
23
23
QUALITY CONTROL
X recovery
DATA
113.4
110.*
112.0
102. *
112.0
124.8*
113.6
110.4
97.6
112.0
110.4
DATA WHICH EICEED 95S CONFIDENCE LEVEL NARKED IY l»); 99! CONFIDENCE LEVEL (*D
95S CONFIDENCE LEVEL ' 1.9if 991 CONFIDENCE LEVEL > 2.38f
E-12
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wad«worth Center for Laboratory** and R»»*arch
Laboratory of Inorganic Analytical Cemimtry
QUALITY CONTROL SUMMARY SHEET COPPER (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
mini n
UPPER 991 a 1105.1X3
UPPER m CL 1101.791*
KAN 91.IM7
LOVER 951 a 80.5480
LOUER m a 77.1B11
Batch Number t at
HAS « -8.8331
991 CONFIDENCE LEVEL *! 15.3*069 \
951 CONFIDENCE LEVEL «+ 11.45M4 I
Batch
Number
1
I
17
18
20
21
S3
24
85
OPERATOR
23
23
23
23
!3
23
23
23
23
QUALITY CONTROL
I recovery
DATA
93.2
K.I
92.1
Ą3.4
too.*
16.9
95.Ł
86.5
90.5
DATA WHICH EICEED 951 CONFIDENCE LEVEL HARKED BY («); 991 CONFIDENCE LEVEL (»«)
951 CONFIDENCE LEVEL > 1.96* 991 CONFIDENCE LEVEL « Z.SBr
E-13
-------
NEW YORK STATE DEPARTMENT OF HEALTH
UadBMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Gemistry
QUALITY CONTROL SUMMARY SHEET IRON (SPIKE)
TARGET 1OO MEAN COMPUTED FROM 1 TO 25 RANGE MEAN *- 20
UPPER 991 CL 1H8.451E
UPPH 93J CL 1114.0533
HEAN 1100.1500 —
LOVER 951 a B6.24AS
LOWER 991 CL 11.8486
Batch Number 1 20
BIAS * »0.130I
99: CONFIDENCE LEVEL •+ 18.27381 :
951 CONFIDENCE LEVEL >i 13.88243 X
Batch
Number
1
Z
1?
18
19
20
81
22
23
25
OPERATOR
23
23
23
23
{3
a
23
23
23
23
OU
%
103.7
104.1
B4.B
111.1
92.1
10S.O
9S.2
103.7
100.6
W.2
A1ITY CONTHOL
recovery
DATA
9ATA WICH EICEED 951 CONFIDENCE LEVEL BARKED BY <•>! HI CONFIDENCE LEVEL (Ml
951 CONFIDENCE LEVEL * 1.9if 991 CONFIDENCE LEVEL « 2.58r
E-14
-------
NEW YORK STATE DEPARTMENT OF HEALTH
UadsMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cenistry
QUALITY CONTROL SUMMARY SHEET LEAD (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
UPPER 991 CL II20.BOO nillllll
UPPER 951 CL 111*.0879
DEAN 92.1556
LWER 951 CL 71.4232
LOWER 991 CL 4*.9068 TTTTTTTTT
Batch Number 1 20
BIAS > -7.UU
991 CONrilENCE LEVEL >t 30.099U I
9SS CONFIDENCE LEVEL *i 22.8M03 1
Batch
Number
1
2
17
II
19
20
22
23
25
OPERATOR
23
23
23
23
23
23
23
83
23
QUALITY CONTROL
* reWAery
102.3
94.2
a?.?
1U.2I
82.7
90.B
87.9
90.*
81.5
DATA HH1CM EICEED ttS CONFIDENCE LEVEL HARKED BY («); 99X CONFIDENCE LEVEL (•*)
931 CONFIDENCE LEVEL * 1.961 991 CONFIDENCE LEVEL « 2.5Bf
E-15
-------
NEW YORK STATE DEPARTMENT OF HEALTH
UadSMorth Center for Laboratories and Re»»arch
Laboratory of Inorganic Analytical Centi»try
DUALITY CONTROL SUMMARY SHEET MANGANES^C SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 23 SCALED BY OUTLIER
UPPER 991 CL 1133.2957 nilllllll
UPPER 931 CL M3.0450
MEAN 110*.4000
LOVER 931 CL 45.7330
LOWER 991 CL 33.5043 TTTTTTTTTT
Batch Number l 21
HAS ' +4.4001
991 CONFIDENCE LEVEL «1 48.73048 I
931 CONFIDENCE LEVEL >i 37.0334 I
Batch
Number
1
1?
11
If
20
21
IS
23
2*
25
OPERATOR
23
23
23
23
23
23
23
21
23
23
QUALITY CJMTROL
% recovery
MTA
124.0
92.0
132.0
?i.O
108.0
10.0
10*. 0
114.0
124.0
86.0
DATA UH1CM E1CEES 951 CONFIDENCE LEVEL HARKED IY («)) 991 CONFIDENCE LEVEL («*>
951 CONFIDENCE LEVEL * I.9tr 991 CONFIDENCE LEVEL * 2.5lf
E-16
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wad*worth Cvntvr for Laboratories and R«»»arch
Laboratory of Inorganic Analytical C*mi»try
QUALITY CONTROL SUMMARY SHEET MOLYDEN (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO 25 RANGE MEAN «•- 17.5 V,
UfPtR 991 CL JIO*.91*7
UPPER 951 CL uw.1936 —
HEM 95.1700
LOUER 951 CL 84.5*6*
LOVER m CL 83.7513
Batch Number i 20
HAS * -4.4301
m CONFIDENCE LEVEL >i 12,17859 1
9SI CONFIDENCE LEVEL «i 9.251957 I
Batch
Number
1
2
17
18
19
to
21
22
23
25
OPERATOR
23
23
23
23
13
23
a
23
23
23
QUALITY CONTROL
* recovery
102.5
12.2
92.6
11.5
I9.f
96.1
98.7
99.8
93.0
98.7
DATA UKICH EICEEB 951 CONFIDENCE LEVEL HARKED BY <»>} 991 COPT IDEUCE LEVEL («*l
951 CONFIDENCE LEVEL * l.96r 991 CONFIDENCE LEVEL * 2.58r
E-17
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
QUALITY CONTROL SUMMARY SHEET NICKEL (SPIKE)
TARGET 100 MEAN COMPUTED FROM 1 TO Ł5 SCALED BY OUTLIER-
UPPER 991 CL 1124.4008 ULUUUU
UPPER 951 CL IU4.9238
HEM 92.4545
LOME* 951 CL 48.3853
LOME* 991 CL 40.7082 —
in in 11 in
Batch Number 1 20
HAS * -7.3451
m CONFIDENCE LEVEL «+ 34.47894 1
HI CONFIDENCE LEVEL •! 24.17331 1
Batch
Number
1
2
17
IB
19
20
21
22
23
!4
K
OPERATOR
23
23
23
23
23
23
23
21
23
23
23
6UM.ITY CONTROL
% rtctyipry
118.41
94.4
83.2
!04.0
99.2
89.4
81.4
97.4
B8.0
fl.2
72.0
DITA UKICH EICEED 9SI COITIDCNCE LEVIL NAKED 8Y (O; f9S CONF1DEICE LEVEL ("I
95S CONFIDENCE LEVEL < 1.94» 99S CONFIDENCE LEVEL • 2.M»
E-18
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemimtry
TARGET 100
QUALITY CONTROL SUMMARY SHEET
MEAN COMPUTED FROM 1 TO 25
VANADIUM (SPIKE)
RANGE MEAN +- 20 '/.
m
rim
UPPER 971 CL
UPPER 951 CL
1108.1138
UN. 9*93
MEAN
LOWER 951 CL
LOWER 991 CL
84.9M&
81.7771
I II I Illl
Batch Number l Ł0 25
HAS ' -5.0551
991 CONHDENCc LEVEL *i 13.86934 *.
951 CONFIDENCE LEVEL *! 10.536* 1
Batch OPERATOR
Number
I 23
I 23
1? 23
IE 23
i • •»
2
Ł
DA
c
c
c
A WHICH E1CEE1
WALITY CONTROL
X recovery
DATA
98.9
86.9
Be. 7
10P.3
96.3
90.9
100.5
100.5
95! CONFIDENCE LEVEL HARKED BY («>; 991 CONFIDENCE LEVEL (»*)
E-19
-------
NEW YORK STATE DEPARTMENT OF HEALTH
WadSMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Ceotistry
OUALITY CONTROL SUMMARY SHEET ZINC 1.9tr 991 CONFIDENCE LEVEL • 2.5Br
E-20
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cenittry
QUALITY CONTROL SUMMARY SHEET BARIUM (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIEF
UPPER 991 CL 9.9797
UPPER 951 CL 1.3198
MEAN 3.3437
LOHER 931 CL -1.442*
LOVER 991 CL -3.2523 TTTTTTTTTTT
Batch Number 1 20 25
HAS < I+3.363E«05J
99S CONFIDENCE LEVEL «i 196,687 1
9SS CONFIDENCE LEVEL «i 149.4211 S
Batch
Number
t
2
17
11
19
20
21
22
23
24
25
OPERATOR
23
23
23
23
23
23
23
23
23
23
23
QUALITY CONTROL
Z difference
DATA
2.8
1.4
4.9
3.4
0.001
2.7
8.61
2.4
7.0
t.B
1.0
DATA WHICH EICEED 951 CONFIDENCE LEVEL HARKED IY <»>; 191 CONFIDENCE IEVEI (II)
9S1 CONFIDENCE LEVEL * 1.96r 991 CONFIDENCE LEVEL • 2.58*
E-21
-------
NEW YORK STATE DEPARTMENT OF
UadSMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
QUALITY CONTROL SUMMARY SHEET CHROMIUM (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO S<* SCALED BY OUTLIER
UPPER 991 CL 4.3*97 TTTTTTTTT
MEAN 1.2473
LOMER ni CL -2.5937
L01IER 99X CL -3.ilSl TTTTTTTTT
Batch Number 1 21
HAS * W.2WE+05X
991 CONFIDENT LEVEL «! Ml,0313 1
991 CONFIDENCE LEVEL *i 304.6594 I
Batch OPERATOR QUALITY CONTROL
Number * difference
DATA
1
2
17
IB
19
21
22
23
24
23
23
23
23
23
23
23
23
23
0.001
0.001
0.001
»,3
4.5
0,001
2,4
0.001
O.OOi
DATA VHICH EICEEI 951 UNHKNCE LEVEL HARKED BY l«); 99S CONFIDENCE LEVEL <")
9SS CONFIDENCE LEVEL * l.9tf 991 CONFIDENCE LEVEL > 2.5Bi
E-22
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
QUALITY CONTROL SUMMARY SHEET COPPER (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
UPPER 991 CL 24.8m ITTTTITTTT
UPPER m CL 22.»061
REAM 8.1700
LOWER 951 CL -5.Wit
LOifER W CL -9.87« TTTTTTTTTT
Batch Number I 20
HAS - 1+M69E»05I
911 CONFIDENCE LEVEL «i 214.5615 I
951 COKF1KNCE LEVEL *! 1M.5348 1
Batch
Number
1
2
17
IB
19
20
2i
23
2<>
25
OPERATOR
23
23
23
23
23
23
23
23
23
23
QUALITY CONTROL
Z difference
DATA
8.0
3.4
3.7
H.I
1.5
1.0
20.4
4.2
8.5
20.5
DATA UMICH EICEH 951 CONFIDENCE LEVEL HARKED BY (•); 99S CONFIDENCE LEVa
9SS CONFIDENCE LEVEL * 1.94* 991 CONFIDENCE LEVEL • 2.58f
E-23
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Uadsworth C*nt»r for Laboratories and R»s»arch
Laboratory of Inorganic Analytical Cwnistry
QUALITY CONTROL SUMMARY SHEET IRON (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO Ł5 SCALED BY OUTLIER
UPPER 99J CL 12.8861
UPPER 931 a 10.9W7
KAN 4.7909
LOWER 951 CL -1.3589
LOyER 991 CL -3.30*3 TTTTTTTTTTT
Batch Number 1 20 25
HAS • S+4.790E+05I
991 CONFIDENCE LEVEL «* 146.9692 1
951 CONFIDENCE LEVEL «! 12B.3M2 1
Batch OPERATOR QUALITY CONTROL
Number * difffATTflce
1
2
17
IB
19
20
21
22
23
24
25
23
23
23
23
23
23
23
23
23
23
23
5.7
1.8
5.3
3.1
6.9
2.4
t.8
12.6*
0.9
*.i
4.*
OATH WHICH EICEED 951 CONFIDENCE LEVEL HARKED IY («); 991 CONFIDENCE LEVEL <»»)
951 CONFIDENCE LEVEL * 1.9if 991 CONFIDENCE LEVEL * 2.58i
E-24
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Wadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
QUALITY CONTROL SUMMARY SHEET LEAD (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 2 TO 25 SCALED BY OUTLIEP
UPPER 991 CL 24.0714 TTTTTTTTTT
UPPER 951 CL 20.2383
KAN 8.1201
931 CL -3.9981
LOWER 991 CL -7.831* TTTTTTTTTT
Batch Number 2 21
BIAS < !«B.119E«05X
991 CONFIDENCE LEVa *! 194.4452 X
951 CONFIDENCE LEVEL '! 149.2374 S
Batch OPERATOR QUALITY CONTROL
Number
2
17
IB
19
20
21
22
23
24
25
23
23
23
23
23
23
23
23
23
23
4.7
19.4
0.001
1.0
7.3
15.2
4.9
13.9
2.2
14.4
DATA MUCH EICEED 951 CONFIDENCE LEVEL HARKED IT (»)( 191 CONFIDENCE LEVEL (»«>
95X CONFIDENCE LEVEL * Mil 991 CONFIDENCE LEVEL • 2.58f
E-25
-------
NEW YORK STATE DEPARTMENT OF HEALTH
Uadsworth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
QUALITY CONTROL SUMMARY SHEET HANGANES (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
UPPER 991 CL 10.5017 TTTTTT
UPPER 95J CL 8.7974
HEAN 3.4094
LOVER 951 CL -1.9784
LOWER 991 CL -3.4830 TTTTTTTTTTT
Batch Number 1 20 25
BIAS - 1+3.408E+051
99X CONFIDENCE LEVEL «! 208.025B 1
951 CONFIDENCE LEVEL '! 158.0351 1
Batch
Number
1
2
17
IB
19
20
2!
22
23
24
25
OPERATOR
23
23
23
23
23
23
23
23
23
23
23
QUALITY CONTROL
Z difference
DATA
0.001
0.001
4.2
2.5
4.3
3.7
7.B
7.4
0.001
2.4
5.0
DATA WHICH EICEED 9SX CONFIDENCE LIVEL HARKED BY (»); 991 CONFIDENCE LEVEL (**>
951 CONFIDENCE LEVEL * M6r 991 CONFIDENCE LEVEL ' 2.5Bf
E-26
-------
NEW YORK. STATE DEPARTMENT OF HEALTH
Wadsworth Canter for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
QUALITY CONTROL SUMMARY SHEET NICKEL (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO 25 SCALED BY OUTLIER
UPPER MI Cl 16.717!
UPPER 931 CL 13.1071 --
BEAN 4.3903
LWER 931 CL -5.1245
LONER 991 CL -8.1349 TTTTTTTTTT
Batch Number 1 g]
HAS • S44.3B9E+OSS
99» CONFIDENCE LEVEL «! 295.3377 I
951 CONFIDENCE LEVEL *i 216.7482 I
Batch
Number
1
2
17
18
20
21
22
23
2*
25
OPERATOR
23
23
23
23
23
23
23
23
23
23
„ QUALITY CONTROL
* difference
DATA
I.I
0.601
2.9
6.4
6.7
0.001
15.61
4.3
6.9
0.001
DATA WHICH E1CEEJ 951 CONFIDENCE LEVEL HARKED BY ID; 991 CONFIDENCE LEVEL (••)
95S CONFIDENCE LEVEL * l.96r 991 CONFIDENCE LEVEL • 2,5Bf
E-27
-------
NEW YORK STATE DEPARTMENT OF HEALTH
WadsMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemistry
DUALITY CONTROL SUMMARY SHEET VANADIUM (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO S5 SCALED BY OUTLIER
1111111111
UPPER 9SX CL 10.9880
HEAN 8.6205
IOHER 951 CL -3.7*70
Batch Number
BIAS ' 1+2.419E+05I
1 20
991 CONFIDENCE LEVEL «t 420.3157 X
951 CONFIDENCE LEVEL *i 319.3097 1
Batch OPERATOR QUALITY CONTROL
Number * diff?F^nce
MT A
1
2
17
18
19
20
21
22
2*
25
23
23
23
23
23
23
23
23
23
23
2.3
0.001
S.6
2.2
13.6*
0.001
0.001
0.001
2.S
0.001
MTA WHICH EICEE9 951 CONFIDENCE LEV& HARKED VI (»>; 991 CONFIDENCE LEVEL (««)
951 CONFIDENCE LEVEL ' 1.9tr 991 COKFIDENCE LEVEL • 2.58r
E-28
-------
NEU YORK STATE DEPARTMENT OF HEALTH
UadCMorth Center for Laboratories and Research
Laboratory of Inorganic Analytical Cemimtry
QUALITY CONTROL SUMMARY SHEET ZINC (DUPLICATES)
TARGET 0.001 MEAN COMPUTED FROM 1 TO Ł5 SCALED BY OUTLIER
UFfER 991 CL 18.8*75 Ulllllll
UPPER 951 CL 15.7922
HEW 4.1333
LO«ER 951 Cl -3.5255
LWER 991 CL -6.SB09 TTTTTTTTT
Batch Number i 20
HAS * I+4.132E+OSX
991 CONFIDENCE LEVEL •+ 207.2944 X
95! CONFIDENCE LEVEL >i 157.1.612 I
Batch
Number
1
2
17
18
19
20
21
23
25
OPERATOR
23
23
23
23
23
23
23
23
23
QUALITY CONTROL
DATA
2.!
7.1
3.0
0.4
5.4
1.5
B.O
12.5
U.i
DATA yHlCH E1CEEJ 951 CONFIDENCE LEVEL NARKEB BY (»); 991 CONFIDENCE LEVEL («•)
951 CONFIDENCE LEVEL • 1.96r 991 CONFIDENCE LEVEL • 2.SB*
B-29
-------
C-l
Appendix C
Methodology
E-30
-------
C-2
Method Summary
Arsenic
One sixth of each filter was digested in an acid bomb according to EPA
Stack method 108, and analyzed by graphite furnace, EPA Method 206.2, EPA
600/4-79-020.
Metals by ICP
One twelfth of each filter was extracted with a nitric acid-hydrochloric
acid mixture in an ultrasonic bath (final acid concentration of 1.6X nitric
acid - 52 hydrochloric acid). Barium, beryllium, cadmium, chromium, cobalt,
copper, iron, lead, manganese, molybdenum, nickel, vanadium, and zinc were
digested using EPA method EQL-0380-043 and determined by ICP, EPA Method
200.7, EPA 600/4-79-020.
Mercury
One sixth of each filter was digested and analyzed by method 3112B, Cold
Vapor Atomic Absorption after persulfate-permanganate digestion, Standard
Methods for the Examination of Water and Wastewater, 17th Edition.
The minimum reportable concentrations of metals in the extracts are
listed in Table C-I.
Analytical Methods are included at the end of this appendix.
E-31
-------
C-3
Table C-I Mlnimuin Reoortable limits
Metal
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Mercury
Molybdenum
Nickel
Vanadium
Zinc
ng/ral extract
10
20
4
20
20
20
20
40
80
20
0.2
80
20
20
40
ng/filter
3000
10000
2000
10000
10000
10000
10000
20000
40000
10000
60
40000
10000
10000
20000
ng/M3'
2
5
1
5
5
5
5
10
20
5
0.1
20
5
5
10
* assuming 2000 M3 air sampled.
E-32
-------
C-4
Arsenic Digestion Procedure - Graphite Furnace Analysis
Each batch will contain 1 filter blank and 1 - 50 rag urban dust sample.
1. Place 2 strips (3/4" x 8") in the Teflon liner of the Parr Bomb (one sixth
of sample).
2. Add 10 ml of concentrated nitric acid.
3. Close bomb and liner and place in 150°C oven for at least 5 hours.
4. Remove from oven and cool.
5. Open bomb and liner and pour off acid from the filter into a 50 ml
volumetric flask. Rinse filter with several portions of distilled
deionized water, pour rinse water into the volumetric flask. Bring to
volume with distilled deionized water. Shake.
6. Evaporate a 10 ml portion of the solution to dryness.
7. Bring back to 10 ml volume with 0.52 nitric acid.
8. Pour in vial and give it to be analyzed using the graphite furnace.
REAGENT
o.52 nitric acid: dilute 5.0 ml concentrated acid to 1 liter.
Reference, Digestion Method - EPA Stack Method 108.
Reference, Graphite Furnace Method - EPA 600/4-79-020. 206.2.
E-33
-------
ARSENIC
Method 206.2 (Atomic Absorption, furnace technique)
STORET NO. Total 01002
Dissolved 01000
Suspended 01001
Optimum Concentration Range: 5-100 ug/1
Detection Limit: 1 ug/1
Preparation of Standard Solution
1. Stock solution: Dissolve 1.320 g of arsenic trioxide, As30j (analytical reagent grade) in
100 ml of dekmtzed distilled water containing 4 g NaOH. Acidify the solution with 20 ml
cone. HNOj and dilute to 1 liter. 1 ml = 1 mg As (1000 mg/1).
2. Nickel Nitrate Solution, 5%: Dissolve 24.780 g of ACS reagent grade Ni(NOj)j«6H,O in
deionized distilled water and make up to 100ml.
3. Nickel Nitrate Solution, 1%: Dilute 20 ml of the 5% nickel nitrate to 100 ml with
deionized distilled water.
4. Working Arsenic Solution: Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. Withdraw appropriate aliquots of the stock
solution, add I ml of cone. HNO,, 2ml of 30% H:O, and 2ml of the 5% nickel nitrate
solution. Dilute to 100 ml with deionized distilled water.
Sample Preservation
1. For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
section of this manual.
Sample Preparation
1. Transfer 100 ml of well-mixed sample to a 250 ml Griffin beaker, add 2 ml of 30% H,O2
and sufficient cone. HNO, to result in an acid concentration of l%(v/v). Heat for 1 hour
at 95*C or until the volume is slightly less than 50 ml.
2. Cool and bring back to SO ml with deionized distilled water.
3. Pipet 5 ml of this digested solution into a 10-ml volumetric flask, add 1 ml of the 1%
nickel nitrate solution and dilute to 10 ml with deionized distilled water. The sample is
now ready for injection into the furnace.
Approved for NPDES and SDWA
Isiued 1978
206.2-1
E-34
-------
NOTE: If solubilization or digestion is not required, adjust the HNOj concentration of
the sample to 1% (v/v) and add 2 ml of 30%H,O, and 2 ml of 5% nickel nitrate to each
100 ml of sample. The volume of the calibration standard should be adjusted with
deionized distilled water to match the volume change of the sample.
Instrument Parameters (General)
1. Drying Time and Temp: 30 sec-123*C.
2. Ashing Time and Temp: 30 sec-1100*C.
3. Atomizing Time and Temp: 10 sec-2700*C.
4. Purge Gas Atmosphere: Argon
5. Wavelength: 193.7 nm
6. Other operating parameters should be set as specified by the particular instrument
manufacturer.
Analysis Procedure
1. For the analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
Atomic Absorption Methods section of this manual.
Notes
1. The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
2100, based on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
graphite. Smaller size furnace devices or those employing faster rates of atomization can
be operated using lower atomization temperatures for shorter time periods than the
above recommended settings.
2. The use of background correction is recommended.
3. For every sample matrix analyzed, verification is necessary to determine that method of
standard addition is not required (see part 5.2.1 of the Atomic Absorption Methods
section of this manual).
4. If method of standard addition is required, follow the procedure given earlier in part 8.5
of the Atomic Absorption Methods section of this manual.
S. For quality control requirements and optional recommendations for use in drinking
water analyses, see pan 10 of the Atomic Absorption Methods section of this manual.
6. Data to be entered into STORET must be reported as ug/1.
Precision and Accuracy
1. In a single laboratory (EMSL), using • mixed industrial-domestic waste effluent
containing 15 ug/1 and spiked with concentrations of 2,10 and 25 ug/1, recoveries of
83%, 90% and 88% were obtained respectively. The relative standard deviation at these
concentrations levels were ±8.8%, ±8.2%, ±3.4% and ±8.7%, respectively.
2. In a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
of 20, SO and 100 ug As/1, the standard deviations were ±0.7, ±1.1 and ±1.6
respectively. Recoveries at these levels were 103%, 106% and 101%, respectively.
206.2-2
E-35-
-------
NEW YORK STATE DEPARTMENT OF HEALTH
DIVISION OF LABORATORIES AND RESEARCH
DETERMINATION OF LEAD CONCENTRATION IN AMBIENT
PARTICIPATE MATTER BY FLAME ATOMIC ABSORPTION
SPECTROMETRY FOLLOWING ULTRASONIC EXTRACTION
WITH HEATED HN03-HC1
EPA DESIGNATED EQUIVALENT METHOD NO. EQL-0380-043
1. Principle and Applicability
1.1 Ambient air suspended participate matter is collected on a
glass-fiber filter for 24-hours using a high volume air sampler. The analysis
of the 24-hour samples may be performed for either individual samples or
composites of the samples collected over a calendar month or quarter,
provided that the compositing procedure has been approved 1n accordance with
section 2.8 of Appendix C to Part 58 of Chapter I of Title 40, Code of Federal
Regulations (40 CFR 58 — 44 FR 27585, May 10, 1979).
1.2 Lead in the participate matter Is sol utilized by ultrasonic
extraction with a heated mixture of nitric add (HN03) and hydrochloric
acid (HC1).
1.3 The lead content of the sample is analyzed by atomic absorption
spectrometry using an air-acetylene flame, the 283.3 or 217.0 run lead absorption
line, and the optimum instrumental conditions recommended by the manufacturer.
1.4 The ultrasonication extraction with heated HN03/HC1 wi"
extract metals other than lead from ambient participate matter. iDo not use
for Cr, Sn or Ti.)
2. Range, Sensitivity, and Lower Detectable Limit
The values given below are typical of the method's capabilities. Absolute
values will vary for individual situations depending on the type of instrument
used, the lead line, and operating conditions.
E-36 Accented 7/80
-------
2.1 Range. The typical range of the method is 0.07 to 7.5 pg Pb/vf
assuming an upper linear range of analysis of 15 pg/ml and an air volume of
2400 m3.
2.2 Sensitivity. Typical sensitivities for a It change in absorption
(0.0044 absorbance units) are 0.2 and 0.5 pg Pb/ml for the 217.0 and 283.3 nm
lines, respectively.
2.3 Lower detectable limit (LDL). A typical LDL is 0.07 v9 Pb/m3.
The above value was calculated by doubling the between-laboratory standard
deviation obtained for the lowest measurable lead concentration in a colla-
borative test of a similar method. An air volume of 2400 m was assumed.
3. Interferences
Two types of interferences are possible! chemical, and light scattering.
3.1 Chemical. Reports on the absence '»z»3»4»5 Of chemical inter-
ferences far outweigh those reporting their presence, therefore, no correction
for chemical interferences is given here. If the analyst suspects that the
sample matrix is causing a chemical interference, the interference can be
verified and corrected for by carrying out the analysis with and without the
method of standard additions.
3.2 Light scattering. Nonatomic absorption or light scattering,
produced by high concentrations of dissolved solids In the sample, can produce
*
a significant Interference, especially at low lead concentrations. The inter-
ference is greater at the 217.0 nm line than at the 283.3 nm line. No Inter-
ference was observed using the 283.3 run line with a similar method.
Light scattering interferences can, however, be corrected for
inst rumen tally. Since the dissolved solids can vary depending on the origin
of the sample, the correction may be necessary, especially when using the
217.0 nm line. Dual beam Instruments with a continuum source give the most
2
E-37
-------
accurate correction. A less accurate correction can be obtained by using a
nonabsorbing lead line that is near the lead analytical line. Information
on use of these correction techniques can be obtained from instrument manu-
facturers' manuals.
If instrumental correction is not feasible, the interference
can be eliminated by use of the ammonium pyrrolidinecarbodithioate-methylisobutyl
p
ketone, chelation-solvent extraction technique of sample preparation.
4. Precision and Bias
4.1 The high-volume sampling procedure used to collect ambient air parti-
culate matter has a between-laboratory relative standard deviation of 3.7 percent
over the range 80 to 125 yg/m . The combined extraction-analysis procedure for
a similar method* ' has an average within-laboratory relative standard deviation
of 5 to 6 percent over the range 1.5 to 15 ug Pb/ml, and an average between-
laboratory relative standard deviation of 7 to 9 percent over the same range.
5. Apparatus
5.1 Sampling.
5.1.1 High-volume sampler. Use and calibrate the sampler as described
1n reference 10.
5.2 Analysis.
5.2.1 Atomic absorption spectrophotometer. Equipped with lead hollow
cathode or electrode!ess discharge lamp.
5.2.1.1 Acetylene. The grade recommended by the instrument manufacturer
should be used. Change cylinder when pressure drops below 50-100 psig.
5.2.1.2 Air. Filtered to remove particulate, oil, and water.
5.2.2 Labware.
3
E-38
-------
5.2.2.1 Centrifuge tubes. 50-tnl polypropylene tubes with polypropylene
screw tops. Nalgene* 3119-0050 polyallomor or equivalent.
5.2.2.2 Volumetric flasks. (Class A borosilicate glass). 100-ml, 200-ml,
1000-ml.
5.2.2.3 Pipettes. (Class A borosilicate glass). To deli-.er 1, 2, 4, 8,
10, 15, 30, 50-ml. An automatic dispensing pipette capable of dslivering 12.0
and 14.0 ml with an accuracy of 0.1 ml or better and a repeatability of 20 yl
may be substituted for Class A pipettes used in sample preparation. Grumann*
ADP-30T1 or equivalent.
5.2.2.4 Cleaning. All labware should be scrupulously cleaned. Wash with
laboratory detergent (or ultrasonicate for 30 minutes in laboratory detergent),
rinse, soak for a minimum of 4 hours in 20 percent (w/w) HNO,» rinse 3 t'imes with
distilled-deionized water, and dry in a dust free manner.
5.2.3 Centrifuge. Capable of holding 50-ml centrifuge tubes and speed
of.2500 RPM.
5.2.4 Ultrasonication water bath, heated. Commercially available
laboratory ultrasonic cleaning baths of 450 watts or higher "cleaning power",
M *., actual ultrasonic power output to the bath) and capable of maintaining
JOO°C nave been found satisfactory, e.g., Branson Cleaning Equipment Co., model
tW?/0-36 ultrasonicator.
5.2.5 Template. To aid in sectioning the glass-fiber filter. See
Figure 1 for dimensions* or 1.75" punch.
5.2.6 Pizza cutter. Thin wheel. Thickness <1 mm.
5.2.7 Polyethylene bottles. For storage of samples. Linear polyethylene
gives better storage stability than other polyethylenes and is preferred.
6. Reagents
6.1 Sampling.
^Mention of commercial products does not imply endorsement by the U.S. Environ-
mental Protection Agency.
E-39
-------
6.1.1 Glass fiber filters. The specifications given below are
intended to aid the user in obtaining high quality filters with reproducible
properties. These specifications have been met by EPA contractors.
6.1.1.1 Lead content. The absolute lead content of filters is not
critical, but low values are, of course, desirable. EPA typically obtains
filters with a lead content of <75 yg/filter.
It is important that the variation 1n lead content from filter to
filter, within a given batch, be small.
6.1.1.2 Testing.
6.1.1.2.1 For large batches of filters ( > 500 filters) select at random
20 to 30 filters from a given batch. For small batches (< 500 filters) a lesser
number of filters may be taken. Cut one 3/4" x 8" or 1" x 8" strip or 2 discs (8X
total) from each filter anywhere 1n the filter. Analyze all strips or 2 discs.
separately, according to the directions in Sections 7 and 8.
6.1.1.2.2 Calculate the total lead in each filter as
F . . n Oh/n.1 v *° ^ - " Strips
Fb « Pb/ml x stnp x filter
where:
F^« Amount of lead per 72 square inches of filter, v9«
n • 12 (for 3/4" x 8" strip) or 9 (for 1" x 8" strip), or ^P- for
discs. w
6.1.1.2.3 Calculate the mean, F~b, of the values and the relative standard
deviation (standard deviation/mean x 100). If the relative standard deviation
1s high enough so that, in the analysts' opinion, subtraction of T^ (Section 10.2)
may result in a significant error In the yg Pb/m , the batch should be rejected.
6.1.1.2.4 For acceptable batches, use the value of T^ to correct all lead
analyses (Section 10.2) of particulate ratter collected using that batch of filters.
If the analyses are below the LDL (Section 2.3) no correction is necessary.
E-40
-------
6.2 Analysis.
6.2.1 Concentrated (16.0 M) HN03> ACS reagent grade HN03 and
commercially available redistilled HN03 have been found to have sufficiently
low lead concentrations.
6.2.2 Concentrated (12.3 M) HC1. ACS reagent grade.
6.2.3 Distilled-deionized water. (D.I. water).
6.2.4 Extracting acid (1.03 M HNOj + 2.23 M HC1). This solution
is used in the extraction procedure. To prepare, place 500 ml of D.I. water
in a 1000-ml volumetric flask and add 64.6 ml of concentrated HN03 and 182 ml
of concentrated HC1. Shake well, cool, and dilute to volume with D.I. water.
Caution: Acid fumes are toxic. Prepare in a well ventilated fume hood.
6.2.5 Calibration matrix (0.31 M HN03 + 0.67 M HC1). This solution
is used as the matrix for calibration standards. To prepare, place 500 ml of
D.I. water in a 1000-ml volumetric flask and add 19.4 ml of concentrated HN03
And 54.6 ml of concentrated HC1. Shake well, cool, and dilute to volume with
D.I. water.
6.2.6 Lead nitrate, Pb(NO,)2. ACS reagent grade, purity 99.0 per-
cent. Heat for 4-hours at 120°C and cool in a desiccator.
6.3 Calibration standards.
6.3.1 Master standard, 1000 yg Pb/ml 1n HN03/HC1. Dissolve 1.598 g
of Pb(N03)2 1n 0.31 M HN03 + 0.67 M HC1 (Section 6.2.5) contained in a 1000-ml
volumetric flask and dilute to volume with 0.31 M HN03 + 0.67 M HC1. Store
standard in a polyethylene bottle. Corraercially available certified lead stand-
ard solutions may also be used.
E-41
-------
7. _Procedure
7.1 Sampling. Collect samples for 24-hours using the procedure
described in reference 10 with glass-fiber filters meeting the specifications
in 6.1.1. Transport collected samples to the laboratory taking care to
minimise contamination and loss of sample.
7.2 Sample preparation.
7.2.1 Extraction procedure.
7.2.1.1 Cut a 3/4" x 8" or 1" x 8" strip or 2 discs (8%) from the exposed
filter using a template and a pizza cutter as described in Figures 1 and 2 or 1.75
punch. Other cutting procedures may be used.
Lead in ambient particulate matter collected on glass fiber
filters has been shown to be uniformly distributed across the filter. |3>
12
Another study has shown that when sampling near a roadway, strip position
contributes significantly to the overall variability associated with lead
analyses. Therefore, when sampling near a roadway, additional strips or discs she
be analyzed to minimize this variability.
7.2.1.2 Using vinyl gloves or plastic forceps, accordion fold or
tightly roll the filter strip and place on its edge in a 50-ml polypropylene
centrifuge tube. Add 12.0 ml of the extracting acid (Section 6.2.4) with
pipettes or the automatic dispensing pipette. The add should completely cover
the sample. Cap the tube loosely (finger tight) with the polypropylene screw top.
Caution; Centrifuge tubes must be loosely capped to prevent elevated pressures
during ultrasonication at elevated temperatures and will not withstand repeated
cycling to elevated pressures.
7.2.1.3 Label the centrifuge tube, place in a sample rack, and place
upright in the preheated (100°C) ultrasonic water bath (in fume hood) so that
the water level 1s slightly above the acid level in the centrifuge tubes but
7
E-42
-------
well below the centrifuge tube caps. This will prevent contamination of the
samples during ultrasonication. Ultrasonicate the sample at 100°C for 50
minutes.
7.2.1.4 Remove the centrifuge tube from the ultrasonic bath and allow
to cool.
7.2.1.5 Uncap the centrifuge tube in the fume hood and add 28.0 ml of
D.I. water with pipettes or the automatic dispensing pipette. Recap the tube
tightly, shake well, and centrifuge for 20 minutes at 2500 RPM.
7.2.1.6 Decant the extract into a clean polyethylene storage bottle
bearing the sample I.D. Be careful not to disturb any solids in the bottom of
the tube. Cap the bottle tightly and store until analysis. The final extract
is now in 0.31 M HN03 + 0.67 M HC1.
8. Analysis
8.1 Set the wavelength of the rconochromator at 283.3 or 217.0 nm.
Set or align other instrumental operating conditions as recommended by the manu-
facturer.
8.2 The sample can be analyzed directly from the polyethylene
storage bottle, or an appropriate amount of sample can be transferred to a sample
analysis tube.
8.3 Aspirate samples, calibration standards, and blanks (Section 9.2)
into the flame and record the equilibrium ebsorbance.
8.4 Determine the lead concentration in vg Pb/ml, from the calibration
curve, Section 9.3.
8.5 Samples that exceed the linear calibration range should be diluted
with acid of the same concentration (Section 6.2.5) as the calibration standards
and reanalyzed.
8
E-43
-------
9. Calibration
9.1 Working standard, 20 pg Pb/ml. Prepared by diluting 2.0 ml
of the master standard (Section 6.3.1) to 100 ml with add of the same con-
centration (Section 6.2.5} as used in preparing the master standard.
9.2 Calibration standards. Prepare daily by diluting the working
standard, with the same acid matrix, as Indicated below. Other lead concen-
trations may be used.
Volume of 20 yg/ml Final Concentration
Working Standard, ml Volume, ml yg Pb/ml
0 100 0.0
1.0 200 0.1
2.0 200 0.2
2.0 100 0.4
4.0 100 0.8
8.0 100 1.6
15.0 100 3.0
30.0 100 6.0
50.0 100 10.0
100.0 100 20.0
9.3 Preparation of calibration curve. Since the working range of
analysis will vary depending on which lead line 1s used and the type of Instrument,
no one set of Instructions for preparation of a calibration curve can be given.
Select standards (plus the reagent blank), In the same acid concentration as the
samples, to cover the linear absorption range Indicated by the instrument manu-
facturer. Measure the absorbance of the blank and standards as 1n Section 8.0.
Repeat until good agreement Is obtained between replicates. Plot absorbance
E-44
-------
(y-axis) versus concentration in pg Pb/ml (x-axis). Draw (or compute) a straight
line through the linear portion of the curve. Do not force the calibration curv*
through zero. Other calibration procedures may be used.
To determine stability of the calibration curve, remeasure - alternately -
one of the following calibration standards for every 10th sample analyzed: con-
centration Ł 1 vg Pb/ml; concentration Ł 10 vg Pb/ml. If either standard deviates
by more than 5 percent from the value predicted by the calibration curve, re-
calibrate and repeat the previous 10 analyses.
10. Calculation.
10.1 Measured air volume. Calculate the measured air volume at
standard temperature and pressure as described In reference 10.
10.2 Lead concentration. Calculate lead concentration in the air sample.
c « (pg Pb/ml x 40 ml/strip x n strips/filter) - Ffa
VSTP
where:
C • Concentration, yg Pb/sm.
ug Pb/ml « Lead concentration determined from Section 8.
40 ml/strip * Total sample volume.
n » 12 (for 3/4" x 8" strip) or 9 (for 1" x 8" strip) strips
per filter, or ^- for discs.
Ffa « Mean lead concentration of blank filter, vg, from
Section 6.1.1.2.3.
y-
STP « Air volume from 10.1.
10
E-45
-------
11. Quality Control
Glass-fiber filter strips (3/4" x 8" or 1" x 8") containing 80 to
2000 vg Pb/strip (as lead salts) and blank strips with zero Pb content should
be used to determine if the method • as being used - has any bias. Quality
control charts should be established to monitor differences between measured
and true values. The frequency of such checks will depend on the local
quality control program.
To minimize the possibility of generating unreliable data, the user
should follow practices established for assuring the quality of air pollution
data, and take part in EPA's semiannual audit program for lead analyses.
12. Trouble Shooting
1. The sample acid concentration should minimize corrosion of the
nebulizer. However, different nebulizers nay require lower acid concentrations.
Lower concentrations can be used provided samples and standards have the same
acid concentration.
2. Ashing of particulate samples has been found, by EPA and contractor
laboratories, to be unnecessary in lead analyses by atomic absorption. There-
fore, this step was omitted from the method.
13. References
1. Scott, D.R. et al. Atomic Absorption end Optical Emission Analysis
of NASN Atmospheric Particulate Samples for Lead. Environ.Sci.and
Tech.. 1Ł, 877-880 (1976).
11
E-46
-------
2. Skogerboe, R. K. ct al. Monitoring for Lead in the Environment.
pp. 57-66, Department of Chemistry, Colorado State University,
Fort Collins. Colorado 80523. Submitted' to National Science
Foundation for publication, 1976.
3. Zdrojewski, A. et al. The Accurate Measurement of Lead in Airborne
Particulates. Inter. J. Environ. Anal. Chem.t 2_, 63-77 (1972).
4. Slavin, U. Atomic Absorption Spectroscopy. Published by Inter-
science Company, New York, N.Y. (1958).
5. Kirkbright, G. F., and Sargent, M. Atomic Absorption and Fluorescence
Spectroscopy. Published by Academic Press, New York, N.Y. (1974).
6. Burnham, C. D. et al. Determination of Lead in Airborne Particulates
in Chicago and Cook County, Illinois by Atomic Absorption Spectroscopy.
Envir. Sci. and Tech.. 3., 472-475 (1969).
7. Proposed Recommended Practices for Atomic Absorption Spectrometry.
ASTM Book of Standards, Part 30, pp. 1596-1608 (July 1973).
8. Koirttyohann, S. R., and Wen, J. W. Critical Study of the APCD-MIBK
Extraction System for Atomic Absorption. Anal. Chem.. 45_, 1985-1989
(1973).
9. Collaborative Study of Reference Method for the Determination of
Suspended Particulates in the Atmosphere (High-Volume Method).
Obtainable from National Technical Information Service, Department of
Commerce, Port Royal Road, Springfield, Virginia 22151, as PB-205-891.
10. Reference Method for the Determination of Suspended Particulates in
the Atmosphere (High-Volume Method). Code of Federal Regulations,
Title 40, Part 50, Appendix B, pp. 12-16 (July 1, 1975).
12
E-47
-------
11. Dubois, L., et al. The Metal Content of Urban Air. JAPCA. 1Ł,
77-78 (1966).
12. EPA Report No. 600/4-77-034, June 1977. Los Angeles Catalyst Study
Symposium. Page 223.
13. Quality Assurance Handbook for Air Pollution Measurement Systems.
Volume 1 - Principles. EPA-600/9-76-005, March 1976.
14. Thompson, R. J. et al. 'Analysis of Selected Elements in Atmospheric
Particulate Hatter by Atomic Absorption. Atomic Absorption News-
letter, Ł, No. 3. (May-June 1970).
15. Long, S. J. et al. Lead Analysis of Ambient Air Participates: Inter-
laboratory Evaluation of EPA Reference Method. JAPCA, 29_, 28-31
(1979).
16. Quality Assurance Handbook for Air Pollution Measurement Systems.
Volume II - Ambient Air Specific Methods. EPA-600/4-77-027a, May 1977.
13
E-48
-------
!
--
-
MANILA TILE rotDEH - TO PREVENT
FILTER FROM STICKING TO PLASTIC
RIGID PLASTIC
CLASS HlfH Fill El •
rOlOCUtlCNGTIIWISmNllALF
Allenoovcs
ImmOCEP
VWOfll OF /
CROOVt I cm -X
Figure 1
-------
i
••'
c.
ISmm (XT
STmrsFon
OTHER ANALYSES
X-»I"STHIP FOR
LEAD ANALYSIS
Figure 2
-------
United Slates
Environmental Protection
Agency
Environmental Monitoring ana
Support Laboratory
Cincinnati OH 45268
Researcn and Development
vvEPA
Test Method
Inductively Coupled Plasma-
Atomic Emission Spectrometric
Method for Trace Element
Analysis of Water and
Wastes—Method 200.7
1. Scope and Application
1.1 This method may be used (or
the determination of dissolved.
suspended, or total elements in
drinking water, surface water.
domestic and industrial wastewaters
1.2 Dissolved elements are
determined in filtered and acidified
samples Appropriate steps must be
taken in all analyses to ensure that
potential interference are taken into
account This a especially true when
dissolved solids exceed 1500 mg/L
(See 5)
1.3 Total elements are determined
after appropriate digestion procedures
are performed Since digestion
techniques increase the dissolved
solids content of the samples.
appropriate sttps mutt be taken to
correct for potential interference
effects (Set 5)
1.4 Table 1 lists elements for which
this method applies along with
recommended wavelengths and
typical estimated instrumental
detection limits using conventional
pneumatic nebuluation Actual
working detection limits are sample
dependent and as the sample maun
varies, these concentrations may also
vary In time, other elements may be
0M Iff*
added as more information becomes
available and as required.
1.5 Because of the differences
between various makes and models of
satisfactory instruments, no detailed
instrumental operating instructions
can be provided Instead, the analyst
is referred to the instructions provided
by the manufacturer of the particular
instrument
2. Summary of Method
2.1 The method describes a
technique for the simultaneous or
sequential multielement
determination of trace elements in
solution. The basis of the method is
the measurement of atomic emission
by an optical spectroscopic technique
Sample* are nebulized and the
aerosol that is produced is transported
to the plasma torch where excitation
occurs. Characteristic atomic-line
emission spectra are produced by a
radio-frequency inductively coupled
plasma (ICP). The spectra are
dispersed by a grating spectrometer
and the intensities of the lines are
monitored by phoiomultiplier tubes.
The photocurrents from the
photomultiplier tubes are processed
and controlled by a computer system.
A background correction technique is
required to compensate for variable
background contribution to the
E-51
-------
determination of trace elements
Background must be measured
'taceni to anaiyte lines on samples
^unng analysis The position selected
for the background intensity
measurement, on either or both stdes
of (he analytical line, will be
determined by the complexity of the
spectrum adjacent to rne anaiyte line
The position used m.i-' be free of
spectral interference and reflect the
same change in background
intensity as occurs at the analyte
wavelength measured Background
correction is not required in cases of
line broadening where a background
correction measurement would
actually degrade the analytical result
The possibility of additional
interferences named in S 1 (and tests
for their presence as described in 52)
should also be recognized and
appropriate corrections made
3. Definitions
3.1 Dissolved — Those elements
which will pass through a 0.45 tim
membrane filter
3.2 Suspended — Those elements
which are retained by a 0 45 um
membrane filter.
Total — The concentration
determined on an unfiltered sample
following vigorous digestion (93). or
the sum of the dissolved plus
suspended concentrations (9 1 plus
921
3.4 Total recoverable — The
concentration determined on an
unfiitered sample following treatment
witn hot. dilute mineral acid (9 4)
3.5 Instrumental detection limit —
The concentration equivalent to a
signal, due to ihe analyte which is
equal to three times the standard
deviation of a series of ten replicate
measurements of a reagent blank
signal at the same wavelength
3.6 Sensitivity — The slope of the
analytical curve, le functional
relationship between emission
intensity and concentration
3.7 Instrument check standard — A
multielement standard of known
concentrations prepared by me
analyst to monitor and verify
instrument performance on a daily
ba«is (See 76 II
& ^f Interference check sample — A
solution containing both interfering
and analyte elements of known
concentration that can be used to
verify background and interelemeni
correction factors (See 762)
3.9 Quality control sample — A
solution obtained from an outside
source having known concentration
values to be used to verify the
calibration standards (See 763)
310 Calibration standards — a
series of know standard solutions
used by the analyst for calibration of
the instrument lie . preparation of the
analytical curve) (See 7 4)
3.11 Linear dynamic range — The
concentration range over which the
analytical curve remains linear
3.12 Reagent blank — A volume of
deiomzed. distilled water containing
the same acid matrix as the
calibration standards earned through
the enure analytical scheme (See
75.21
3 13 Calibration blank — A volume
of deiomzed. distilled water acidified
with HNOj and HCI (See 751)
3.14 Method of standard addition —
The standard addition technique
involves the use of the unknown and
the unknown plus a known amount of
standard (See 106 1)
4. Safety
4.1 The toxicity or carcmogenicity of
each reagent used m this method has
not been precisely defined however.
each chemical compound should be
treated as a potential health hazard
From this viewpoint, exposure to
these chemicals must be reduced to
the lowest possible level by whatever
means available The laboratory is
responsible for maintaining a current
awareness file of OSHA regulations
regarding the safe handling of the
chemicals specified m this method A
reference die of material daia
handling sheets should atso be made
available to all personnel involved in
the chemical analysis Additional
references 10 laboratory safety are
available and have been identified
(147. 14 8 and 14 9) for the
information of the analyst
5. Interferences
5.1 Several types of interference
effects may contribute to inaccuracies
in the determination of trace
elements. They can be summarized as
follows
5.1.1 Spectrel interferences can be
categorized as 1) overlap of a spectral
line from another element: 2l
On 19B2
unreso .T; overlap of molecular ftano
spectra 3 background contribution
from CC" - jous or recombination
phenorr— -a. and 4) background
contribution from stray light from me
line er- :• :i of high concentration
elemer.n "ne first of these effects
can be c:~ipensated by utilizing a
compute' correction of the raw data
requirinc ~e monitoring and
measure— ent of the interfering
element The second effect may
require selection of an alternate
wavelenpn The third and fourth
effects can usually be compensated by
a background correction adjacent to
the analyte line In addition, users of
simultaneous multielement
instrume— anon must assume the
responsis- *v of verifying the absence
of spect's -nterference ''om an
element —at could occur in a sample
but for M- ch there is no channel in
the insi'_-ent array Listed m Table 2
are som* -terference ejects for the
recomrr*-3ed wavelengths given in
Table 1 "•* data m Table 2 are
intended "' use only as a
rudiment*", guide for the indication of
potential siectral interferences For
this purpose, linear relations between
concentration and intensity for the
analytes and the mterferents can be
assumed
The interference information, which
was collected at the Ames Laboratory. '
is expressed at analyte concentration
eqivaients d e false analvte concen-
trations) arising from 100 mg L of the
interferent element The suggested use
of this information is as follows
Assume that arsenic (at 193 696 nmi
is to be determined m a sample
containing approximately 10 mg L of
aluminum According to Table 2. 100
mg L of aluminum would yield a false
signal for arsenic equivalent to
approximately 1 3 mg L Therefore
10 mg L of aluminum would result m
a false signal for arsenic equivalent to
approximately 0 1 3 mg L. The reader
is cautioned that other analytical
systems may exhibit somewhat
different levels of interference than
those shown in Table 2. and that the
interference effects must be evaluated
for each individual system
Only those mierferents listed were
investigated and the blank spaces m
Table 2 indicate that measurable inter •
ferences were not observed for the
interferent concentrations listed in
Table 3 Generally, interferences were
discernible if they produced peaks or
background shifts corresponding 10
of the peaks generated by the
Am"* town SOCn
USOOC low* Si«i» unwcmu
E-52
-------
analyte concentrations also listed m
Table 3
At present, information on the listed
silver and potassium wavelengths are
not available but it has been reported
that second order energy from the
magnesium 383 231 nrn wavelength
interferes with the listed potassium line
at 766491 nm
S.I.2 Physical interferences are
generally considered to be effects
associated with the sample nebuhza-
tion and transport processes Such
properties as change m viscosity and
surface tension can cause significant
inaccuracies especially m samples
which may contain high dissolved
solids and -or acid concentrations The
use of a peristaltic pump may lessen
these interferences If these types of
interferences are operative, they must
be reduced by dilution of the sample
and' or utilization of standard addition
techniques Another problem which
can occur from high dissolved solids
is salt buildup at the up of the
nebulizer This affects aersol flow-rate
causing instrumental drift. Wetting
the argon prior to nebuluation. the
use of a tip washer, or sample dilution
have been used to control this
problem Also, it has been reported
that better control of the argon flow
rate improves instrument
performance This is accomplished
with the use of mass flow controllers.
5.1.3 Chemical Interferences are
characterized by molecular compound
formation, lomzanon effects and
solute vaporization effects Normally
these effects are not pronounced with
the ICP technique, however, if
observed they can be minimized by
careful selection of operating
conditions (that is. incident power.
observation position, and so forth), by
buffering of the sample, by matrix
matching, and by standard addition
procedures These types of
interferences can be highly dependent
on matrix type and the specific
analyte element.
6.2 It is recommended that
whenever a new or unusual sample
matrix is encountered, a series of
tests be performed prior to reporting
concentration data for analyte
elements. These tests, as outlined in
5.2.1 through 5.2.4. will ensure the
analyst that neither positive nor
negative interference effects are
operative on any of the analyte el-
ements thereby distorting the
accuracy of the reported values.
5.2.1 Sena/ dilution—H the analyte
concentration it sufficiently high (min-
imally a factor ol 10 above the instru-
mental detection limit after dilution).
an analysis of a dilution should agree
within 5 % of the original determina-
tion (or within some acceptable con-
trol limit (14 3) that has been estab-
lished for that matrix) If not. a
chemical or physical interference ef-
fect should be suspected
5.2.2 Spike addition—The recovery
of a spike addition added at a
minimum level of 10X the in-
strumental detection limit (maximum
100X) to the original determination
should be recovered to within 90 to
110 percent or within the established
control limit for that matrix If not. a
matrix effect should be suspected The
use of a standard addition analysis
procedure can usually compensate for
this effect Caution The standard ad-
dition technique does not detect coin-
cident spectral overlap If suspected.
use of computerized compensation, an
alternate wavelength, or comparison
with an alternate method is recom-
mended (See 5 23)
5.2.3 Comparison with alternate
method ol analysis—When investi-
gating a new sample matrix, compari-
son tests may be performed with other
analytical techniques such as atomic
absorption spectrometry. or other
approved methodology
5.2.4 Wavelength scanning of
analyte line region—If the appropriate
equipment is available, wavelength
scanning can be performed to detect
potential spectral interferences
6. Apparatus
6.1 Inductively Coupled Plasma-
Atomic Emission Spectrometer.
6.1.1 Computer controlled atomic
emission spectrometer with background
correction.
6.1.2 Radiofrequency generator.
6.1.3 Argon gas supply, welding
grade or better.
6.2 Operating conditions — Because
of the differences between various
makes and models of satisfactory
instruments, no detailed operating
instructions can be provided Instead.
the analyst should follow the
instructions provided by the
manufacturer of the particular
instrument Sensitivity, instrumental
detection limit, precision, linear dy-
namic range, and interference effects
must be investigated and established
for each individual analyte line on that
particular instrument It is the
responsibility o< the analyst to verify
that the instrument configuration and
operating conditions used satisfy the
analytical requirements ana to
maintain quality control data
confirming instrument performance
and analytical results
7. Reagents and standards
7.1 Acids used in the preparation
of standards and for sample processing
must be ultra-high purity grade or
equivalent. Redistilled acids are
acceptable
7.1.1 Acetic acid, cone Isp gr 1 06)
7.7.2 Hydrochloric acid, cone (sp gr
1.191
7.1.3 Hydrochloric acid. (1»1) Add
500 ml cone. HCI Isp gr 1 19) to 400
ml deionized. distrilled water and
dilute to 1 liter
7.1.4 Nitric acid. cone, (sp gr 1 411
7.1. S Nitric acid. (1»1) Add 500 ml
cone HNOj (sp gr 1 41) to 400 ml
deionized. distilled water and dilute to
1 liter
7.2 Dionited. distilled water: Prepare
by passing distilled water through a
mixed bed of cation and anion ex-
change resins. Use deionized. distilled
water for the preparation of all
reagents, calibration standards and as
dilution water The purity of this water
must be equivalent to ASTM Type II
reagent water of Specification 01193
(146).
7.3 Standard stock solutions may be
purchased or prepared from ultra high
purity grade chemicals or metals All
salts must be dried for 1 h at 105°C
unless otherwise specified.
(CAUTION. Many metal salts are ex-
tremely toxic and may be fatal if swal-
lowed. Wash hands thoroughly after
handling.) Typical stock solution pre-
paration procedures follow:
7.3.1 Aluminum solution, stock. 1
mL * lOOpg Al: Dissolve 0.100 g of
aluminum metal in an acid mixture of 4
ml of (1*1) HCI and 1 ml of cone. HNOj
in a beaker. Warm gently to effect
solution. When solution is complete.
transfer quantitatively to a liter flask.
add an additional 10 ml of (1*1) HCI
and dilute to 1.000 ml with deionized.
distilled water.
7.3.2 Antimony solution stock. 1 ml
« 100 «ig Sb: Dissolve 0.2669 g K(SbO)
C«H«0» m deionized distilled water.
add 10 ml (1*1) HCI and dilute
to 1000 ml with deionized. distilled
water
Mtlilt-3
Dec 1982
E-53
-------
733 J'M-" i %ii/(/.''ii/' i/ncA 1 ir,L
100 i/u. As, Dissolve i> 1320 y of As-O
' m 100 ml of Oeioni/ed distilled waier
contammy 0 A g N.iOH Acidilv Hit-
solution with 2 mL cone HNOi and
(Miit? 10 1 000 ml with deionued
distilled watfr
734 Banunt solution stock 1 mL
• 100 ug Ba Dissolve 0 1516 g BaCl
(dried at 250 C (or 2 hrsi in 10 ml
deionized distilled water with 1 mL
(1 -11 HCI Add 10 0 mL 11 • 11 HCI
and dilute to 1.000 mL with deionized.
distilled water
7 3.5 Beryllium solution, stock. 1
mL : 100 ,ug Be Do not dry Dis-
solve 1 966 g BeSO< • 4 4H,0. in
deionized distilled water add 100 mL
cone HNOj and dilute to 1 000 mL
with deiomzed. distilled water
736 Boron solution stock 1 mL
- 100 ug B Do not dry Dissolve
0 5716 g anhydrous HiBO. m deiomzed
distilled water dilute to 1 000 mL
Use a reagent meeting ACS specifica-
tions, keep the bottle tightly stoppered
and store m a desiccator to prevent
the entrance of atmospheric moisture
7.3.7 Cadmium solution stock, 1
mL - 100 ug Cd Dissolve 0 1142 g
~ CdO m a minimum amount of 11 • 1)
HNOi Heat to increase rate o* dis-
solution Add 10 OmL cone HMO,
and dilute to 1.000 mL with deionized.
distilled water
738 Calcium solution stock. 1 mL
= 100 »g Ca Suspend 0 2498 g
CaCOi dried at 180-C for 1 h before
weighing in deionized. distilled water
and dissolve cautiously with a min-
imum amount of (1-11 HNOi Add
10 0 mL cone HNOj and dilute to
1.000 mL with deionized distilled
water
7.3.9 Chromium solution, stock. 1
mL : 100,vg Cr Dissolve 01923
g of CrOj m detomzed. distilled
water. When solution is complete.
acidify with 10 mL cone HNO-. and
dilute to 1.000 mL with deiomzed
distilled water
7.3.10 Cobalt solution, stock. 1
ml = 100 ug Co Dissolve 0 1000 g
of cobalt metal in a minimum amount
of <1»1)HNO.. Add 100 mL (1*11 HCI
and dilute to 1 000 mL with deionized.
distilled water
7.3.11 Cooper solution, stock. 1
~~-L - 100/jg Cu Dissolve 0 1252 g
.. xiO in a minimum amount of (I'D
HNOj Add 10 0 mL cone HNOi and
dilute to 1.000 mL with deionized.
distilled water
73 12 Imii illinium \: . i I 'i>L
!O()//yfM [}i*hiilvr U 1 ; ji) c|
F* -0 in A >/uarm mi>itni> c>i 20 mL
1 1 • 1 ) MCl .mil 2 nit .il cone HNO
Cool adrt an aorttnonHi 5 ml of rone
HNO .md rtilul" in 1000 mL iviiii
dPioni/ed disiilled wnirr
7313 Lead solution i/c/vA 1 mL
• 100 ug Pb Dissolve 0 1 b99 g
Pb(NOi) in minimum amount of
(1-1 1 HNO. AddlOOinLconc HNO.
and dilute to 1.000 mL with deioni/ed
distilled water
73.14 Magnesium solution, stuck. 1
mL - lOOjyg Mg Dissolve 0 1658 g
MgO m a minimum amount of 1 1 • 1 )
HNOi Add 10 OmL cone HNO .and
dilute to 1 000 mL with deionized
distilled water
7.3. 1 S Manganese solution, stock. 1
mL = 100 ug Mn Dissolve 0 1000 g
of manganese metal m me acid mm-
ture 10 mL cone HCI and 1 mL cone
HNOj. and dilute to 1 000 mL witn
deiomzed distilled water
73.16 Molybdenum solution stock.
1 mL = 100 ug Mo Dissolve 0 2043 g
iNHj),MoOj m deionized distilled
water and dilute to 1 000 mL
7.3.17 Nickel solution stock 1
mL - 100 ug Ni Dissolve 0 1000 y
of nickel metal m 10 ml hot cone
HNOr cool and dilute to 1 000 mL
with deionized. distilled
7318 Potassium snlution stock. 1
ml 100 ug K Dissolve 0 1907 g
KCl dried at 110 C. m deionized
distilled w.iter dilute to 1 000 mL
7319 Selenium solution, stock 1
mL - 100 ug Se Do not dty Dissolve
0 1727 g H,SeO . (actual assay 94 6"«l
m deionized distilled water and dilute
to 1.000ml
7.3.20 Silica solution, stuck. 1 mL
s 100 ug SiO» Do not dry Dissolve
0 4730 g Na*SiOj • 9H?O m deiomzed.
distilled water Add 10 0 mL cone
HNOj and dilute to 1.000 mL with
deionized. distilled water
7.3.21 Silver solution, stock. 1
mL - 100 ug Ag Dissolve 0 1575 g
AgNOi m 100 mL of deiomzed. dis-
tilled water and 10 mL cone HNOi
Dilute to 1.000 mL with deionized.
distilled water
7 3.22 Sodium solution, stock. 1
mL = 100 ug Na Dissolve 0 2542 g
NaCI in deiomzed. distilled water
Add 100 mL cone HNO. and dilute
to 1.000 mL with deiomzed. distilled
water
7 3 23 r/iattium solution stock 1
mt 100 pg Ti Dissolve 0 1303 g
TiNC m deiomzed distilled water
Add 10 0 ml cone HN05 and dilute
to 1 000 ml with deionized distilled
water
7 3.24 Vanadium solution stock 1
mL 100/yg V Dissolve 02297
NH«VOi m a minimum amount of
cone HNOi Heat to increase rate
of dissolution Add 10 0 mL cone
HNCh and dilute to 1.000 ml with
deionized distilled water
7 3.25 Zinc solution, stock. 1 mL
-• 100«/g Zn Dissolve 0 1245 g ZnO
in a minimum amount of dilute HNO)
Add 10 0 mL cone HNOi and dilute
to 1.000 ml with deiomzed. distilled
water
7.4 Mined calibration standard so
lutions—Prepare mixed calibration
standard solutions by combining ap-
propriate volumes of the stock solu-
tions m volumetric flasks (See 7 4 1
thru 745) Add 2 mL of (1 • 1)
HCI and dilute to 100 mL with
deiomzed distilled water (See Notes
1 and 6 I Prior to preparing the mixed
standards, each stock solution should
be analyzed separately to determine
possible spectral interference or the
presence of impurities Care should
be taken when preparing the mixed
standards that the elements are com-
patible and stable Transfer the mixed
standard solutions to a FEP fluoro-
carbon or unused polyethylene bottle
for storage Fresh mixed standards
should be prepared as needed with
the realization that concentration can
change on aging Calibration stand-
ards must be initially verified using
a quality control sample and moni-
tored weekly for stability (See 7 6 31
Although not specifically required.
some typical calibration standard com-
binations follow when using those
specific wavelengths listed in Table
1
7.4.1 Mined standard solution I—
Manganese beryllium, cadmium, lead.
and zmc
7.4.2 Mined standard solution II—
Barium, copper, iron, vanadium, and
cobalt
7.4.3 Mi ted standard solution III—
Molybdenum, silica, arsenic, and
selenium
7.4.4 Mned standard solution IV—
Calcium, sodium, potassium, alumi-
num, chromium and nickel
Dn if/82
Mntlt-4
E-54
-------
74.5 Mixed standard solution V—
Antimony, boron, magnesium, silver.
and thallium
NOTE 1 II the addition of silver
to the recommended acid combination
results m an initial precipitation.
add 15 mL of deiomzed distilled
water and warm the flask until the
solution clears Cool and dilute to 100
mL with deiomzed. distilled water For
this acid combination the silver con-
centration should be limned to 2
mg/L Silver under these conditions
is stable in a tap water matm
for 30 days Higher concentrations
of silver require additional HCI
7.5 Two types of blanks are required
for the analysis. The calibration blank
(3 13) is used m establishing the
analytical curve while the reagent
blank (3 12) is used to correct for
possible contamination resulting from
varying amounts of the acids used in
the sample processing
7.5.1 The calibration blank is pre-
pared by diluting 2 mL of (1 • 1) HNOj
and 10 mL of (1>1) HCI to 100 mL
with deiomzed. distilled water (See
Note 6 I Prepare a sufficient quantity
to be used to flush the system be-
tween standards and samples
7.5.2 The reagent blank must con-
contain all the reagents and m the
same volumes as used in the pro-
cessing of the samples The reagent
blank must be carried through the
complete procedure and contain the
same acid concentration in the final
solution as the sample solution
used for analysis
7.6 In addition to the calibration
standards, an instrument check stan-
dard (37). an interference check
sample (3 8) and a quality control
sample (39| are also required for the
analyses
7.6.1 The instrument cheek standard
is prepared by the analyst by com-
bining compatible elements at a con-
centration equivalent to the midpoint
of their respective calibration curves
(See 12.1.1)
7.6.2 The interference check sample
is prepared by the analyst in the
following manner. Select a
representative sample which contains
minimal concentrations of the
analytes of interest by known con-
centration of interfering elements that
will provide an adequate test of the
correction factors Spike the sample
with the elements of interest at the
approximate concentration of either
100 ny 'I or S times the estimated
detection limits given m Table 1 (for
effluent samples of expected high
concentrations, spike at an
appropriate level) If the type of
samples analyzed are varied, a
synthetically prepared sample may be
used if the above criteria and intent
are met A limited supply of a
synthetic interference check sample
will be available from the Quality
Assurance Branch of EMSL
Cincinnati (See 1212)
7.6.3 The quality control sample
should be prepared in the same acid
matrix as the calibration standards
at a concentration near 1 mg L and in
accordance with the instructions
provided by the supplier The Quality
Assurance Branch of EMSL-Cmcmnati
will either supply a quality control
sample or information where one of
equal quality can be procured (See
12 1 3)
8. Sample handling an
preservation
4
8.1 For the determination of trace
elements, contamination and loss are
of prime concern Oust in the labora-
tory environment, impurities in
reagents and impurities on laboratory
apparatus which the sample contacts
are all sources of potential
contamination Sample containers can
introduce either positive or negative
errors m the measurement of trace
elements by (a) contributing con-
taminants through leaching or surface
desorption and (b) by depleting
concentrations through adsorption
Thus the collection and treatment of
the sample prior to analysis requires
particular attention. Laboratory
glassware including the sample bottle
(whether polyethylene, polyproplyene
or FEP-fluorocarbon) should be
thoroughly washed with detergent
and tap water: rinsed with (1*1) nitric
acid, tap water. (1*1) hydrochloric
acid, tap ar.d finally deiomzed, distilled
water in that order (See Notes 2 and
3).
NOTE 2. Chromic acid may be useful to
remove organic deposits from glass-
ware: however, the analyst should be
be cautioned that the glassware must
be thoroughly rinsed with water to
remove the last traces of chromium
This is especially important if chromium
is 10 be included in the analytical
scheme A commercial product. NOCH-
ROMIX. available from Godax Labor-
atories. 6 Varick Si, New York. NY
10013. may be used in place of
chromic acid. Chom* acid should not
be used with plastic bottles
NOTE 3 If it can be documented through
Dee 1982
an active analytical quality control
program using spiked samples and re-
agent blanks, that certain steps in the
cleaning procedure are not required for
routine samples, those steps may be
eliminated from the procedure
8.2 Before collection of the sample a
decision must be made as to the type
of data desired, that is dissolved.
suspended or total, so that the appro-
priate preservation and pretreatmem
steps may be accomplished Filtration.
acid preservation, etc . are to be per-
formed at the time the sample is
collected or as soon as possible
thereafter
8.2.1 For the determination of dis-
solved elements the sample must be
filtered through a 0.45-j/m membrane
filter as soon as practical after collec-
tion (Glass or plastic filtering appara-
tus are recommended to avoid possi-
ble contamination ) Use the first 50-
100 mL to rinse the filter flask. Dis-
card this portion and collect the
required volume of filtrate. Acidify the
filtrate with (1*1) HNOj to a pH of 2
or less Normally. 3 mL of (1*1) acid
per liter should be sufficient to pre-
serve the sample
8.2.2 For the determination of sus-
pended elements a measured volume
of unpreserved sample must be fil-
tered through a 0 45-
-------
beaker with a watch glass and heat
gently The warn acid will soon dis
solve the membrane
Increase the temperature of the
hot plate and digest the m.itenal
When the acid has nearly itvaporated
cool the beaker and watch glass and
add another 3 mL of cone HNO-.
Cover and continue heating until the
digestion is complete, gent-rally indi-
cated by a light colored digestate
Evaporate to near dryness (2 mL). cool.
add 10 ml HCM1-1) and 15 mL
deionized. distilled water pur 100 mL
dilution and warm the beaker gently
for 15 mm to dissolve any precipi-
tated or residue material Allow to
cool wash down the watch glass and
beaker walls with deionized distilled
water and filter the sample to remove
insoluble material that could clog the
nebulizer (See Note 4.) Adjust the
volume based on the expec ed con-
centrations of elements present This
volume will vary depending on the
elements to be determined (See Note
6) The sample is now read" for
analysis Concentrations so determined
shall be reported as "suspended "
NOTE 4 In place of filtering, the
sample after diluting and mixing may
be centnfuged or allowed tc settle by
gravity overnight to remove insoluble
'•material
9.3 For the determination of total
elements, choose a measured, volume
of the well mixed acsd preserved
sample appropriate for the rxpected
level of elements and transfer to a
Griffin beaker (See Note 5.) Add 3 mL
of cone HNO) Place the beaker on
a hoi plate and evaporate to near dry-
ness cautiously, making ceram that
the sample does not boil anil that no
area of the bottom of the beaker is
allowed to go dry Cool the beaker and
add another 5 mL portion of cone
HNO 3 Cover the beaker with a watch
glass and return to the hot plate
Increase the temperature of the hot
plate so that a gentle reflux action
occurs Continue heating, adding addi-
tional acid as necessary, until the
digestion is complete (generally indi-
cated when the digestate is light
in color or does not change n appear-
ance with continued refluxirg) Again.
evaporate to near dryness and cool
the beaker. Add 10 mL of M HCI
and 15 mL of deionized. distilled
water per 100 mL of final sclution
and warm the beaker gently for 15
_mm to dissolve any precipiMte or
*'«sidue resulting from evapc ration
^tllow to cool, wash down the beaker
walls and watch glass with deionized
distilled water and filter the sample to
remove insoluble material that could
clog the nebuh/nr (See Note 4 i Adjust
the sample to a predetermined volume
based on the expected concentrations
of elements present The sample is
now ready for analysis (See Note 6>
Concentrations so determined shall be
reported as total
NOTE 5 If low dr terminal ions of
boron are critical, quaru glassware
should be use
NOTE 6 If the sample analysis solution
has a different acid concentration
from that given in 9 4. but does not
introduce a physical interference or
affect the analytical result, the same
calibration standards may be used
9.4 For the determination of total
recoverable elements, choose a mea-
sured volume of a well mixed, acid
preserved sample appropriate for the
expected level of elements and trans-
fer to a Gnffm beaker (See Note 5 )
Add 2 mL of (1-1) HNOi and 10 mL
of (1-1l HCI to the sample and heat
on a steam bath or hot piate until the
volume has been reduced to near 25
mL making certain the sample does
not bod After this treatment, cool
the sample and filter to remove inso-
luble material that could clog the
nebulizer (See Note 4 i Adjust the
volume to 100 mL and mix The sample
is now ready for analysis Concentra-
tions so determined shall be reported
as 'total "
10. Procedure
10.1 Set up instrument with proper
operating parameters established in
62 The instrument must be allowed
to become thermally stable before be-
ginning This usually requires at least
30 mm of operation prior to calibra-
tion
10.2 Initiate appropriate operating
configuration of computer
10.3 Profile and calibrate instru-
ment according to instrument
manufacturer's recommended
procedures, using the typcal mixed
calibration standard solutions
described in 7 4 Flush the system
with th« calibration blank (751)
between each standard (See Note 7 )
(The use of the average intensity of
multiple exposures for both
standardization and sample analysis
has been found to reduce random
error)
NOTE 7 For boron concentrations
greater than 500 pg L extended flush
times of 1 to 2 mm may be required
10.4 Before beginning the sample
run. reanalyze the highest mixed
calibration standard as if n were a
D»e 1962
Concentration values ootamed
not deviate from the actual
values !>v more than - 5 percent
IP- the established control limits
wi
-------
3 The interference effect must be
constant over the working range of
concern
4 The signal must be corrected for
any additive interference
11. Calculation
11.1 Reagent blanks (7 5.2) should
be subtracted from all samples. This is
particularly important tor digested
samples requiring large quantities of
acids to complete the digestion.
11.2 If dilutions were performed.
the appropriate factor must be applied
to sample values
11.3 Data should be rounded to the
thousandth place and all results
should be reported in mg L up to
three significant figures
12. Quality Control
(Instrumental)
12.1 Check the instrument
standardization by analyzing
appropriate quality control check
standards as follow
12. f. 1 Analyze an appropriate
instrument check standard (761)
containing the elements of interest at
a frequency of 10% This check
standard is used to determine
instrument drift If agreement is not
within =5% of the expected values or
within the established control limits.
whichever is lower, the analysis is out
of control The analysis should be
terminated, the problem corrected.
and the instrument recalibrated
Analyze the calibration blank (751)
at a frequency of 10% The result
should be within the established
control limits of two standard devia-
tions of the mean value. If not. repeat
the analysis two more times and
average the three results. If the
average is not within the control limit.
terminate the analysis, correct the
problem and recalibrate the
instrument.
12.1.2 To verify interelement and
background correction factors analyze
the interference check sample (7.6.2)
•t the beginning, end. and at periodic
intervals throughout the sample run.
Results should fall within the
established control limits of 1.5 times
the standard deviation of the mean
value. If not. terminate the analysis.
correct the problem and recalibrate
the instrument.
12.1.3 A quality control sample
(7.6.3) obtained from an outside
source must first be used for the
initial verification of the calibration
standards A fresh dilution of this
sample shall be aniayzed every week
thereafter to monitor their stability If
the results are not withm =5% of the
true value listed for the control
sample, prepare a new calibration
standard and recalibrate the
instrument If this does not correct the
problem, prepare a new stock
standard and a new calibration
standard and repeat the calibration
Precision and Accuracy
13.1 In an EPA round robin phase 1
study, seven laboratories applied the
ICP technique to acid-distilled water
matrices that had been dosed with
various metal concentrates. Table 4
lists the true value, the mean reported
value and the mean % relative
standard deviation
References
1 Wmge. R.K.. V J Peterson, and
V A Fassel. "Inductively Coupled
Plasma-Atomic Emission
Spectroscopy Prominent Lines." EPA-
600/4.79-017
2 Wmefordner. J 0.. 'Trace
Analysis Spectroscopic Methods for
Elements." Chemical Analysis. Vol.
46. pp 41-42
3 Handbook for Analytical Quality
Control in Water and Wastewater
Laboratories. EPA-600/4-79-019
4 Garbanno. J R and Taylor. HE..
"An Inductively-Coupled Plasma
Atomic Emission Spectrometnc
Method for Routine Water Quality
Testing," Applied Spectroscopy 33.
No 3(1979)
5. "Methods for Chemical Analysis of
Water and Wastes." EPA-600/4-79-
020.
6. Annual Book of ASTM Standards.
Pan 31.
7. "Carcinogens • Working With
Carcinogens." Department of Health.
Education, and Welfare. Public Health
Service. Center for Disease Control.
National Institute for Occupational
Safety and Health. Publication No. 77-
206. Aug. 1977.
8. "OSHA Safety and Health Stan-
dards. General Industry." (29 CFR
1910). Occupational Safety and Health
Administration. OSHA 2206. (Revised.
January 1976)
9. "Safety in Academic Chemistry
Laboratories. American Chemical So-
ciety Publication. Committee on
Chemical Safety. 3rd Edition. 1979.
Mnnt'7
Due. 1982
E-57
-------
Table 1. Recommended Wavelengths ' and Estimated Instrumental
Detection Limns
Element
Aluminum
Arsenic
Antimony
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Selenium
Silica (SiOt/
Silver
Sodium
Thallium
Vanadium
Zinc
Wavelength, nm
308215
193696
206 833
455 403
313.042
249 773
226502
317933
267716
228.616
324754
259.940
220353
279079
257670
202.030
231604
766491
196.026
288.158
328068
588.995
190864
292.402
213.856
Estimated detection
limit. iig/L1
45
S3
32
2
0.3
5
4
10
7
7
6
7
42
30
2
a
15
see1
75
55
7
29
40
8
2
' The wavelengths listed are recommended because of their sensitivity and
overall acceptance. Other wavelengths may be substituted if they can
provide the needed sensitivity and are treated with the same corrective
techniques for spectral interference (See 5.1. tj.
'The estimated instrumental detection limits as shown are taken from
"Inductively Coupled Plasma-Atomic Emission Spectroscopy-Prommant
Lines. "EPA-600/4-79-017. They are given as a guide tor an instrumental
limn The actual method detection limits are sample dependent and may vary
as the sample main* varies
^Highly dependent on operating conditions and plasma position
Dec 1982 Mtitlt-t
E-58
-------
INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION
ANALYSIS OF DRINKING WATER
APPENDIX TO METHOD 200.7
"Inductively Coupled Plasma Atomic Emission Spectrometric
Method for Trace Element Analysis of Water and Wastes"
Theodore 0. Martin, Eleanor R. Martin
and Gerald 0. McKee
Physical and Chemical Methods Branch
Environmental Monitoring and Support Laboratory
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
CINCINNATI, OHIO 45268
SEPTEMBER 1985
E-59
-------
Acknowledgements
The authors gratefully acknowledge Paul W. Britton r* the Quality
Assurance Branch, Environmental Monitoring and Support ^asoratory -
Cincinnati for his guidance and assistance in the statistical Interpretation
of the data presented, and William H. McDaniel, U.S. Environmental
Protection Agency, Region 4, Gerald L. McKinney, U.S. Environmental
Protection Agency, Region 7, Nancy S. Ulmer, U.S. Environmental Protection
Agency, Water Engineering Research Laboratory, Thomas C. Trible, Department
Environmental Conservation, State of Alaska and John F. Kopp, Esq. for their
technical and edUorial comments.
E-60
-------
1. Scoae and Application
1.1 This procedure is designed to be a supplement to Method 200.7 (1)
and is to be used in processing drinking water supply samples prior
to inductively coupled plasma-atomic emission spcctrometric
(1CP-AES) analysis. This appendix does not super-cede Method 200.7,
but provides elaboration on the analysis of drinking water using
Method 200.7. For a listing of the recommended wavelengths,
Definitions, and discussions on Safety, Reagents and Standards, and
Sample Handling and Preservation see the appropriate Sections of
Method 200.7.
1.2 This procedure is to be used for the total element determination of
primary and secondary elemental drinking water contaminants
included In Method 200.7. It is only to be used for compliance
monitoring when the determined method detection limit (HDL) (2) for
a particular contaminant is no greater than 1/5 its respective
maximum contaminant level (MCI) concentration. For these reasons,
mercury, and selenium have been omitted from th-i* artst-inn nf the
appendix^ A listing of the contaminants for which the procedure is
applicable along with their MCLs and MOLs is given as Table 1.
1.3 This procedure is to be used in al/pneunflticnfrbulization 1CP
analyses for compliance monitoring 6T~dr'nking water, and is
recommended for the analysis of ground and surface water where
determination at the drinking water MCL Is requested.
1.4 This procedure also can be used to determine the concentration of
calcium (Ca) for calculating corrosivity and for the required
monitoring of sodium (Na). Since these two elements can occur in
waters at concentrations greater than 25 mg/L, particular care must
be taken that concentrating the sample does not cause the analysis
of these two elements to exceed the calibration limit of
linearity. If standardization of the instrument does not include
provision for non-linear calibration, a more convenient and
allowable determination of these two elements 1s the direct
aspiration analysis of the acidified unprocessed sample.
2. Summary of Method
2.1 For a description of the analytical technique and method summary
see Section 2 of Method 200.7.
2.2 Analytical Discussion
2.2.1 The analysis of drinking water for elemental contaminants
requires that a "total* element determination be made.
Irrespective of the valence state or chemical species, the
term "total" refers to the sum of the elemental
concentration In the dissolved and suspended fractions of
the sample. The sample Is not filtered, but Immediately
preserved with nitric acid to pH of less than 2 at the time
of collection.
-1-
E-61
-------
2.2.2 Although most finished drinking waters are free of suspended
matter, aT samples must be subjected to a pretreatment acid
dissolution to solubilize that portion of the contaminant
that may be occluded or adhering to minute suspended
matter. This is especially true for-water supplies that
receive only chlorination pretreatment. Once solubilized,
the energy of the plasma is sufficient that all species in
the nebulized droplets are desolvated, dissociated and
raised to an energetic excited state for atomic emission
spectrometric analysis.
2.2.3 Method 200.7 describes two acceptable sample preparation
procedures for "total" element analyses. One is a vigorous
nitric acid digestion (Section 9.3), while the other is a
total recoverable acid solubilization procedure (Sectio-.
9.4). These procedures are essentially the sarr.e as those
used for flame atomic absorption analysis, except the final
acid concentration has been changed to match the ICP
calibration standards. The total recoverable procedure is
preferred for drinking water analyses because there is less
chance of losses from volatilization, the formation of
insoluble oxides or occlusion in precipitated silicates.
2.2.4 Data that are to be used for compliance monitoring should Jc
reported with a known estimate of uncertainty. The
uncertainty of the analysis should be determined at the
critical MCL concentration and should be a precision of
small enough variance to determine that the contaminant is
either in-or-out of compliance. A guide for evaluating oata
to be reported can be described as data with sufficient
precision at the MCL, that when two standard deviations are
either added to or subtracted from the K.CL concentration,
the value is not changed by more than 10*. An example is As
(MCL • 0.05 mg/L) where data reported with a precision of
two standard deviations equal to less than 0.005 mg/L would
be acceptable as shown in the preconcentration data of
Table 2 with the interval values of 0.048 to 0.052 mg/L.
2.2.5 As indicated in Table 1, the MCLs for As and Pb are close to
their estimated Instrumental detection limits. A single
analysis of these two elements using the total recoverable
procedure 9.4 of Method 200.7 lacks the precision needed for
compliance monitoring at their respective MCLs. As a
consequence inaccurate determinations can result. Only with
repeated analyses of the sample can an average value with
acceptable precision be determined. The number of analyses
required can be specified by the following equation:
-2-
P-62
-------
where: n • the number of replicate analyses required,
Sa • the determined standard deviation of a single
observation, and
Sx • the standard deviation deemed acceptable around
the mean value for n determinations.
Using the preceding equation the number of repeated analyses
required for the procedure 9.4 can be calculated from the
direct analysis standard deviation data given in Table 2.
For each element the listed determined standard deviation is
Sa and the acceptable standard deviation is Sx. From the
calculation the number (n) of repeated analyses required for
As is 8, while for Pb the number is 6. (Note: From the
standard deviation data listed for analysis after 4X
concentration, the number for both elements is 1.)
i
2.2.6 The drinking water procedure that follows (5.1) is a
modification of the total recoverable procedure 9.4 Method
200.7 that provides for Improved precision and accuracy by
concentrating the contaminants 4X prior to ICP analysis.
With preconcentration the determination is made on a more
reliable portion of the calibration curve. Also, since the
variability over the narrow concentration range in question
is nearly constant and does not change significantly by
concentrating the sample 4X, the precision of the
determination improves when the concentrated value is
divided by 4 to calculate the analyte concentration in the
original sample. Table 2 gives a comparison of precision
and accuracy for the two elements As and Pb as determined by
direct analysis and after preconcentration. The data for
the direct analysis were determined from seven replicate
analyses of a single unconcentrated aliquot while the
preconcentration data were determined from the analysis of
seven aliquots after preparation using the procedure
described In 5.1. The percent recovery range data are the
spread of the average percent recoveries from the seven
replicate analyses determined on four separate days. The
mean value is the average of the spread. The listed
standard deviation 1s from the set of replicate analyses
having the greatest variance.
3. INTERFERENCES
3.1 Concentration of surface, ground and drinking water supply samples
can produce slight spectral and matrix interferences in ICP
analysis. Reported effects have not been severe with the^pectral
-3-
E-63
-------
interference being an elevated shift in background intensity, while
the matrix interference causes the signal intensity of some
analytes to be reduced. In both cases the alkaline earth elements,
calcium (Ca) and magnesium (Mg), are the primary interferents. For
a complete description of interferences affecting ICP analysis see
Section 5 of Method 200.7.
3.2 Spectral Interference
3.2.1 The technique of "off-the-line background correction
adjacent to the wavelength peak," as required in Method
200.7, is usually adequate to compensate for shifts in
background intensity. To test the spectral location
selected for background correction, analyze analytically
pure, single element Ca and Mg solutions of high
concentration (>500 mg/L} and compare the data to the
instrumental detection limit from acid blank
determinations. If a value falls outside a confidence
interval of *2 standard deviations around the instrumental
detection limit, the wavelength should be spectrally scanned
for selection of a different background location. If it is
not feasible to change the background correction location,
an interelement correction factor can sometimes be used. An
example is the effect of Ca on the recommended wavelength
for Pb (220.353 nm). A non-uniform background shift occurs
on the low side of the wavelength peak; however, the
location is not changed because of a possible severe
spectral interference from Al on the high side of the
wavelength peak. For the situation described only a very
small correction factor (-0.00002) is required for the
EMSL-Cincinnati instrument. When using Interelement
correction for this purpose, the correction should not be
completed when the determined interferent concentration
deviates from linearity by more than 10? or unless the
equation used in standardization Includes terms for
non-linear calibration.
3.2.2 Although no significant Interelement spectral line
interferences have been reported from the alkali and
alkaline-earth elements on the wavelengths specified for the
contaminants listed In Table 1, the EKSL-Cincinnat1
Instrument does experience a weak Mg interference at
0.037 nm below the recommended Zn wavelength (213.856 nm)
read in the second order. To avoid a possible Mg spectral
Interference, background Intensity should be read on the
high side of the Zn wavelength peak. Another possible
spectral Interferent whose effect should be deteruined Is
that of Al on the recommended wavelengths for As. Kn and
Pb. Also, care must be taken that spectrally Interfering
elements are not Mixed 1n the same calibration standard
unless the computer program provides for their correction
during standardization.
E-64
-------
3.3 Matrix Interference
3.3.1 As the dissolved solids in the solution to be nebulized
increase to exceed a concentration of 1500 mg/L, a
suppressive effect on the analyte signal can occur. The
most noticeable effect has been observed on certain analytes
where a characteristic ion line is the preferred wavelengtn
for the analysis. To determine the presence of a
suppressive interference because of concentrating the
matrix, a second aliquot of the sample should be spiked with
each element to a concentration above 10X its determined MD,.
(but not to exceed its MCL), concentrated and analyzed.
Recoveries outside the interval of 901 to 1101 of the
expected value can be used to indicate the presence of a
matrix interference.
3.3.2 At EMSL-Cincinnati, using a fixed crossflow nebulizer with
the instrument conditions given in Section 4.2, it has been
observed that high concentrations of Ca (>400 mg/L) can
cause a 5% suppressive effect on the emision signal of
certain analytes; Cd and Pb experience the greatest
suppression. As the concentration of Ca increases, its
suppressive effect becomes more pronounced. Also, Mg has an
additive suppressive effect on Pb, and this combined effect
must be recognized when considering matrix interferences.
3.3.3 When the concentration of a primary contaminant 1s
determined to be within 10% of Us MCL or above, and the Ca
concentration exceeds 400 mg/L (100 mg/L in the original
sample concentrated 4X) or the combined Mg and Ca
concentration equals 500 mg/L, a matrix matched calibration
standard must be used. Otherwise the sample should be
analyzed by the standard addition technique (see Section
10.6 of Method 200.7).
4. APPARATUS
4.1 In addition to the minimum requirements listed in Section 6 of
Method 200.7, the use of mass flow controllers to regulate the
argon flow rates, especially through the nebulizer, provide more
exacting control and reproducible plasma conditions. Their use is
highly recommended, but not required.
4.2 Operating conditions — Because of differences between various
makes and models of satisfactory Instruments, no detailed operating
instructions can be provided. However, the following Instrument
conditions were used In conjunction with a fixed crossflow
nebulizer In developing the analytical data contained 1n this
appendix:
-5-
E-65
-------
Qpgr aiju.t: Coi'.r "i I ' un»
rcr.vi-H rf co*!:r (~"" 1100
kef'tccteri r* po» ?r iV; < 5 waits
wt'rk coil ?5 me
Ar«r: sur;*1; Liquid Argon
Arcon pressure 40 pr-i .'
Coolant arvun flew rite 19 L ml:L.~l
Aerosol ci.Titr aryor
flow r;it« 630 cc nsin-1
Aunlliary {plasma)
o-non flcn rate 300 cc min-1
San.vie uptake rate
•-•strolled to 1.2 nl min-1
5 . SAW. C PR[°-..>A'nj'l
.1 TraOii'e- a 200 «>L aliquc-t O'T a »g/L Au per 50 ml sample) to each sample after
dissolution, but befcre final dilution. If the analyzed Au
value is net within *&S of the true value, either the
nebulizer or torch has become partially clogged or a
suppresslve nai-ix effect has occurred. An analysis of the
instrument check standard will Indicate If shutdown end
cleaning Is required. (Note: EMSL-Cii.cinnati has been able
to use the *hign surge" argon flow when the nass flow
controller 1s first opened', to flush clean the argon port of
the nebulizer. This purging Is usually done during the
print-out of analytical c'ata and his proven in almost ill
'nsttnces to restore calibration drift back to
calibration.)
-6-
E-66
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OOLD-VAPOR ATOMIC ABSORPTION SPECTROMETRY (3112)
3-29
3112 B. Cold-Vapor Atomic Absorption
Spectrometric Method
1. General Discussion
This method i: spplicable to the deter-
mination of mercury.
2. Apparatus
a. Atomic absorption spectrometer and as-
sociated equipment: See Section 3111 A.6.
Instruments and accessories specifically de-
signed Tor measurement of mercury by the
cold vapor technique are available com*
nercially and may be substituted.
b. Absorption all a flats or plastic tube
approximately 2.S cm in diameter. An
11.4-cm-long tube has been found satisfac-
tory but a 15-cnvlonf tube is preferred.
Grind tube ends perpendicular to the lon-
gitudinal axis and cement quartz windows
in place. Attach fas inlet and outlet ports
(6.4 mm diam) 1.3 cm from each end.
e. Cell support: Strap cell to the flat ni-
trous-oxide burner head or other suitable
support and align in light beam to give
maximum transmittance.
d. Air pumps: Use any peristaltic pump
with electronic speed control capable of
delivering 2 L air/min. Any other regu-
lated compressed air system or air cylinder
also b satisfactory.
e. Flowmeter. capable of measuring an
air flow of 2 L/min.
/ Aeration tubing, a straight glass frit
having a coarse porosity for use in reaction
g. Reaction flask. 250-mL erleiuneyer
flask or a BOD bottle, fitted with a rubber
stopper to hold aeration tube.
n, Drying tube. 150-mra X IS-mm-diam,
Containing 20 g Mg (GO.),. A 60-W light
ulb with a suitable shade may be substi-
tuted to prevent condensation of moisture
inside the absorption cell. Position bulb to
maintain cell temperature at IO*C above
ambient.
L Connecting tubing, glass tubing to pass
mercury vapor from reaction flask to ab-
sorption cell and to interconnect all other
components. Gear vinyl plastic* tubing
may be substituted for glass.
3. Reaoentst
a. Metal-free water: See 3111B.3c.
b. Stock mercury solution: Dissolve 1.354
g mercuric chloride, HgG,, in about 700
mL water, add 10 ml cone HNO,. and
dilute to 1000 mL with water, 1.00 mL •
1.00 mg Hg.
e. Standard mercury solutions: Prepare a
series of standard mercury solutions con-
taining 0 to 5 jig/L by appropriate dilution
of stock mercury solution with water con-
taining 10 mL cone HNO/L. Prepare
standards daily.
d. Nitric acid. HNO), cone.
e. Potassium permanganate solution: Dis-
solve SO g KMnO. in water and dilute to
I L
/ Potassium pemlfate solution: Dissolve
SO g K&O, in water and dilute to 1 L.
g. Sodium chloride-hydroxylamine tut-
fait solution: Dissolve 120 g NaCI and 120
g (NH,OHVH,SO4 «n w»«« and dilute to
1 L. A 10% hydroxylamine hydrochloride
solution may be substituted for the hy-
droxylamine suUate.
h. Stannous chloride solution: Dissolve
100 g SnCI, in water containing 200 mL
cone HO and dilute to 1 L On aging, this
• Tjrfoi or
t Uw tpKiilly pnpsnd rnfnts to* M
-------
3-30
METALS (3000)
» MM «K Mg,}l vim*
t GUu kie*
-------
COLO-VAPOR ATOMIC ABSORPTION SPECTROMETRY (3112)
TABLE 3112:1. INTE«LAM*ATO«Y PRECISION AND BIAS
or COLO-VAFOB ATOMIC Aa*o«moN SPECTBOMETRIC METHOD FOR MEBCU«Y'
3-31
Focn
Inorganic
Inorganic
Organic
Cone.
M/L
0.34
4.2
4.2
SD
MI/L
0.077
0.36
0.36
Relative
SD
*
22.6
13.3
16
Relative
Error
%
21.0
144
1.4
No. of
Participants
23
21
21
6. Precision and Bias
DiU on interltboritory precision and
bias for this method are given in Table
3112:1.
7. Reference
. Korr, J.F, M.C. LoNoaoTTOM A UB. Lo-
BUNG. 1972. "Cold vapor- method for deter-
mining mercury. / Amir. Waitr Works Aaac.
64 JO.
B. Bibliography
HATCH. W.R. A W.L. Orr. 1961. Oeiermination
of Mibmieroinm quantities of mercury by
atomic tbsorpoon ipectrophotometry. Anal
Chtm. 40:201$.
UTHE. J.F.. F.AJ. AiMfraow; It M.P. STAIN-
TON. 1970. Mercury deicrmirutioe in Ash
umpla by wet dilation and (Umeles atomic
ttaorption spwtropbotoenciry. / /u*. Mti
toe* CM. 27:IOJ.
FUOMAN, C 1974. PrcMrvatkM of diluu mer-
cury solutions. Ami Ottm. 4649.
BOTHNUU M.H. * D.E. RoacanoN. 1975. Mer-
cury contamination of sea water samples
stored in polyethylene containers. Anal
Cktm. 47:392.
HAWLEY. J.E. A J.D. INGLE. Ja. 1973. Improve-
ments in cold vapor atomic absorption deter-
mination of mercury. AnaL Ctitm 47:719.
Lo. J.M. A CM. WAL. 1973. Mercury loss from
water during storage: Mechanisms and pre-
vention. Anal. Oirm. 47:1169.
EL-AWADY. A.A.. R.B. MILLEB A MJ. CA*TE»
1976. Automated method for the determi-
nation of total and inorganic mercury in water
and wasiewater samples. AnaL Chtm. 48:110.
OOA. C.E. A J.D. INGLE, JR. 1911. Speciation of
mercury by cold vapor atomic absorption
spectrometry with selective reduction. AnaL
CluiiL 33:2303
SUDDENDORF. R.F. 1911. Interference by selen.
ium or tellurium in the determination of mer-
cury by cold vapor generation atomic
absorption spectrometry. AnaL Cktm.
33:2234.
HEIOEN.R.W A DA AIKENS. 1913. Humicacid
as a preservative for trace mercury (II) so-
lutions stored in polyolefin container!. AnaL
Cktm. 53:2327.
CHOI). H.N. A CA. NALEWAY. I9M. Detenni-
nation of mercury by cold vapor atomic ab-
sorption spectrometry. AnaL CMtm. 56:1737.
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