vvEPA
-United States
lEnvbonnwntal Protection
Agency
Office Of
The Administrator
(A101F)
EPA 171-R-92-013
PB-92-182385
Jury 1992
Inventory Of Organic
And Metal Contamination
In-
Massachusetts Bay,
Cape Cod Bay,
And Boston Harbor
Sediments;
And An Assessment Of
Regional Sediment Quality
Printed on Recycled Pap6f
-------
DISCLAIMER
This report was furnished to the U.S. Environmental Protection
Agency by the student identified on the cover page, under a National
Network for Environmental Management Studies fellowship.
The contents are essentially as received from the author. The
opinions, findings, and conclusions expressed are those of the author
and not necessarily those of the U.S. Environmental Protection
Agency. Mention, if any, of company, process, or product names is
not to be considered as an endorsement by the U.S. Environmental
Protection Agency.
-------
AN INVENTORY OF ORGANIC AND METAL CONTAMINATION IN
MASSACHUSETTS BAY, CAPE COD BAY, AND BOSTON HARBOR SEDIMENTS
AND ASSESSMENT OF REGIONAL SEDIMENT QUALITY
Jeanne Cahill
and
Karen Imbalzano
National Network of Environmental Management Studies Interns
Environmental Protection Agency Region 1
Water Management Division
Massachusetts Bays Program
Final Report
December, 1991
Address correspondence to:
Jeanne Cahill or Karen Imbalzano
Environmental Sciences Program
University of Massachusetts-Boston
Harbor Campus
Boston, MA 02125
(617) 287-7440
Matthew Liebman
EPA Region 1
JFK Federal Building
(WOE)
Boston, MA 02203
(617) 565-4866
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
-------
TABLE OF CONTENTS
Acknowledgements
List of Tables ' '
List of Figures 'm
Abstract
Introduction
••••••......,. ••,«»,». ••••••••••••••••••••«««.....„..„tB-BB>
-------
ACKNOWLEDGEMENTS
We thank Matthew Liebman for his support, suggestions, and comments
throughout the duration of this project. In addition, valuable dialogue and
suggestions were made by Beverley Baker, Kymberlee Keckler and Dave
Toomey at EPA Region 1; David Hansen from EPA-Narragansett; Jack
Hathaway and Frank Manheim at USGS in Woods Hole, MA; and Dillon Scott
at MA Coastal Zone Management. Data was generously provided by John
Cardin, Ken Perez, and Rich Pruell, EPA-Narragansett; Joseph Cooney,
Gordon Wallace, and Mike Shiaris, UMASS/Boston; Susan Curran and Wendy
Smith, MWRA; Terry Fleming, U.S. Army Corps of Engineers; Tom
Gulbranson, Battelle; Steve Halterman, MA DEP; Kymberlee Keckler and
Dave Toomey, EPA Region 1; Donald MacDonald, NOAA; Kevin McManus,
Metcalf and Eddy; and Judy Pederson, MA CZM. Computer support for this
project was provided by the Information Management Branch-EPA, Region
1 and we would like to specially thank Greg Charest, Pat Ausman and
Marcie Berbrick. Lastly, this project was supported by the EPA-National
Network for Environmental Management Studies and the Massachusetts
Bays Program.
-------
LIST OF TABLES
Table 1. Summary of existing and proposed sediment quality criteria.
Table 2. Summary of data sources compiled in the Excel database and
used for the GIS analysis.
Table 3. SQC exceedences determined by database screening.
LIST OF FIGURES
Figure 1 Boston Harbor, Massachusetts Bay, and Cape Cod Bay with
sampling sites indicated.
Figure 2. Geographical Distribution of Copper with SQC violations
indicated.
Figure 3. Geographical Distribution of Mercury with SQC violations
indicated.
Figure 4. Geographical Distribution of total PCBs normalized to %TOC
with SQC violations indicated.
Figure 5. Geographical Distribution of Phenanthrene normalized to %TOC
with SQC violations indicated.
Figure 6. Geographical Distribution of Benzo[a]pyrene normalized to
%TOC with SQC violations indicated.
-------
ABSTRACT
Records of organic and.metal contamination in Boston Harbor,
Massachusetts Bay, and Cape Cod Bay (Massachusetts Bays) were obtained
from reports by the U.S. Army Corps of Engineers (ACOE), National Oceanic
and Atmospheric Administration (NOAA), Massachusetts Water Resources
Authority (MWRA), U.S. Environmental Protection Agency (EPA), other state
agencies, private consulting firms, and independent researchers, and
compiled into a Microsoft Excel database. Sediment contaminant levels in
the Massachusetts Bays region were compared to Sediment Quality
Criteria (SQC) compiled from Massachusetts state regulations, Washington
state standards, and EPA interim criteria. The degree and regional extent
of sediment contamination with copper (Cu), mercury (Hg), total
polychlorinated biphenyls (PCBs), phenanthrene, and benzo[a]pyrene were
analyzed using a Geographical Information System (GIS). Graphical
presentation of the distributions of selected contaminants and comparison
with their criteria values has shown nearshore coastal exceedences of
SQC by the two metals in Boston Inner Harbor, Dorchester Bay, and Salem
Harbor, as well as in Hull Bay and Cohasset for mercury. Copper also
exceeded SQC at the Massachusetts Bay Disposal Site (MBDS). The organic
contaminants were found at concentrations greater than SQC in both
nearshore and offshore areas including Boston Inner Harbor, Dorchester
Bay, at the planned MWRA outfall site, and at the MBDS.
-------
INTRODUCTION
Description of Study Site
Boston Harbor is severely impacted by anthropogenic sources of
contaminants, including sewage and industrial effluents, sewage sludge
combined sewer overflows (CSOs) and storm drains. Massachusetts Bay'
and Cape Cod Bay. receive contaminant loading from Boston Harbor sources
as well as from the Merrimack River, coastal municipal treatment plants '
and effluent permitees, atmospheric deposition, and dredged material
(Menzie-Cura Associates, 1991). Additional sources of contaminants to
sediments include resuspension events and deposition in low energy
environments.
Specifically, Boston Harbor sediments are highly contaminated with
particle-reactive metals and hydrophobic organic compounds (Shiaris
1986; EPA, 1988a; White, 1972) (for detailed review, see MacDonald,'
1991). The accumulation of toxic metals, polyaromatic hydrocarbons, and
chlorinated organic compounds in sediments has distinguished Boston
Harbor as among the most impacted of coastal sites sampled in the NOAA
Status and Trends Program (Long and Morgan, 1990). MacDonald (1991)
found a gradient of contamination extends from the Harbor into
Massachusetts Bay, which suggests a declining influence of sewage and
industrial sources and increased importance of atmospheric sources of
organic contaminants from the Harbor to the Bay. In addition, localized
areas of elevated metal and organic contaminant burdens occur in
proximity to ocean disposal sites (Boehm, 1984; for detailed maps see
Shea et a/., 1991).
For the purposes of this report, Boston Harbor is defined as the
waters bounded by Deer Island and Hull. Massachusetts Bay and Cape Cod
Bay are defined by the waters bounded by an imaginary line drawn from
Cape Ann to the tip of Cape Cod and will hereafter be referred to as
Massachusetts Bays (Figure 1).
-------
Objectives
The overall goal of this study was to assess regional sediment
contamination in Massachusetts and Cape Cod Bays, including Boston
Harbor. Specifically the objectives of this study were to compile data on
sediment metal, chemical, and physical characteristics into a master
database/spreadsheet and to evaluate the regional distribution of selected
contaminants, in relation to sediment quality criteria (SQC).
The EPA is currently in the process of developing SQC that would
protect aquatic resources and human health. This report identifies areas
of Massachusetts Bays that are likely to violate SQC. Areas of
Massachusetts Bays that are in exceedence of national standards will have
to be specially considered and managed by EPA. Regulatory applications of
SQC include site cleanup and restoration (US EPA, 1987).
The regional evaluation was completed by entering data from the
database directly to a GIS (ARC/INFO) for locational plotting by EPA
Region 1 Information Management Branch. In addition, organic
contaminant levels in sediments were compared to proposed SQC, with
normalization to variables influencing bioavailability (i.e., total organic
carbon). The database and GIS was designed to be usable by other
interested agencies/individuals for expanded evaluation of critical areas
such as those where exceedences of SQC potentially cause biological
impacts. The compilation of our sediment data inventory was coordinated
with existing efforts, specifically those of the MWRA and U.S. Geological
Survey Branch of Atlantic Marine Geology in Woods Hole, MA.
Problem of Sediment Contamination
Many metal and organic contaminants are preferentially sorbed to
particles due to their high particle reactivity and hydrophobicity. Metals
and organic compounds accumulate in the sediment reservoir as a result of
physical interactions with the solid phase, such as interaction of metals
with mineral oxides, sulfides, carbonates, and clays, and adsorption of
hydrophobic non-ionic organic compounds to organic matter (Shea, 1988).
The complexation of contaminants with particle surfaces or organic
7
-------
their
Benthic -organisms that live in contact with sediment (and
associated porewater) are at risk of acute or chronic toxicity due to
°rganisms ^'accumulate
b. h H C°mpOUndS' which ™* ^agnify along the food web
benthic dwellers to consumer species, such as fish and Crustacea
Accumulate of contaminants in commercially important species poses a
nek to human consumers of seafood. Direct contact with contaminated
sediment, may a.so pose a risk to human health. To protect the aquatic
aneS°UrC °f 3quatic resource*. the EPA
i devnH- .
•8 developing sed.ment quality criteria to identify specific concentrations
above wh,ch deleterious effects are expected to occur. centratl°ns
In order to develop numerical criteria for sediments knowledge of
the factors that control the bioavailable fraction of a toxicant in
effeCtS" Two ™J°r determinants
are acid volatile su.fides (for meta.s) and total organic
carbon (or non-ionic organics). The bioavailability of metals has yet to
be modeled, due to multiple possible interactions with a number of
nr-H ,n
the ac,d volatile sulf.des (AVS) in sediment, and preliminary studies
suggest metal bioavailability may be controlled by AVS (D.Toro et al
1990). AVS content in sediment may be adopted as a normalization factor
for developing sediment quality criteria for metals. To date however
tf!el!,cr! ^^ ^ ^^ Where AVS C0ntent has been measured. No survey
of AVS has been done in Boston Harbor or Massachusetts Bays The
concentrations of metals in sediments, therefore, can not yet be
normalized, and proposed criteria for metals are based on only absolute
concentrates. Absolute concentration may not, however, accurately
reflect the bioavailable fraction of metals in sediments.
For non-ionic organic compounds, the dissolved phase is considered
to be bioavailable, with maximum concentration in sediment pore water
Based on the bulk toxicant concentration and organic carbon (OC) content
of the sediment, the dissolved concentration can be predicted by
assumptions of equilibrium partitioning and a measure of the affinity of
8
-------
the chemical for organic carbon (partition coefficient, Kp):
[tox]w . [tox]s /{Kp * [TOC]}
where [tox]w is the concentration of a toxicant in water, [tox]s is the bulk
sediment concentration of a toxicant, Kp is the empirically determined
partition coefficient, and [TOC] is the sediment total organic carbon
concentration (Shea et al., 1991).
Development of Sediment Quality Criteria (SQC)
Sec. 304 (a)(1) of the Clean Water Act requires the establishment of
water quality criteria (WQC) in order to protect the health and welfare of
organisms, biological communities, aesthetics, recreation, and from the
adverse impacts of pollutants. Over 65 metal and chemical priority
pollutants have been tested for toxicity to representative aquatic
organisms and bioaccumulation potential (US EPA, 1986). These results
are used to recommend numerical limits for ambient concentrations of a
given contaminant in water. WQC do not, however, take into account the
accumulation of contaminants in sediments. Sediments may be an
important source of contaminants even when WQC are met in the overlying
waters. Sediment quality criteria are therefore needed in addition to WQC
for use in regulatory decisions such as effluent discharge limits,
remediation of contaminated areas, and for management of transfer and
disposal of contaminated sediments. The EPA's goal is to develop general,
numerical criteria that can be applied nationally in a manner analogous to
WQC (Shea, 1988).
There are at least nine different methods that have been proposed
for determining sediment quality criteria (Becker et al., 1989). These
include five field approaches: reference area; field collected sediment
bioassay; screening level concentration; sediment quality triad, and
apparent effects threshold (AET), and four laboratory approaches: WQC;
equilbrium-partitioning (EP) (sediment-water); EP (sediment-biota); and
spiked sediment bioassay. Becker et al. (1989) reviewed these
approaches, including the advantages and limitations of each, and
-------
recommended the adoption of the AET approach to derive sediment quality
criteria for Puget Sound.
The apparent effects threshold specifies a concentration for a given
chemical in sediments above which significant biological effects would
always be expected to occur. Adverse effects at a site are determined by
comparison to conditions at a reference site. The advantages to this
approach include the following: 1. effects of individual chemicals in a
sediment can be distinguished; 2. AET values can be derived for all types
of chemicals and metals; and 3. many different biological indicators can
be used (e.g. community structure, histopathology). The main disadvantage
of AET is the extensive database needed for both chemical and biological
effects parameters. A large database of information on Puget Sound
sediments, including contaminant measures and biological indicators,
exists. Therefore, the AET approach is acceptable for this region. In fact,
the Washington Department of Ecology has released state Sediment
Management Standards for both metals and organics based on the AET
method (Table 1).
The EPA, on the other hand, has adopted the Equilibrium Partitioning
(EP) approach to derive several sediment quality criteria (DiToro et al.,
1989; Shea, 1988). This approach is based on on the finding that total
organic carbon determines bioavailability for non-ionic organics (see
section above). The application of equilibrium partitioning models to
predict the dissolved porewater concentration of non-ionic organic
chemicals utilizes organic carbon-specific partition coefficients (Koc)
for a particular chemical. The SQC is calculated from the WQC for that
chemical, assuming reversible equilibrium between phases:
SQCoc = Koc * WQC (criteria continuous concentration)
The criteria continuous concentration is the lower of the WQC final
chronic values, which protect aquatic life from chronic toxicity, and the
WQC final residue values, which protect uses of aquatic life (US EPA,
1988b). The advantages of the EP approach to SQC determination include
its use of the existing WQC database, its support of the model by
empirical data, and its applicability to different environments and to
different levels of sediment organic carbon content. The major
10
-------
disadvantage to the approach is that it only applies to non-ionic organics,
not to metals or ionizable compounds. In addition, one assumption of the
model is not unanimously accepted, {that reversible equilibrium is
attained between sediment and porewater phases}. Moreover, questions
remain regarding whether the EP approach adequately protects benthic
organisms that ingest as well as inhabit sediment and that are exposed to
complex mixtures of contaminants. Despite the criticisms of the EP
approach, the EPA is continuing the process of developing national SQC. In
fact, the EPA office of Water Regulations, Criteria and Standards division,
has already set interim sediment quality criteria values for nonpolar
hydrophobic organic contaminants based on the equilibrium partitioning
approach (Table 1) (US EPA, 1988b).
The Commonwealth of Massachusetts has regulations for the
concentrations of metals and polychlorinated biphenyls (PCBs) in
sediments under the state dredging and disposal laws (314 CMR 9.00). The
concentrations of metals are evaluated according to a three tiered
classification of sediment contamination levels. Sediments determined to
be of Class I type are not considered contaminated. Sediments classified
as types II and III automatically require that biological testing be done.
State regulations for dredging projects specify standards for metal and
PCB concentrations in sediments for each of the three sediment
classifications (Table 1). The purpose of these regulations is to aid in
management decisions for any proposed dredging projects in the state.
In addition, the Commonwealth of Massachusetts is in the process of
developing sediment quality criteria for polycyclic aromatic hydrocarbons
(PAHs) and draft criteria currently exist (Judy Pederson, Massachusetts
Coastal Zone Management, personal communication) (Table 1). These draft
criteria are based on Gulf of Maine sediment data (low values) and Boston
Harbor paired benthic community and sediment analysis transect data
(high values).
Evaluations of Sediment Quality
Boston Harbor has been ranked the second most contaminated site
tested in the National Status and Trends Program (Long and Morgan, 1990)
Long and Morgan (1990) compiled a large number of studies that relate
11
-------
concentrations of individual sediment contaminants to associated toxicity
or benthic community impacts. The range of concentrations that showed
biological effects, related to a given contaminant were ranked, and the
10th and 50th percentile values were determined. The 10th percentile is
defined as the effects range-low (ER-L) value and represents the
concentration at which effects are seen in sensitive organisms. The 50th
percentile is defined as the effects range-median (ER-M) value and
represents the concentration above which effects are usually seen in most
species. Though the ER-L and ER-M were not intended to be used as
standards, the approach combines several independent methods to derive
consensus values (equilibrium partitioning, spiked sediment bioassays,
and methods matching chemical/biological field data), and thus derived
values are listed along with proposed criteria and standards in Table 1.
The low and median effects levels were compared to National Status
and Trends sediment chemistry data from representative coastal areas of
the U.S. (Long and Morgan, 1990). Sites were ranked by their potential for
the sediments to cause biological effects, as predicted by the overall
number of exceedences of ER-L and ER-M values at a site. Several sites
sampled in the Status and Trends program exceed the effects range values,
and the sites with the highest potential for bioeffects were identified. A'
site in the Hudson-Raritan estuary ranked highest, and a Boston Harbor
site ranked second among the 212 sites sampled in the Status and Trends
program.
These effect level values were also used to analyze metals data
from the pre-1983 Boston Harbor Data Management (BHDM) file database,
with the percent of samples exceeding the ER-L and ER-M reported
(Manheim and Hathaway, -1991). Of metals analyzed, cadmium exceeded its
ER-L with the lowest frequency (21.4%), copper was intermediate (61.4%),
while mercury exhibited the highest exceedence (91.4%).
The following is an evaluation of surface sediment contamination in
Massachusetts Bays in relation to existing or proposed SQC for five
compounds - copper, mercury, total PCBs, phenanthrene, and
benzo[a]pyrene.
12
-------
METHODS
Sediment Quality Criteria Compilation
Sediment quality criteria were gathered and included both proposed
and existing criteria (Table 1). Criteria were compiled in a form that was
normalized to organic carbon content if appropriate (see discussion in
introduction). Various methods used to generate SQC are identified and
discussed. The lowest SQC compiled was used to evaluate sediment
concentrations throughout Boston Harbor and Massachusetts Bays. This
provides the most sensitive measure by which regional sediment
contamination can be evaluated. The effects range - low (ER-L) and
effects range - median (ER-M) values are also listed in Table 1.
Complementary Database Efforts
A number of agencies concerned with Boston Harbor and
Massachusetts Bay water and sediment quality are in the process of
evaluating sediment contamination in this region. Cooperative efforts
were made to complement rather than duplicate the work of many
agencies, as follows:
1. Manheim and Hathaway (1991) reviewed and reorganized the
Metcalf & Eddy compilation of pre-1983 sediment data, Boston Harbor
Data Management File (BHDMF). They have transferred the dBase files into
a Paradox summary spreadsheet. All available parameters for more than
800 sediment samples are included in this database. We agreed to
complement the preparation of this data by locating and entering post-
1983 data for the Boston Harbor/Massachusetts Bays region in a master
database in an Excel spreadsheet file.
2. MacDonald (NOAA, 1991) compiled historical data for Boston
Harbor, and analyzed status and trends in harbor sediment contamination.
Dr. MacDonald contributed his data files that summarized Massachusetts
Bay sediment data through 1988. The Microsoft Excel spreadsheet files
were compiled into a single spreadsheet, organized into a standard
format, and purged of any pre-1983 data that is found in the BHDMF.
13
-------
3. The MWRA contracted Battelle Ocean Sciences to compile
Massachusetts Bay chemical, physical, and biological data for sediments
MVA/O! P * C°ntOUr mapS °f these Para™ters (Shea et al., 1991) '
MWRA and Battelle data managers provided data from the 1991 report
synthesizing Massachusetts Bay sediment data. MWRA's intent is to enter
his data into Massachusetts GIS via the relational database Oracle Due
to difficulties with combining the MWRA's ASCII files into our database
data tables from the appendix to their report were entered into a Lotus '
123 spreadsheet using a Xerox Kurtzweil scanner. Lotus 123 files were
then converted to Microsoft Excel files, organized into a standard format
and added to our master database. In addition, tables of PAH and organics
m?t r.rol8600^^ Treatment FacMitieS Plan P'annin9 documents
(Battelle, 1987a,b) were also scanned into Lotus 123, converted to
M,crosoft Excel files, organized into a standard format, and added to our
master database.
Database Compilation
The data sets mentioned above include many of the known sources of
data on the Boston Harbor/Massachusetts Bays sediment regime. As much
of the data from these reports that could be obtained as electronic files
were transferred into our database. The database was condensed by
removing redundant reports, and reports contained in the pre-1983 BHDM
files.
Our efforts concentrated on obtaining new data sources not covered
m these reports. Requests for data were made to independent
investigators, consulting firms (Metcalf and Eddy, Battelle), and state and
federal agencies (EPA Region 1, EPA Environmental Research Laboratory-
Narragansett, Massachusetts Department of Environmental Protection US
Army Corps of Engineers, and Massachusetts Coastal Zone Management)
All data entered into the Excel database are listed in Table 2. Not all data
available to us were entered into spreadsheet files due to incomplete
information, unpublished data, and time limitations.
Recorded in our master database were the source document, sample
identification number, site description, location coordinates, sediment
grain size parameters, percent organic carbon, and concentrations of
14
-------
individual metals, polychlorinated biphenyls, and individual PAHs. The
methods employed, detection limits, and quality assurance/quality control
measures (replicates, blanks, standards used) were also recorded when
available. Biological data were not compiled, but it was noted if
biological data were gathered in the original report. Additional
parameters are listed at the end of the spreadsheet. These parameters are
neither complete nor standardized, and for the most part are only
measured by one investigator.
Hardcopy of the Excel database file is in Appendix 1. The Excel file
is available on disc to those interested.
Geographical analysis
In order to be included in the GIS analysis, the following information
must have existed for each sample:
1. latitude and longitude coordinates of the sampling location; and
2. the depth of sediment sampled was indicated to be surface only.
We analyzed two metals.copper and mercury, total PCBs, and two
individual PAHs, phenanthrene and benzo[a]pyrene.These were selected as
representative sediment-associated toxicants that are found in high,
potentially toxic concentrations in Boston Harbor, that are routinely
measured, and that are known to persist and accumulate in the sediment
reservoir. In addition, proposed SQC and Washington state sediment
standards exist for the selected metal and organic contaminants. Mercury
was chosen because historical data showed consistently high
concentrations in sediments throughout the Harbor (Metcalf and Eddy,
1984). In their analysis of Boston Harbor metal contamination, Manheim
and Hathaway (1991) found that mercury exceeded its ER-L concentration
(as determined by Long and Morgan, 1990) in 91.4% of the Boston Harbor
sites sampled. Copper, on the other hand, was intermediate in its
exceedences (61.4%) and may, therefore, better represent metal
contamination in general. Phenanthrene was chosen as a representative
low molecular weight PAH, and benzo[a]pyrene was analyzed as a
representative high molecular weight and carcinogenic PAH.
The selected parameters were extracted from the database, and
entered into ARC/INFO, which geographically plots the values for a
15
-------
specified parameter. The following parameters were extracted from the
Excel database file into a second Excel file: an identification number for
each sediment sample, latitude/longitude, % TOC, concentrations (in units
of ppm-dry weight) of copper, mercury, total RGBs, benzo[a]pyrene, and
phenanthrene, and the concentrations of the three organic compounds
normalized to sediment organic carbon content (ug/g-OC). This file was
transferred to an ASCII format, with parameters in comma-delimited
columns. The Information Management Branch at EPA Region 1 converted
this file to ARC/INFO, geographically plotted the contaminant data, and
produced maps for individual contaminants indicating areas with
concentrations in exceedence of SQC.
The GIS analysis provided only limited coverage of the study area
due to the lack of latitude/longitude information in many studies. The
number of SQC exceedences in the entire database were therefore
independently determined and compared to the results of the geographic
analysis.
16
-------
RESULTS
Sediment Quality Criteria Comparison
Sediment quality criteria and standards have been compiled from
three sources: Massachusetts state regulations (314 CMR 9.00),
Washington state sediment management standards (1991), and EPA
Interim Criteria (1988b) (Table 1). The effects level values (ER-L and ER-
M) developed by Long and Morgan (1990) are also listed in Table 1.
Comparison of the SQC values derived by different methods shows
close agreement among criteria for certain contaminants, but up to order
of magnitude differences in criteria values for others. The range of
values defined by the Massachusetts classification criteria for metals
agrees closely with the AET-based Washington state sediment standards
for most metals, except the latter sets 2-fold higher standards for
arsenic and lead. For PCBs, the Massachusetts criteria are non-
normalized, while the Washington AET-based standard and EPA EP-based
criterion are normalized to sediment organic carbon. If the Massachusetts
PCB criteria are normalized to a typical sediment (1% TOC), this
corresponds to a concentration of 50-IOOu.g/g-OC, which is 1 to 2-fold
higher than the EPA interim criterion (41.8 jig/g-OC), and 5 to 10-fold
higher than the Washington state PCB standard (12 |ig/g-OC). For PAHs,
the reference area-based Massachusetts draft criteria low-effects
concentrations exceed Washington state standards for all PAHs except
pyrene. The EPA criteria for PAHs are an order of magnitude higher than
that of Washington for three PAHs, but are similar for phenanthrene and
pyrene. While the EPA phenanthrene criterion is 10-fold lower than the
other EPA PAH criteria, the Washington pyrene standard is 10-fold higher
than the other Washington PAH standards.
The Washington standards are similar to or less protective(/.e. =
higher) than Massachusetts sediment classification criteria for metals,
but are generally more protective (i.e. » lower) than Massachusetts (draft)
criteria and EPA criteria for organics. The Massachusetts criteria and
Washington standards for metals fall within the range of ER-L and ER-M
values. The effects range values for organics are not normalized to TOC,
17
-------
but in a 1% TOC sediment, the ER-L and ER-M would bracket the
Washington state standards for all organics except pyrene. In summary,
agreement is -seen among criteria values for metals derived by different
methods, while AET and the consensus-based effects range levels are 4-
10 fold more protective than the equilibrium partitioning and reference
area-based approaches for deriving criteria for organics.
Database Analysis
The Excel database contains contaminant concentration data,
sediment texture data, and quality control information for 1,085 unique
sediment samples. Several reports were not included in the geographical
analysis. Of the 31 source documents in the database, data from only 16
were included in the GIS analysis (Table 2). Fifteen reports lacked
latitude and longitude data or gave state plane coordinates, which could
not be entered into GIS. An additional four reports were excluded from
both the database and GIS because the data was in progress or because the
report was included in the BHDMF. A large number of different dredging
reports were compiled by MacDonald (1990), and are listed as a single
source of data in Table 2.
Of the 1,085 sediment samples in the database, copper was
measured in 60%, mercury in 54%, total PCBs in 28%, and the two PAHs in
18% (Table 3)
The percent of samples which exceed the SQC for each contaminant
is indicated in Table 3, along with a listing of the sites from which these
samples were taken. Of the 5 contaminants analyzed, mercury exhibits
the highest frequency of exceedence of AET-based Washington standards
(25% of samples ^ 0.41 ppm), and copper the lowest (1.5%). The three
organic contaminants exceed the Washington standards in 5.5% (OC-
normalized benzo[a]pyrene) to 7.6% (OC-normalized phenanthrene) of
samples. The EP-based EPA interim criteria for PCBs and benzo[a]pyrene
were infrequently exceeded (0.5-1% of samples), while the EPA interim
criterion for phenanthrene (which is 10-fold lower than the criteria for
other PAHs) was exceeded in 7.6% of samples.
18
-------
Geographical Analysis
We chose the most protective of the Massachusetts state,
Washington state, and EPA SQC values for the regional evaluation of
Boston Harbor/Massachusetts Bays. The GIS maps indicate samples below
the lowest SQC with a blue dot, and those in exceedence of the SQC for a
given contaminant are indicated with a red dot. Because few sites
exceeded the lowest criterion we did not further differentiate sites that
exceeded the higher criterion. The SQC values chosen were:
copper £. 200 jig/g (Massachusetts class 1)
mercury ^ 0.41 u.g/g (Washington AET-based standard)
PCBs 2. 12 u.g/g-OC (Washington standard)
benzo[a]pyrene ^ 99 u,g/g-OC (Washington standard)
phenanthrene > 100 jig/g-OC (Washington standard)
GIS analysis of two metals, total PCBs, and two organic
contaminants has shown both nearshore and offshore sites that exceeded
SQC. Copper concentrations exceeded SQC in Salem Harbor, the Mystic
River, Fort Point Channel, and Dorchester Bay (Figure 3). All of these
sites are coastal locations. In addition, copper exceeded 200ppm in
Massachusetts Bay at the MBDS.
Mercury exceeded the SQC in many coastal locations as well as
Salem Harbor and the MWRA outfall site (Figure 4). Specific coastal sites
that were shown to have concentrations greater than 0.41ppm include the
Mystic River, Fort Point Channel, Deer Island, Dorchester Bay, Hull Bay,
Salem Harbor, and Scituate. Additional sites of high levels of mercury
outside the scope of our study site are also indicated in Figure 4 and
include the Bass River, Falmouth Harbor, and Rhode Island Sound.
Figure 6 shows sample locations where normalized total PCB's were
measured in levels that exceed 0.12ppm-OC. Although exceedences are
seen at only the MBDS and the outfall site, it is noted that most coastal
sampling locations had no organic carbon data or lacked latitude/longitude
coordinates. Therefore, normalized PCB data for coastal locations could
not be calculated or plotted, and interpretation of sites that are likely to
exceed SQC must take this lack of data into account. It is interesting to
19
-------
note that non-normalized PCS data did not show SQC violations at the
outfall site but the normalized data did.
Analysis of phenanthrene and benzo[a]pyrene showed concentrations
exceeding 100ppm-OC and 99ppm-OC, respectively, at the MWRA outfall
site and in the outer harbor near Deer Island (Figures 7 and 8). In addition,
phenanthrene exceeded 99ppm-OC in Dorchester Bay. Compared to the two
metals analyzed and total PCBs, the organic contaminants showed
relatively few sites that are in exceedence of proposed or existing SQC.
In summary, mercury, PCBs, and PAHs were all found at
concentrations greater than proposed or existing SQC at the outfall site,
and mercury and PCBs are found at higher than criteria concentrations at
the MBDS. Boston Inner Harbor (specifically, Deer Island, the Mystic River,
and Fort Point Channel) also consistently had concentrations of
contaminants that were above SQC levels. In addition, both metals and
PCBs were identified at high concentrations in Salem Harbor.
20
-------
DISCUSSION
Regional Evaluation of Sediment Quality
Our analysis showed low frequencies of exceedences of proposed and
existing sediment quality criteria for all of the contaminants evaluated,
except for mercury. Mercury exceeded the most protective criterion in
25% of the samples for which mercury was measured, whereas the other
contaminants evaluated exceeded their criteria in 5.5% - 7.6% of the
samples Manheim and Hathaway (1991), on the other hand, found higher
frequencies of exceedences of ER-L and ER-M values for both copper and
mercury in the historical Boston Harbor database, BHDMF. Their data,
which are confined to Boston Harbor, are consistent with our results,
which show higher concentrations of contaminants in nearshore areas. In
addition, MacDonald (1991) found that for Boston Harbor sediments, the
mean concentration of mercury exceeded its ER-M value and the mean
concentration of copper exceeded its ER-L value.
The geographic analysis and screening of this database located areas
in Boston Harbor and Massachusetts Bays with potentially toxic
sediments. While primarily clustered in Boston Harbor, coastal
embayments on the northern perimeter of Massachusetts Bay and Cape Cod
are also affected. The outfall site and MBDS also exceed two or more
different SQC. MacDonald (1991) used evidence from individual reports to
define trends in contamination of Boston Harbor. Despite the limitations
of the data and sources of variability encountered, he found a decreasing
gradient in several metal concentrations from the inner Harbor to the
southwest Harbor. Our analysis showed appreciable contamination with
mercury throughout the Boston Harbor and Massachusetts Bays region, and
a lower frequency of SQC exceedences with the other four contaminants
analyzed.
Analysis of sediment contamination of Boston Harbor and
Massachusetts Bays shows very limited coverage of the study site. This
limited number of sampling sites is primarily due to the exclusion of
studies that did not contain latitude and longitude information from the
GIS analysis. In addition, when single latitude/longitude coordinates were
21
-------
given for multiple samples, GIS only plotted a single point. Quantitative
analysis of the GIS results was not possible because of the limited
coverage and inability to differentiate data points from similar locations
on the maps.
Sediment Quality Criteria
Sediment quality criteria compiled from three sources
(Commonwealth of Massachusetts, State of Washington, and U.S. EPA)
were developed by independent methods. These approaches (AET, EP, and
reference area) show a surprising amount of similarity in the SQC derived
from them. In general, the AET-based approach used by Washington state
and the Massachusetts sediment classification method provide similar
SQC for metals. In addition, the AET approach consistently yields lower
SQC for organics than either of the other two approaches. The AET
approach may therefore be a more protective method for determining SQC
for organic contaminants. The reference area approach requires that
suitable reference sites and data exist, and thus may not be applicable on
a nation-wide basis. The EP approach has potential for developing
broadly-applicable SQC from the existing database used in determining
water quality criteria. However, the EP approach is presently limited to
non-ionic organics for which WQC are available, and provides significantly
higher criteria values than those derived by the field-based
chemistry/bioeffects AET. In addition, the EP approach does not account
for biota which are exposed to contaminated sediments either through
ingestion or through direct contact. The derivation of SQC by combining
the results of several approaches, as done by Long and Morgan (1990) to
define the ER-L and ER-M, may provide a more balanced criteria than
reliance on a single approach.
Our efforts have shown that it will be essential for future
investigators to measure both total organic carbon content and acid
volatile sulfides if evaluation of sediment contamination with any
normalized/standardized sediment quality criteria is to be achieved.
Comparison of Figures 5 and 6 shows the striking lack of data for TOC
content in the Massachusetts Bays region. Coastal contamination of PCBs
could not be definitively evaluated due to the lack of corresponding TOC
22
-------
and PCB data in coastal sampling sites. There has been no survey of AVS
in Massachusetts Bays; therefore, the concentrations of metals in
sediments can not be normalized and only absolute concentrations may be
compared with SQC. Absolute concentration may not, however, accurately
reflect the bioavailable fraction of metals in sediments.
Database
The database compiled here includes almost all of the post-1983
data available for sediment contamination in Boston Harbor and
Massachusetts Bays. This database is easily accessed and readily
available in a standardized spreadsheet form in Microsoft Excel. It is
hoped that this will form the basis for any future sediment quality
analysis of the region. All or some of this database will be entered into
the ARC/INFO -Oracle system at Mass-GIS. Our database should aid future
investigators, in particular, the database can aid in survey design and
selection of parameters to measure.
Statistical analysis of the data has not been attempted due to the
variability in the data. Sources of variability include different
investigators, sampling methods, analytical methods, detection limits,
quality assurance/quality control measures, as well as natural factors,
such as biota and grain size. The lower quality of data obtained from
dredging reports, with detection limits of 0.66 ng/g of individual PAHs, is
difficult to compare with studies in which 0.003 fig/g detection limits
were achieved.
Each individual study compiled here had its own objectives and
focus. Therefore the spatial and temporal coverage of data for
Massachusetts Bays is not comprehensive. Other than a general nearshore
to offshore gradient in sediment contamination, spatial trends in the data
are not discernable from our limited analysis of the data. Analysis of
temporal trends was not attempted. An analysis of more a comprehensive
spatial and temporal database is needed.
23
-------
Recommendations
Database compilation efforts would benefit greatly, with time and
effort conserved, by designating a common location and cataloging system
for holdings of regional environmental reports. Attempts to locate
sediment data by contacting individuals proved time-consuming and
unproductive. The new information identified in this manner were most
often incomplete raw data or reports already in hand.
In the future, all sediment chemistry analyses of Boston Harbor and
Massachusetts and Cape Cod Bays should include measurements of %TOC,
grain size information, and acid volatile sulfide content. Knowledge of'
factors controlling bioavailability will allow better prediction of the
biological effects of a given contaminant. Sites which exceed SQC should
be further investigated to determine potential for biological effects.
Stricter standards for analytical methods and lower detection
limits should be in place to allow comparison of data generated by
different analytical methods and laboratories. For example, PAH data
obtained from Battelle with a limit of detection of 3ng/g cannot be
directly compared with data reported to the U.S. Army Corps of Engineers
with a limit of detection of 660ng/g.
The GIS analysis could be significantly expanded both spatially and
temporally by locating the latitude and longitude data from the 15 reports
included in our database that are missing this information. Detailed maps
of the sampling locations exist for most of these studies, but time and
expertise did not permit translation of the information to the GIS program
for the study.
Caution is advised in synthesizing and transferring large databases
such as this (Manheim, personal communication). Entering data into a
relational database with a minimum of reformatting would avert the
introduction of error or loss of data with repeated transfer from hardcopy
to files and between files. It is recommended that this database and all
future data collected on Boston Harbor and Massachusetts Bay be placed
into an accessible database for entering and analyzing coastal water and
sediment quality trends.
24
-------
It is hoped that agencies interested in sediment quality will
combine efforts to establish a common database and build on the data
compiled to date for the Boston Harbor/Massachusetts Bay region. Such
cooperative efforts might also be fruitful for development of a
comprehensive GIS database, .of interest to MWRA, U.S. EPA, U.S. ACOE, and
MA CZM. Other EPA regional offices are conducting similar sediment
surveys, and this could perhaps be incorporated into a national assessment
of contaminated sediments.
25
-------
REFERENCES
Arthur D. Little. Sept 28, 1990. Final Data Report for Evaluation of the
Reference Site Suitability for the Massachusetts Bay Disposal Site.
Submitted to US EPA, Region 1. Water Management Division. Contract No
68-D-90164.
Battelle Ocean Sciences. 1984. Unpublished metals data from NOAA-NEMP
(in Shea et al., 1991).
Battelle Ocean Sciences. 1987a. Marine Ecology and Water Quality Field
Studies for Outfall Siting for the Deer Island Secondary Treatment
Facilities Plan: Concentrations of Polynuclear Aromatic Hydrocarbons and
Metals in Surface Sediment at Selected Sites in Massachusetts Bay. Draft
report to CZM, Oct 21, 1987.
Battelle Ocean Sciences. 1987b. Technical Memorandum to Camp Dresser
and McKee. Marine Ecology and Water Quality Field Program for Deer
Island Secondary Treatment Facilities Plan. Concentrations of
Polychlorinated Biphenyls in Surface Sediments at Selected Stations in
Massachusetts Bay.
Battelle Ocean Sciences. May 20, 1991. CSO Effects on Contamination of
Boston Harbor Sediments. MWRA Task Order No. 18. Draft Report.
Becker, D.S., R.A. Pastorok, R.C. Barrick, P.N. Booth, and L.A. Jacobs. April
1989. Contaminated Sediments Criteria Report. Submitted by PTI
Environmental Services to Washington Dept. of Ecology, Olympia WA.
Ecology Contract No. C0088171.
Boehm, PD. 1983. Chemical contaminants in Northeast United States
marine sediments. NOAA Technical Report NOS 99. Rockville, MD: NOAA.
82pp.
26
-------
Boehm, PD and JW Farrington. 1984. Aspects of the polycyclic aromatic
hydrocarbon geochemistry of recent sediments in the Georges Bank region.
Environ. Sci. Technol. 18:11:480-485.
Boehm, PD, W Steinhauer, and J Brown. 1984. Organic pollutant
biogeochemistry studies Northeast U.S. marine environment. Final Report
Contract No. NA-83-FA-C-00022. Duxbury, MA: Battelle, New England
Marine Research Laboratory. 60pp.
Camp, Dresser and McKee. 1990. Spectacle Island Sediment Sampling
Results (data received from Kevin McManus, Metcalf and Eddy, Wakefield
MA - Table 1.)
Chesmore, AP. 1972. A study of the marine resources of Lynn-Saugus
Harbor. Monograph Series, Boston, MA: Massachusetts Department of
Natural Resources Division of Marine Fisheries. 40pp.
Chesmore, AP. 1973. A study of the marine resources of Essex Bay.
Monograph Series, Boston, MA: Massachusetts Department of Natural
Resources Division of Marine Fisheries. 38pp.
Cudmore, J, R Schumacher, and B Poole. 1988. Ecological evaluation of
proposed oceanic discharge of dredged material from Harbor View Marina,
Town River, Quincy, MA for Quinoil Industries, Inc. SP, Inc. Salem, MA.
34pp.
DiToro, D.M., et al. April 1989. Briefing Report to the EPA Science
Advisory Board on the Equilibrium Partitioning Approach to Generating
Sediment Quality Criteria. EPA Office of Water Regulations and
Standards, Criteria and Standards Div.
DiToro, D.M., J.D. Mahoney, D.J. Hansen, K.J. Scott, M.B. Hicks, S.M. Mayr, and
M.S. Redmond. 1990. Toxicity of Cadmium in Sediments: The Role of Acid
Volatile Sulfides. Environmental Toxicology and Chemistry 9: 1487.
27
-------
Enseco Inc. 1987a. Ecological evaluation of proposed oceanic discharge of
dredged material from Marina Bay/Squantum Point, Quincy, MA. Enseco
Inc. Doaks Lane at Little Harbor, Marblehead, MA 25pp.
Enseco Inc. 1987b. Ecological evaluation of proposed oceanic discharge of
dredged material from Little Mystic Channel/ Charlestown Navy Yard.
Enseco Inc. Doaks Lane at Little Harbor, Marblehead, MA 27pp.
Farrington, J., E. Gallagher, and G. Wallace. March 1990. Progress Report -
To MWRA. Boston Harbor Study of Sources and Transport of Harbor
Sediment Contamination. Part II: Sediment-Water Exchange of
Contaminants in Boston Harbor.
Gardner, G.B., R.P. Eganhouse, and G.T. Wallace. 1986. Baseline
Assessment of Salem Harbor - Salem Sound and Adjacent Waters. Report
prepared for the South Essex Sewage District.
Gilbert, TR. 1975. Studies of the Massachusetts Bay foul area. Report No.
1-75. Boston, MA: Commonwealth of Massachusetts Division of Water
Pollution Control. 197pp.
Gilbert, TR, GC McLeod, R Maehl, KV Ladd, A Clay, A Baker. 1972. Volume
II. Trace metal analysis of Boston Harbor waters and sediments. Boston,
MA: New England Aquarium, Research Department. 98pp.
Hubbard, WA. 1987. A draft environmental assessment of the proposed
Boston Harbor Improvement Dredging Project in Boston, Massachusetts,
Boston, MA: Army Core of Engineers. 180pp.
Isaac, RA and J Delaney. 1975. Toxic element survey. Final Report.
Research and Demonstration Project 71-06. Massachusetts Department of
Environmental Quality Engineering, Westborough, MA 40pp.
Iwanowicz, HR, RD Anderson, and BA Ketschke. 1974. A study of the
marine resources of Plymouth, Kingston, and Duxbury Bay. Monograph
28
-------
Series, Boston, MA: Massachusetts Department of Natural Resources
Division of Marine Fisheries. 37pp.
Jason M. Cortell & Associates, Bechtel/Parsons Brinckerhoff. May 1990.
Draft, report. The Aquatic Resources of Spectacle Island. Central Artery
(l-93)/Third Harbor Tunnel (I-90) Project.
Long, E.R. and L.G. Morgan. March 1990. The Potential for Biological
Effects of Sediment-Sorbed Contaminants Tested in the National Status
and Trends Program. NOAA Technical Memorandum NOS OMA 52.
MacDonald, D.A. June 1991. Status and Trends in Concentrations of
Selected Contaminants in Boston Harbor Sediments and Biota. NOAA
Technical Memorandum NOS OMA 56.
Manheim, F.T. August 20, 1991 update memo to: Respondents to June 1990
Meeting on Contaminated Sediments, Woods Hole.
Manheim, F.T. and J.C. Hathaway. 1991 - Final Report. Polluted Sediments
in Boston Harbor - Massachusetts Bay: Progress Report on the Boston
Harbor Data Management File. US Geological Survey, Woods Hole MA. Open
File Report.
Massachusetts Department of Environmental Quality Engineering. Division
of Water Pollution Control. 1985. Boston Harbor, 1985. Water quality and
wastewater discharge data. 14,4771-80-20-10-86-CR. Westborough, MA:
MASS-DEQE, Division of Water Pollution Control, Technical Services
Branch. 72pp.
Massachusetts Department of Environmental Quality Engineering. 1986.
Boston Harbor, 1986. Water quality and wastewater discharge data.
#15.063-75-75-10-87-CR. Westborough, MA: MASS-DEQE, Division of
Water Pollution Control, Technical Services Branch. 67pp.
Massachusetts Department of Public Works. March 25, 1991. Evaluation
of Third Harbor Tunnel Dredged Material Disposal at MBDS. Central
29
-------
Artery/Tunnel Project. Rowars Task Assignment #7. Characterization of
Dredged Material. Final Draft, Vol.s 1 and 2. Camp Dresser & McKee Inc.
Massachusetts State Sediment Classification for Dredge Material
Disposal. State regulations section 314 CMR 9.00,
Massachusetts Water Resources Authority. March 31, 1988. Secondary
Treatment Facilities Plan. Volume V. Appendix S. Benthic Chemistry
Sampling. Submitted by Battelle to CZM (cf. Battelle, 1987a).
Metcalf and Eddy. November 1983. Boston Harbor Data Management:
References and Data Summaries. Vol 1: Preliminary Listing, July 1983;
Preliminary Listing, Vol. 2.
Menzie-Cura & Associates. April 1991 - Draft Report. Sources and
Loadings of Pollutants to Massachusetts Bay: Task 1 of the Massachusetts
Bays program.
NET Atlantic, Cambridge Div. October, 1990. Mid-year report
for:Engineering Services for the 301 (h) Effluent Monitoring Program.
Submitted to Glouchester Dept. of Public Works.
NOAA. Unpublished. Trace metal data from the North East Monitoring
Program survey in Massachusetts Bay, 1983. (taken from Table C-2 in:
Shea et a/./Battelle, June 1991).
Perez, K. and J. Cardin. unpublished data. Boston Harbor sediment
sampling, metals concentrations, July 1990. EPA-Narragansett
Laboratory, Narragansett Rl.
Phillips, S. 1985. Letter to Atkinson ACOE 10-31-85.
Pruell, R.J., McKinney, R.A., Boothman, W.S., Cobb, D.J., LiVoIsi, J.A., Bowen,
R.D., and F.A. Osterman. Jan. 1989. Contaminant concentrations in
sediments from the Foul Area Disposal Site in Massachusetts Bay. Final
Report to US EPA Region 1.
30
-------
Robinson, WE, TJ Coffey, and PA Sullivan. 1990. New England Aquarium's
ten year Boston Harbor monitoring program (draft). First Report March
1987- July 1989. Boston, MA: New England Aquarium Edgerton Research
Laboratory. 184pp.
Shea, D. 1988. Developing National Sediment Quality Criteria.
Environmental Science and Technology 22: 1256.
Shea, D., D.A. Lewis, B.E. Buxton, D.C. Rhoads, and J.A. Blake. June 20, 1991.
The Sedimentary Environment of Massachusetts Bay: Physical, Biological,
and Chemical Characteristics. Prepared for MWRA, by Battelle and SAIC.
Shiaris, MP and D Jambard-Sweet. 1986. Polycyclic /aromatic
hydrocarbons in surficial sediments of Boston Harbor, Massachusetts, USA.
Marine Pollution Bulletin 17(10): 469-472.
US Army Corps of Engineers. 1980. Boston Harbor Massachusetts. Final
environmental impact statement on debris removal. Waltham, MA: US
ACOE. 53pp.
US Army Corps of Engineers. 1981. Environmental assessment for Boston
Harbor maintenance dredging Boston Harbor, Boston, Massachusetts. Data
sheets. Waltham, MA: Department of the New England Division, COE. 70pp.
US Army Corps of Engineers, New England Div. October 1987. Disposal
Area Monitoring System DAMOS. Analysis of Sediment Chemistry and Body
Burden Data Obtained at the Massachusetts Bay Disposal Site.
Contribution #75, August 1990b. Prepared by Science Applications
International Corp, Newport Rl.
US Army Corps of Engineers. 1988. Boston Harbor, Massachusetts.
Feasibility report and environmental assessment for deep-draft
navigation improvements to Boston Harbor including Mystic River, Chelsea
River, and Reserved Channel. Boston, MA: Department of the Core of
Engineers New England Division. 523pp.
31
-------
US Army Corps of Engineers, New England Div. August 1990a. Boston
Harbor, Mass. Mystic River, Chelsea River, and Reserved Channel.
Navigation Improvement Study Dredge Material Disposal Plan. Supplement
to Feasibility Report, and Supporting Documentation (2 vols.).
United States Environmental Protection Agency. 1986. Quality criteria
for Water. EPA 440-5-86-00. Office of Water Regulations and Standards
Criteria and Standards Div. Washington. D.C.
United States Environmental Protection Agency. 1987. Regulatory
applications of sediment quality criteria. Washington, D.C.
United States Environmental Protection Agency. 1988a. A
histopathological and chemical assessment of winter flounder, lobster,
and soft-shelled clam indigenous to Quincy Bay, Boston Harbor and an in
situ evaluation of oysters including sediment (surface and cores)
chemistry. Quincy Bay Study. Narragansett, Rl: United States
Environmental Protection Agency, Environmental Research Laboratory
108pp.
US Environmental Protection Agency. May 1988b. Interim Sediment
Criteria Values for Nonpolar Hydrophobic Organic Contaminants. Office of
Water Regulations and Standards, Criteria and Standards Div.
US Environmental Protection Agency. 1989. Unpublished Massachusetts
Bay Disposal Site Sediment Data from 7 Dec 1988. 5 July 1989 Memo from
Sue Cobler to Kymberlee Keckler, EPA Region 1, Div. of Water.
Wallace, GT, RP Eganhouse, LC Pitts, and BR Gould. 1988. Analysis of
contaminants in marine resources. Final report. Contract No. 85-18.
Project 812527-01-0. Boston, MA: University of Massachusetts,
Environmental Sciences Program. 144pp.
Washington State Department of Ecology. April 1991. Chapter 173-204
WAC Sediment Management Standards.
32
-------
White, RJ, JR. 1972. The distribution and concentrations of selected
metals in Boston Harbor sediments. Msc. Boston, MA.
33
-------
TABLE 1. Summary of existing and proposed Sediment Quality Criteria,
SOURCE
CCMPCUM)
Metals.
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Silver
Zinc
Total PCBs
Pesticides
Total DOT
Dieldrin
Endrin
Chlorpyrifos
Heptaclor
PAHs
Acenapthane
Anthracene
Benzo(a]anthracene
Banzofluoranthracene
Benzo[a]pyrene
Benzojghqperylene
Chrysene
Oibenzo[a,h]amhracene
Fluoranthene
Fluorene
Napthalene
Phenanthrene
Pyrene
Massachusetts State Criteria
Sediment Classification
1 II III
(Dredge Material Criteria)-
(ppm-dw)'
Effects Range
<10
<5
<100
<200
<100
20
>10
>300
>400
>200
>1.5
>100
<200
<0.5
200 - 400
0.5 • 1.0
>400
(Draft Only)"
Low effects High effects
(ppm-OC) (ppm-OC)
3.3
2.9
1.6
12.5
3.3
4
28.1
28.1
30.2
48.2
27.2
45
Low
(ppm-dw)
33
5
80
70
35
0.15
30
1
120
0.05
0.003
0.00002
0.00002
0.15
0.085
0.23
0.4
0.4
0.06
0.6
0.035
0.34
0.225
0.35
Medium
(ppm-dw)
85
9
145
390
110
1.3
50
2.2
270
0.4
0.35
0.008
45
Washington State
Sediment Standards
(Apparent Effects Threshold)
(ppm-dw)
57
5.1
260
390
450
0.41
6.1
410
(ppm-OC)
12
EPA Interim
Criteria
(Equilibrium Partitioning)
(ppm-OC)
(ppm-dw) (ppm-dw)
0.65
0.96
1.6
2.5
2.8
0.26
3.6
0.64
2.1
1.38
2.2
(ppm-OC)
16
220
110
230
99
31
110
12
160
23
99
100
1000
41.8'
0.828
0.13
0.0532
0.44
0.104
(ppm-OC)
1317
1063
1883
102
1311
Sources: MA State - Metals - State regulations section 314 CMR 9.00
• PAHs - Judy Pederson-MA Coastal Zone Management
Effects Range - Long and Morgan. 1990
Washington State - Sediment Management Standards. 1991
EPA - US EPA-OHfce of Water Regulations and Standards Criteria, 1988
- ppm-dw . parts per million dry weight - |tg/g
- OC - organic carbon
' - PCB congener 1254 only
- Massachusetts draft criteria based on benthic community structure Indices
34
-------
Table 2. Sources of data compiled in the Excel database and used for the CIS analysis.
Report
AD Little, 1990
Bajek, 1983
Battelle. 1984
Battelle, 1987a,b
Boehm. 1983
Boehm et al, 1984
Boehm & Farrington, 1984
Chesmore, 1972
Chesmore et al, 1973
Cudmore et all 1988
Enseco. 1987a
Enseco, 1987b
Gardner, 1986
Gilbert, 1975
Gilbert et al, 1972
Hubbard, 1987
Isaac & Delaney, 1975
Iwanowicz et al, 1974
Jason Cortell, 1990
MacDonald, 1991
MADEQE, 1985
MADEQE, 1986
MA DPW, 1991
NET Atlantic, 1990
Phillips, 1985
Pruell et al, 1989
Robinson et al, 1990
Shea et al, 1991
Shiaris et al, 1986
USACOE, 1990a
USACOE. 1990b(DAMOS)
USACOE. 1981
US EPA, 1988
USEPAMBDS.1989
White, 1972
Agency Used
EPA
USACOE
NOAA/NEMP
MWRA
NOAA
NOAA
X
MA-DMF
MA-DMF
USACOE
USACOE
USACOE
S Essex SD
MA-DEQE/DWPC
NEA
USACOE
MA-DEQE/DWPC
MA-DMF
MA DPW
USACOE
DEE
DB3E
MA DPW
Gloucester-DPW
USACOE
EPA
NEA
MWRA
EPA
USACOE
USACOE
USACOE
EPA
EPA
X
in Database
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
N
ID #s in
database
'1-24
10466-10471
255-269
120-254
10232-10251
10252-10399
10184-10231
10400-10431
10432-10440
10456-10457
10458-10461
10462-10465
270-276
10614-10631
X
10632-10658
10659-10701
10702-10734
74-92
10000-10183 &
10476-10491 &
10735-10770
10492-10510
10511-10521
25-35
68-73
10472-10475
93-106
10771-10785
36-65
10786-10809
X
107-115
10441-10455
10522-10613
66-67
X
Used ir
Y
N
Y
Y
N
Y
N
N
N
N
Y
N
Y
Y
N
Y
N
N
N
Y
N
N
Y
Y
N
N
Y
Y
Y
N
Y
N
Y
Y
N
Comments
Only 1 location for 24 samples
No latitude and longitude data
Scanned into supplemental database
Scanned into supplemental database
No latitude and longitude data
No latitude and longitude data
No latitude and longitude data
No latitude and longitude data
No latitude and longitude data
No latitude and longitude data
Scanned into supplemental database
Excluded non surface samples
INBHDMF.
Excluded non surface samples
No latitude and longitude data
No latitude and longitude data
Only state plane coordinates available
Excluded sites not in Mass Bay
& sites without lat/long data
No latitude and longitude data
No latitude and longitude data
No latitude and longitude data
No latitude and longitude data
Draft report not for release
No latitude and longitude data
No latitude and longitude data
IN BHDMF
in
ro
-------
Table 3. SQC exceedences determined by database screening.
Compound
Copper
(n=649)
Mercury
(n=585)
Total PCBs
(n=304)
Benzo[a]pyrene
(n=201)
Phenanthrene
(n=197)
Low Criteria
(SQC Source)
>200ppm
(MA Class I)
>0.41ppm
(AET)
% Exceedence Sites In Exceedence High Criteria
of low criteria (SQC Source)
>12ng/g-OC
(AET)
>99|ig/g-OC
(AET)
>100mj/g-OC
(AET)
6.50% Quincy Bay
Greene Harbor
Smith Cove (Gloucester)
Spectacle Island
25% Taunton River
Falmouth
Nantucket
Hyannis
Beverly
MBOS
MWRA Outfall site
5.90% Inner Boston Harbor
MBDS
MWRA Outfall site
5.50% Inner Boston Harbor
MWRA Outfall site
7.60% Inner Boston Harbor
Deer Island
Spectacle Island
Dorchester Bay
MWRA Outfall site
>390ppm
(AET)
>1,5ppm
(MA Class III)
.8ng/g-OC
(EPA)
>1063jig/g-OC
(EPA)
>102ng/g-OC
(EPA)
% Exceedence Sites In Exceedence
of high criteria
1.50% Inner Boston Harbor
Salem Harbor
Dorchester Bay
Bass River
11% Inner Boston Harbor
Salem Harbor
Boston Outer Harbor
Bass River
Scituate
Smith Cove (Gloucester)
1% Spectacle Island
0.50% Deer Island
7.60% Inner Boston Harbor
Deer Island
Spectacle Island
Dorchester Bay
MWRA Outfall site
n=the number of samples in the database in which a given contaminant was measured
ppm=parts per million dry weight
OC=organic carbon
-------
I0stoa Harbor lisct
Boston Harbor, Massachusetts Bay and Cape
Cod Bay with sampling sites indicated
37
M«llf 1
HA l*|l*l I, Vtltl •tttftattl Hfltltt
•ititckiitttt Itjt ftt|tia • Otltktr.
-------
J*tl« <|
-------
lid '
•ultij
VII
I IlltU
put
$ sAeg poo
uojsog u|
put
^ 1°
-------
Legend
B » or . 41.1 ppa-oc
S » or • 12 *»d <41.1 ppa-o
H »12 ppn-oc
Notes:
lostoi Harbor liset
41.1 f»-»» . ir* ituti*
II >«< • *MkU|IM lltl* Ctltttli
Distribution off Total PCB's in B o s t o nr o r
and Massachusetts and Cape Cod Bays Sediments
Normalized to Total Organic Carbon with
Sediment Quality Criteria Violations Indicated
riant 4
40
IfA l»|l*i I, *«t*r Mti»f«B*tl tlvlti**
rr»|tta - OcUktr, 1**1
-------
Legend
B >or • 1143 pp«-oc
GO ..» or • fl lid i1ti3 pp»-o
ID «t* ppa-oc
los to* Harbor Iiset
till »»•••« • I** Uliil* telltflt
• I »»••«« . •ltkll|l*> Ittlt tH««ll«
Distribut ion of Phenanthrene in Boston Harbor
and Massachusetts and Cape Cod Bays Sedinents with
Sedinent Quality Criteria Violations Indicated
ricni i
41
I, *tt«r
Hittt«ki»«ltt lift
• Ocltkcr,
-------
Legend
B » or • 112 ppa-oc
S . or . ill aid <1I2 pp«-o
El <1II ppa-oc —
loitoa Harbor liset
^ ^
Distribution of Benzoapyrene in Boston Harbor and
Massachusetts and Cape Cod Bays Sediments with
Sediment Quality Criteria Violations Indicated
FICIII I
42
*tl«r Mit
-------
APPENDIX - MICROSOFT EXCEL DATABASE
Explanation of Database
The database is in Microsoft Excel version 2.2 and is available
to those who would like a copy.
Each row in the database contains a single sample entry. For
ease in using this database, new and unique identification numbers
have been assigned to each sample entry and appear in column A-
Sample numbers and identifiers assigned by the original
investigators have been retained.
Columns A through £G_ are identical for every sample in the
database. The parameters we chose to record in the database
include location information, sediment chemistry data,
concentrations of contaminants, and quality assurance/control
information. Several columns beyond CG contain parameters
measured only by one or a few investigators and are not identical
throughout the database.
Where blanks occur in the database, the parameter was either
not measured or not recorded by the original investigator.
A supplemental file was scanned into the database from
Battelle (1987a,b), Gardner (1986), and NOAA/NEMP (1983). This
portion of the database does not contain complete records, QA/QC
information is missing, and of the PAH's measured in these original
reports, only benzo[a]pyrene and phenanthrene values were entered in
our database.
43
-------
-------
-------
88|8|g|g|g|g|g|g|gl8l8lg|g|gl*
-------
-------
-------
-------
-------
-------
-------
-------
-------
«9
_LL
TT
it
_u
("
it
-Al-
oE
Lid
40
Li!_l
LuJ
l_i«J
hH
19
-IL
67
»•
60
61
6S
•,L
67
61
•o
-it
71
72
'»
70
7f
77
70
'•
At
-JJ-
_ii.
.1.'.
.li
61
61
•«
66
•7
•0
109
101
10}
101
P II A* PC* 1204 ONLY:
""*
NO Cd.C«.P»,HD; 010.7.2.0. OS Mn
P NO P».PC>: OL 2 «, 01 :
P NO PCI: OL. 01 MM:
P NO PCI: OL 0.2 MM 12001: NA A4.M.Zn>
NO PCI.OOO: OL 0212*01.1 W. NA A.AI.Z
II C..PO.W.PCI
P NO Cd.P»: OL 2 0 2 .1: NA PCI
P NO Cd.Pe.NJ; OL 2.21 ». NA PCI
NO Cd: OL 0.4 MID: NA AtM.In.PCI
P NO Cd: OL 07 MmttA AiM.2n.PCI
NOPCi.O»0;DL 01.42MM
NO PC*: OL .01 Mm: II P»
NDCd.OOOiOL.32.4Mm
NDCd: OL 20 nm
NDC4tOLO3MM
II Pk
P Ml A4
P II Zn
NO CdM.000: OL J7..00.ZOO:NA 2H.PC*
NO Cd.0*0: OL 37.200 MUVNA Zn.PCO
NAZuPCI
NO C4O, PL iOOjtm NA InfG*
P NO Cd: OL 02 Mm- NA A4M.Zn PCI
P NOCd: OL 07 Mm: NA A4M .Zn.PCI
P NO PCI-OL no*"""- IIA4.Cd.OOO-
P NO PCI: II A4.Cd.Main.WX (OL:
P NO Ha: OL OOOMm:NA OflAM SIZE
II PCI: NAM. (MAM SIZE
II At,Zn: NA M OfUIN SIZE
II A4.P».PCI: NAM. OMAINSIZE
NO Cd- OL O.SMm- NA M OMA04 SIZE
P NA At.Nl.Zn.PCI
P NO Cd-OL 0 *Mm: NA At/0,Zn,PCI
NDCd HaM- NA PCI
NDCd.HO.M
NDCdMNAPCI
NDCd,Hl
ND Cd HaM- NA PCI
NOCdcNAPCI
— S —
j
*
2'OPO
00"
2450
2.7M
POOP
15000
POOP
7SOOO
1 OOOO
oooo
oooo
20000
31 OM
4200
20000
OOOO
75*0
«'M
1440
0 000
0 000
4540
13 MO
1 100
1 300
OOOO
0 000
3 200
2000
4000
4 700
4(00
4 400
4 100
a (M
5 700
S 100
4(00
32M
4 200
5700
4 400
4 300
3 700
3 400
3 (00
4 1001
57 MO
0 000.
51 000'
16 000
0 4*0 )
8 2301
6 940
4 740;
0 000
0 000
0 000'
1 1 1 5001
4 000
•00
400
3 000'
3: 000!
1 000!
000!
0001
0001
500|
900 {
900!
500:
•00<
'300
1 440
LSOO
0900
P«OO
3»PP
"PP
I 000
1 400
o.soo
0.3*0
4500
0*40
0200
0 100
1 '-1001
0 700
4 400
3210
S520
3900
2 ISO
4 570
2000
2000
0400
0 070
OSSO
0 430
0400
0370
0600
0 320
0340
0 330
2 $00
o no
2 400
0690
t 100
I 000
0320
0 330
0 440
0 260
0 300
0 610
1 710
0300,
0 320
0 260
0 370'
0 370
0 &40
9 4(0
0 iSO
3 020
0 070
29 630
1 1 OOOl
2 100i
3 800 1
4 2001
2 900;
0 OSO
0 220
0 SOO
3 000
30001
3 0001
3 000
3 000
3 000
«•*»
1U400
-IM.OOO
— ?40O°
40.000
— 1222
"oooo
•0-W.
1 .
'3*70
"POOP
50 000
*0 MO
7000
24.MO
"OOPO
"oooo
'00*00
317400
"OOP
7*00
«ooo
SMO
204000
2M.MO
"PPP
300<
2 I0(
'PP-PPO
HOMO
•0000
•2.MO
110000
SMO
2. SOO
1 »-«00
7500
• MO
14 OOC
2*0400
2 100
2 100
10M(
• 100
•2000
34 MO
IS MO
13000
93000
If MO
OOOO
•40 MO
1 10 MO
$0 Mfl
70 Mfl
51 000
3* OOQ
74000
1(000
20 Mfl
35000
lOOOfl
It MO
SOO Mfl
141.010
4. Mfl
17 Mfl
(700
7 MO
147MO
17300
71 700
1 MO
14 MO
I03.MO
M.OOO
4* 000
70320
20ft. MO
27 MO
170. MO
1SO.MO
240.MO
110000
33 MO
31 000
»OOPO
40000
• t 000
40000
40000
S3 MO
191 MO
OMO
0-1*0
'OOP
I 000
'OOP
«»p
POOP
POOP
O.*40
1 200
0.0*0
0.000
00*0
p«»p
o*to
0"0
0.040
oooo
0.010
0.020
0340
0400
1 100
0.0*0
O'OO
Q"Q
0.140
oo«o
0.0*0
0543
3_430
43«
0040
o too
0520
0070
o.ioo
0200
0072
0032
0(70
0 M7
0.020
0 2*0
0 740
0410
0 SOO
0.330
0 MO
0.370
o no
0 110
0. IM
0.0*7
0 IM
0440
10.7*0
0.0*0
0 013
0023
0 074
0.2*0
0 4*2
0 173
0.040
0 070
00*0
1 3*0
1 300
1 170
0013
O.OM
1 200
0070
1 100
OOOO
0.070
0 170
O.IM
o too
0 100
O.IM
o too
0 7M
'3*00
PPM
•POOP
»ooo
12000
oooo
POOP
'7000
30040
57440
oooo
OOOO
oooo
PPOO
POOP
4.0M
HOOO
1 '7000
73M
70M
MOOO
OOOO
OOOO
24 100
2««M
PPOO
OOOO
OOM
" OMI
10550
42 OM
2SM
OOM
OOM1
12 OM
13000
IS 000
IS OM
IS OMI
!• OMI
24 000!
13 OMI
19 OMI
12000
14 OM
1(000
3000
3 000-
1 OM:
t 000.
3 000'
1( OM'
14500
OOOO
45 000
1 000
940
1 300
710
900
000
two"
0 000
*• 500
4* 130
70 100
77 000
40 000
0 000
0 000
OOOO
0 000
oooo
oooo
23000
24 000
24 000
23000
24 000
13 000
1
!
1
-------
IM44I4 Mm
-------
W|4i
li
'
I
£
I
I
-------
-------
F. - .—— -x-ff -f-frr • •
> '.".'. ,".".".
I
I
S R
513
111
15SI
S3
8S3
SS 2
SS3
CSS
S3
888
ill
ji
i
188888
u
••
"•"I"
-------
-------
i
-------
•
ITT
\
mi
,
Issi
essass
st
-------
-------
-------
f PA-OU WU
_!_
if
_!_
19
i«
'1
'.•.
.11
J.1L
11
?•
If
"
II
»•
»
fl
«
77
«
if
i<
f7
»«
11
<•
—»T~
KM
0.0«
00«
0.01C
001<
030C
O.IK
o.ooc
0.041
o.tia
I.OOC
IOOC
100C
10M
o.ooc
o.ooc
o.ooc
oooc
oooc
2 IOC
O.iOC
o.ooc
o.ooc
o.ooc
O.OM
0.910
o.ooc
oooc
04M
0424
04K
oooc
oooc
0010
0.010
0010
0200
0200
020C
1 OK
OIM
3130
0000
O.OM
0000
O.OM
0.070
0020
0010
OOM
0140
0010
OOlt
0010
0 110
0 IM
0.330
0020
0220
0 120
0 020
0 IM
0 IM
O.OK
O.OM
O.OM
0070
1.0M
O.OM
0003
0014
0 OM
O.OM
0 OM
OOM
OOM
OOM
OOM
OOM
0.00$
ooot
0170
0030
1 IM
0 770
2300
0320
0 OM
0000
0001
OOM
0 IM
0 OM
0030
OOM
»«"*>
"""•I
1242
I2M
*,«.<
1210
"
101
r"
U3
13«
121
***»
M^MMtof
Oi«tJ»n
btr1
-
i
M»i
1
'.g.21
-------
-------
JUtL|
Oil
, 'U
114
til
J3J.
til
til
141
241
IO
241
147
141
lit
lit
HI
114
111
til
II*
"£
Jli
110
It*
nt
114
111
117
111
111
170
171
171
171
V*
171
171
171
110
111
III
til
114
111
111
117
111
111
110
111
lit
111
114
111
til
2*7
111
211
100
101
101
101
104
101
101
107
101
301
310
111
lit
111
114
111
114
117
111
111
110
111
111
111
114
J?f
in
117
111
111
-122.
fits —
«*gr —
2S
»»^>u
"i"*""
**•»
*"•
4.0001
00001
0.0007
00007
0.0011
0.0004
o.oooi
4.0001
4.0001
4.0001
O.OH
O.OM
0.001
0.00)
0.001
0.0021
0.0077
O.OOM
OOOM
0.0047
0.0312
00404
0.107
0.07M
00471
00704
0 111
0.177
0 112
0.134
0.111
O.I 11
041
.301
14*
.314
.421
073
O.OMI
0.127
O.OW*
0 123
0.1
0.0*71
O.OM2
OMI
0447
05|4
( 010*
0223
(0071
0131
0144
0421
0271
07M
0.020*
0 0211
031.3
0.0321
0011
0.0241
0 0121
00113
*n*»
1142
*»*«
1242
1214
12*4
1210
12*0
il
»
1101 I
111 j
111
1*1
111
1121 j
121
1
US —
no
i
]
1
I
i
1
j
***
104
: ; [
• ]
1 •. ;
i '
; i
1
1
i
»'*
m — |
DOTi
OOTi
•^•H
M^««^'
Dt«Mrx
«*"•
U»J
Lfc-
!
i
t^*
**»•«
1000
BttSL
(
(
- •
-------
.211.
Ml.
4333.
^
J1I
"1
55
Oil
411
ft
Ml
«•
**
*H
.us
>M
5s
JM
JU.
"».
-Ill
n«
[HI
»•»
^•5:
M§
.»?«,
.111
571
J7J
SI
IJTI
-Mi
1»T
iifil
171
.?•«.,
311
m
111
m
i»
in
117
?•?
JSl
Itl
. 1,M,
Oil
in
JSi.
40t
1^?,
401
-in.
401
-i£l
407
401
401
«J».
411
41J
»'?
4 4
4 f
4 1
4 7
4 1
« •
410
4J1
491
411
414
411
«?t
417
411
1 "*
43f
411
4?t
411
-Hi
411
«»*
; 440
r~3T~
»*=_
[—"
| *J
Fiy»jgtun
1 «<
tu»
[— *t
»•»
• AM
0.00*1
00441
OOTM
..««"«
o.out
OOMI
««»•
OOJM
00»47
O.OJ74
00111
00114
OOMI
OOJ44
oom
«»»»'
•M*
«•««'»
00011
OOMI
»o»«
0.0177^
»«»««
OOJl^
00071
OWMll
ooottl
0.007^
00(M«J
0.007^
0.00411
0.00*7
00101
00101
000*4
0.00*1
0 0101
0.0071
o.ooa
0 0011
00071
OOWJ
0.021
00177
ooan
00301
00311
o.oiia
own
00307
00*41
00111
00241
OOMI
r«i«i
-ML.
*»^
1141
_JB_
A»»H»«
12*4
_aa_
lUMttt
11**
pq
»
rsn
101
«»
It*
IPA44
~««~
111
u •••
111
in
~*"~
121
1
_&2_
110
_4H_
101
_JHL_J
10*
r««i
XXTi
0001
o.ioa
1 021
ooo;
0.01
0001
o.oo;
0011
0001
0 OOi
0 001
o 02:
-«4
"»»»
1
00*i
OM1
1
0771
oua
007(
1.1
1
0.1W
00*1
O.OT:
1.M1
0**
O.M1
000
000
0.00!
0 Oft
>*»la«la»
00.
in<
0.0*1
0011
0.011
0.371
0.0
OK
«.01
SO
DM
ooos
001-
0.231
1.TI
01*1
4.071
0.171
0.00
00»
*la»tn
iKj
1
•"*""
.M»»i
-------
u
i
88
!§
«
!
is
!i
h
.;;
•-
ss
1
1
J
------- An error occurred while trying to OCR this image.
-------
sc
Is
iSIE
88
88
§335
ii
§§§
E
inJrLL
1-1
-------
-------
sl
M
slsls
38
III
111
1 LI
Ii
ii
11
ii
U
-------
-------
IPA4M <*•»»
-------
*t
SI
LIU
ty
'?»
'11
^ff
r>i7
114
EH
1t<
'If
.in.
11*
Jit
HI
Lml
i«
JJ1,
.Hi
141
.121
14*
-ill
,.','•,
,'U,
tit
'•?
"1,
i»
'Jt
117
Ml
111
110
'•'
*
»»K»*>0«
•a
i
E_
tl>.hHKh»iK»fi»
•«
na •>!(%•*•«•
II—
MMM
«<
•» j
««•
-JS_.
""»*^
10*>
o oon
930*
-------
-------
I
K
Is]
-------
-------
I I I I I I I I I
*
i
o o
Wl
o *
s J
s It
i
=1
i=
-------
JE_
on tua-
,»di*H«lh»*
.li.ni.nhi.Mn. nMUMI»»
*****
-111
| 7"
I >I4
i 717
Uu
usi
^11
211
-------
togtM
-------
-------
-------
-------
-------
??
L.II
ft
lUi
1"
»
11
»*•
Jit
?»•
SI
»»?
LUI
114
ill
?M
JU
.111
»•
l»
7i?
14*
in.
»«
ju.
147
ill
«•
Tif
in
in
JU.
»4
lit
It*
-Ul
TM
Lajl
»•«
T5?
"?
UtiJ
i*i
!«
liT
»1
.US
in
ITS
?"
Oil
17*
?"
in
ill
JiO
?f
MI
,Ui
114
IK
1M
?M
tit
?•»
>M
in
?M
in
?M
117
?M
Zll
jai
304
»9»
jj£i
101
-HI
no
ill
in
Jii
J14
111
H»
n;
JII
in
ill
111
ill
111
U'
Ml
in
ill
"1
321
"
m.lK,l-
tmmmtmim
'•"•••".I-
«
0.1
«.M1
II NUMMV
mweoi
Tnt
O.J33
l^rrwrtJOtl
I '?!
O.M
0.17
Oil
IJ
0071
0.31
0043
0.014
Oil
o.a
OOM
0011
o.oia
on
— a_
1.3.1-lfl
•*»"""•""•
l.l.l-lrl
«»
ixaxoc
OMO
IO.MO
0.041
«a*.oc
1.741
'Ml
0.4*0
T*T*
I.M7
I. Mt
iTIO
1131
>. Ml
.Ml
1»
l.00«
O.M3
'.411
Illl
'.Ml
o.ta
'MO
Ml
.404
Ml
Ml
1*3
Ml
171
Oil
.3*1
Ml
.017
•1*
.717
Ml
.000
.Ml
.107
.111
.3*1
.Ml
M*
.111
.1*1
11*
_ju
o
••"•PC
O.Moi
1.111
U»»40C
11*0.117
1*3*
H7M
11 171
11.131
0000
MM3
141*
7M*
L*il
1 10*
3.171
1471
11.MO
<3M
• on
1171
0000
Mil
B—
r>HP»oc
••**>
1.1M
BW.OC
'™T
1214.111
• 3M
"1M
172*3
172*71
0000
1171
'»•»*»
37*1
1.1(7
"»'
0133
• in
7011
1 4M
S131
S.I14
1000
0.000
11.17*
«
00011
0.0011
0.001
iSSl
IOMJ
IOMJ
&001
o»i>
0.03
101]
&*» »»
L!4
110
eiotriiMi
°-»*»
LI
103*
iSSl
ooot
»00»i
iS*i
OOM
0031
0001
0009
0011
0013
0003
0001
OOM
0047
"
«•«•*
»»o««
»»•«
»»"
2A.
»**
0.01
»•»'
0.004
III U*~**~
*<*i*C*Ci>
ll
C1MT11111
«i
007)
«"77
o.oo:
••"
00*1
o.oot
<0001
0001
0001
0001
0001
0003
0073
]
I
aj
— ooen
— &OOJ;
— »**««
— ISOii
2J3
12.
Ill
«"»
LHZ
0.*7
1«I
C3MTI1MI
O.OJ
U
0.11
1SJ4
0001
.O.MI
101
»•*•*
rtOOl
OOM
0.00*
<0001
<0001
O.OM
0001
*»«
"^»~
1
as
a**"""!
I*""*'*
»•»"
'Of
»»»«
»«««
0«M
«-»M
0.001
0.011
«-»»T
«0.001
«"••*•'
"rl^lPl
«.«
*2
«»
O.M
0.11
»«"
oo«
*•'«
o.oa
0.11
«••»
0.001
0001
0.0*1
*.««
o.on
0.01
o.oa
0.41
•»«
"X"
«•"
1 &
0.71
?'t
»»*
»•«•
»1»
••**»
O.M7
0.11
OOM
0001
o.oa
0.03
OOM
O.OM
O.OM
ox>
Lml
MX**
»«4
— 11
0.11
»»y»
«»•*
««•»'
»»"
»••*«
<0001
0.01*
• «*
-------
*
4fi
»»«
#
JU
«f
-111
>.u
LUI.
Jil
Tfft
111
ill
lit
IE
.ui
ou
.MI
55
S3
HI
117
LuiJ
littl
Ml
"1
UnJ
1M
,?,".
->I»
JZ1
17t
111
.lit
"*
?ft
?f»
!••
Jf7
>i«
w
i to
'•'
•itt
;?M
JIM
?fl
1M
?»r
Hi
in
<00
111
«?l
111
401
101
•?»
407
40f
410
411
«'l
111
414
i 4M
411
III
4fl
i 4](
[417
lit
_12i
«*'.
uiU.
43i
Hlil
1111
ML
_U1
-lit
•fn*thvl-
=5=:
i.j.t-ifi
••BHHMIMIII
MM
4M
M»
>UT
.141
'»»
.171
J»l
-»J
JIM
•»«»
J1Z
»Jt7
an
^HJ
TTl
J4J
JH
DMt
Mil
101T I
rui 1
1.0M I
1.4M I
»t«t
• 11
74|
JM
t.»4
Ml
•M
.411
.711
.Ml
.ait
041
Oil
ati
.in
in
.01)
.171
101
000
.701
111
UO
170
.Oil
241
Ml
7M
JOT
4»7
470
4M
.Oil
.Ml
.177
.441
too
.714
i-mss:
01
O.I
OIH
019
007
0 17
001
2
It4
j 2J
«J«
001
041
012
tl |
j
|
1
1
T
j —
-------
-i
-------
ff
ft
8
8
I
1
=
995
99999
I
-------
-------
!"77f
"7
"f
711
7*1
7»4
'•1
711
707
711
700
711
701
701
r»j
7lf
7ti
7«7
7if
•00
•91
«»
•41
• 04
• 01
• 07
•00
• 00
110
• 11
• 19
• 14
• 10
• It
• 17
• IB
Mi.
•11
-ill
-1U
JU
^
-Hi
Jill
-111
-Ui
-•21
Lilt
JUi
-lii
-ill
Oil
-111
-Ui
rfj
|7
! 17
«Wh>l-
•MMMn*
L2!
iSl
0.01
Jto
OJ
, I*
2J
2
t<
!
L.
•Z
«*
«
*•
H
at
JH
0!
•.'
m^
t»ir
««-W
»•'*»!
1 M
'370
O'M
MJfJ
'«*«
til
2.«
ti
oj.
1 l-lrl
1 «-»-»•"
>
«
0*40
0714
ttti
«"'
nooi
"•«'
tat
»i*
tii
__!OJ»
1 to
• H
1 It
• til
U4IMMMV
0.11
0411
0'0«
>
lomomMi***
4.0*3
Tii
1U2
03*4
0'
tooo
0.0*4
w
..07
04H
««
*
«
4'M
MM
001
a
-------
8
a
a
9
a
:
j,
a
!
a
-------
-------
f'A-Mu
-------
•w
TB~-
TB
"1J ~
•B—
J
i
1
f~ ~
-TSti
TiT
tu
T7TT
•nrr
TT
7TT
tii
TTF
TT77
•sir
•fnr
mr
mr
TnT
•ftoT
TToT
7i>r
wr
tiir
•iT
nrr
TTT
1 >'• i
77T
T!iT
JiT
TiT
^
It—
il.
ITT
foTT
»rr
77T
TTT
rtrr
mn
mn
MI
TIT
7J71
rnrl
TTT
ITT
•7T
RT
7TT
WT
ttT
TTl
trn
Tfil
TTT1
""M
ivr
•srn
TTT
7»T
im
77T
TR-
T»T1
T7T
WT
«rl
»rr
Tti^
nr1
s«r
TT
RT1
ITT
i5T
SIT
iTT
BTJ
JFTJ
ITT
FTP
TT
TT
TT
Fir1!
TT
TT
-------
TS-
i
100 0»
wo>
io7~
00 0>
»0
« 0»
I'O
iotSco
13— f-
tMO
SoTo —
100 O>
100 0»
MOO
1000
MOO
MOO
I000>
toTo"
'000*
tooo
200
fl
IwiHw
« |
EOOO
1000
MOO
JCO'O 1
1000
WOO
1000
XIOO
i
coo
lotl)J13
T5—
ifo —
ism
too
>oo
*o>
(joj,_
«0
~o —
oooTT
00
ntmo
iB
(iro—
coco
1 100
1000
1100
cooT-
1100
:i o
EOOO
100
KO'O
l»
^mt
m.TW
^•1
^•1
—
•8S-
Otl
in
in
TH
TT
fit
IT!
in
in
CM
MC
fit
ur
TiT
oTr
•floe
lot
•or
far
TnT
7ST
me
ToT
nr
liT
nr
XT
fir
toTF
itT
wr
TiT
titT
tT
•r
ITT
K
TiT
ST1
/r
r/rr
XI
PTTI
PcTT
7T
rnr
roTT
ir
ST
7?r
ir
~TT
ii
rr
rni
mjj
r
-------
lit 1
lit I
tit I
tit i
lit i
Itt 1
Bit
lit
tit
tit
|it
fir
-------
-------
-------
1
J.
1
1
1
!_
i
i
»
A
i
i
.i
i_
"
«
IT
'•
.»«
"•»
"••
n
r
r
ia
*
Pa»*»HW
12
12
. '2!
121
1*1
13C
113
114
13!
137
111
141
!«•
147
ISO
151
1S9
172
112
**4T
IIS
in
119
1(2
193
194
19SIC
t»«IE
197 i
1911
199 I
200 e
202 1
203 1
2048
205 B
20118
207 B
201 B
: 1 — ; —
Baaaw. 19(7 a and k
Baaaaa. 1917 a and b
laaaaa. 1997 a and b
HBaaoM. 1997 a and b
BaaaM! I9a7 a and b
taaaaa. 1917 a and b
aaaaai. 1997 a and b
MJMM. 1997 a and b
taaaaa! 1917 a and b
la«K.. 1«» a and b
Sanaa. 1997 a and b
taaaaa. 1997 a and b
MOM. 1917 a and b
*•«••• '«•» • •"""5
•MM. 1917 a and b
BMOM. 1997 a and b
Sanaa! 1997 a and b
Sana.. 1997 a and b
Baaaaa. 1997 a and b
BaaaM. 1997 a and b
aaaaai. 1997 a and b
Sanaa, 1917 a and b
Baaaaa. 1997 a and b
into. 1917 a andb
Baaata. 1917 a and b
BaaaM. 1M7 a and b
BaaaM. 1917 a and b
BaaaM. 1997 a and b
BaaaM. 1997 a and b
BaaaM, 1917 a and b
BaaaM. 19(7 a and b
Buata. 19(7 a and b
Mau», 19(7 a and b
laaaM. 19(7 a and b
la«M. i((7 a and b
laaaM. 1997 a and b
iaaaM. 1997 a and b
laaaM. 1917 a and b
laaaM. 1917 a and b
laaaM 1W7 a and b
laaaM. 1M7 a and b
laaaM. 1917 a and b
laaaM. 1M7 a and b
laaaM, 19*7 a and b
laoiM 1917 a and b
laaaM. 1 9(7 a and b
laaaM. 1917 a and b
laaaM 19*7 a and b
laaaM 19(7 a and b
laaaM. 1997 a and b
laaaM. 1997 a and b
«aaM, 19(7 a and b
•BOM, 19(7 a and b
•outo. 19(7 a and b Is
1 •
STFP am* MB*
;ig«^«« *•"•, —
ITFP outfall aiana
STFP outfall uana
[STFP outfall Mna
STFP outM! aiana
STFP outfall aiana
tTFP outfall Dana
STFP oulMI uana
STFP auKM uana
ITFP outfall aiana
ITFP outfa* alana
iTFP oullall uana
TFP outfall aiana
STFP oullall aiana
STFP outfall liana
TFP ounall uane
TFP outfall aiana
TFP outfall uana
TFP outfall aiana
TFP OUIMI uana
TFP anno* Mna
TFP outfox Mna
TFP outfall aiana
STFP outfall aiana
STFP outfall alana
STFP outfall anna
STFP outfall Mna
STFP outfall aiana
STFP outfall uana
$TFP outfall uana
»TFP outfaa uana
ITFP outfal uana
>TFP outiaH uang
ITFP outfaa Mna
ITFP omlaa Mna
ITFP outfall uana
ITFP auttui uana
ITFP autlM uana |<
ITFP outtui uana
STFP outf.il uana
STFP outfUl uana
ITFP outfall uang
(TFP ouriui uana
ITFP outlaw uana
iTFP autfUl uana
>TFP ouMm uane
ITFP outfall Mna
>TFP outtaK uana
ITFP outtM «na
TFP outtui along
TFP outton Mne f
tTFP outfall Mna If;
TFP outfaN aiona I
TFP outiui uana If
*'•"
*«»'»
A1S1J
*«*"
A2B12
*««»
A3B11
\»ia
•'an
i2bll
03611
a»1J
rtaii
«»'»
«»"
«»»"
«»»'»
'»'»
">«»
»*"
4012
4btl
"»»'
022
»»'
2b22
2b21
»»'
»« I
'Ml
«•»
"»«
MM'
»»'
•»»
M<
»»
12021 |
•»'
021
»«
o»» i
I2b21
a»»
nb2i I
13021
»»
11021 1
M»
ib2i 1
b2l
'»»»
2b23 |
Ib21
*»" '
«»««
4223.1
4222.96
«»»»»»
**«-ty
4223.2(1
«»«»»
4222.92
4220.244
4220 521
4220.521
4222.191
4222. ISi
4223.328
4222.9S
««».(*'
4223 311
«2i ua[
4224 0741
4224 015
4224 Ol|
422374
4223 73
4223 714
4223 391
4221 437
42 20.21 9|
4220 113
4219129
4219(09
4220.531
7053.91
70S3.SK
7093.11
MB*.**
70*1.444
^««»
70S2.M
70(1.93
7080394
70S0.39
7050.211
705022;
7053*21
7051.195
7051.474
^<»»'»«
7050.213
7041*91
7°«»»^
*>««.«*
7041 139
7041 947
7041 9*»
7041 452
7
-------
-------
88
88
I
i
-------
HI 0
PS
r"°
li«re 1
ICO
HO
100
100
00
CO'O
100
too
ico'b
too
noo
100
too
so'o
Cl 0
zoo
too
900
(00
10
iOO
00
00
{00
ore
II 0
iro
coo
010
•00
• 10
:tl'
>OE
tov
>to
•0
Itt
ilE
III
[•t
ItO
1
M
A
etE
Tt
i\
n
X
- •
• >
Hi
iE't
;o?i
» t
il t
It'S
l» t
M'CI
IC'tt
It It
IO'(I
It IZ
U'tr
wt»
It OS
U.'tl
rc'tz
rt IE
it n
it it
Wff
not
rt it
rC'*«
» IS
MZ
10'S
I^'EI
KOI
n't
IS
tort
1C
t»-»t
IZ'EI
»
e
4
o
N
PI
tso
«T5
E»TE
ttTT
ml
ZFo
an
tc o
tE 0
M 0
90 0
Et 0
El 0
•t 0
EC 0
K 0
It 0
91 0
V£ 0
10
1C 0
to
rt'o
M'O
ti 0
no
rto
wo
M'O
•C'O
IE'0
IfO
•1 0
EZ'O
ic o
11 0
C9 0
It 0
">
TT
TT
—
tTT
MI
lit
1C I
'*'
>lt
CC 1
EEI
ill
1*1
Itt
• il
Li 1
til
Hi
tii
Cil
til
ill
til
191
'•
Ml
1*1
Iti
>tl
ttt
It I
itl
191
•1
91
*«
•<
it
-------
-------
IMl
• 4
ff
••
It*
*•!
l«»
191
111
IU
114
111
ltt
Us
TM
!»
rn
MI
ta»
77!
14»
14.
l,!«l
"I
1M
111
"•
h.oj
b»J
!•»
••
•'
••
170
"TST
— ttl
_ — ass
17.2.
13.11
JO 14
33.M
S2.lt
24.1!
M.17
31.1t
10.7*
31 .4*
M.OS
t.72
21. M
4122
It!
21.27
2313
23.1*
2255
2121
55155
31.42
44 11
112.
20 2«
SIM
304S
40.3
67 IS
».4«
_ UJ
17.11
I.H
42.
'«*«
l.«
11 M
12.M
1S.M
11.33
31.1
431
1*1
1114
4.51
771
4.71
4.0t
3.1*
t.ll
7.72
10.143
1.741
11.14
7472
U.WI
II.MI
1.122
1.0711
_..„ , '*•»»
'»
21
121
»"»
1.745
SM
=•
11
3.31
&M
It
M«*
i*,»7
*««
1107
"-»
25.32
| ZZJS
Mill
I aa
iTii
21.11
»o««
27.41
MJ
M.M
»«»»
»««
Jta
»ii
22.M
'«»'
«*.M
33.17
'•«•
"0*
y
"•«
15
"W
120.M
ZiS
"•«
52.121
<*•'•
»«'»
'»o«
»
4.71
121
'T»«
10
»'•»
11.1*
32J|
4S__
«•
«'*«
0.201
»"•
0.1M
0.119
SJH
«"
o»»»
«JK
0.077
«"»•
0.117
o»««
»B»*
«»»«
3
0.173
'»*»
O.OM
°»'»
1 ^
&*j
U*
ill
U«
I.M
»«
7M
4.77
LS*
.11
su
1.71
!i«2
1*
i«a
iSZ
L*
S.I
Mj
US
3.71
">"
S.02J
LS2
i.ilj
1«»
5.131
L!»
'»«»
"«»
'»«
1..3
ZJSS
1.242
N
*"
24.SI
»•*«
iSi
«»««
1»
— «a
Ml__
fti
4i
• 14.27
1.79
10.1
2..W
32.14
14.11
Sill
"««
M«*
10.32
U.71
13.M
«^»«
12
14.15
««
13 1<
20.0!
21.1
31.1!
40.'
23.11
!1S!
»M
»«>
zn
7S4J
SLM
M.12
^M
«*M
»«•«
»
1»>
»»»
"•
-------
i * fM dm «M< 0*1
11
'»
TT
»»
'•
T*
??
?'
*'
u*.
»1
»«
M^
SI
L>jJ
11
.*»
,?..•
»•
"
.?•
«•
LiiJ
««
.«!
47
«•
41
LuJ
H
Si
"
IT.
SI
••
>»
LI
••
17
• •
L£
'0
''
•a
73
7S
•
•
10
1
I
9
4
1
•
17
•
1*
•
1
»
i
*L
TTW5
- ««a
0.03
0004
5!o"
O.OM
o.o»
0.02
>*
*
o.«
0.02
0.001
0.001
0.02:
0001
0.001
0.001
0.001
0031
0.02!
0.007
0.01 1
nd
0.019
0.021
0.001
0.001
0.009
t
0.003
0.012
0.00*
0.001
0.00*
0.024
0002
0.003
0002
0.002
0005
0.004
0.003
0005
0.000
Ml ..
1 '
— ffi_
— it —
•a
««
j
*•
*T
*"
*»
*•
-------
WA dm MX tm
it
£
£1
*•
1M
121
1*1
H,
b«rJ
LM
"J
Ml
Ml
Ml
111
L!
in
L J
UJ
Mi
U4.
IIS
'?T
in
lit
in
'.M
131
111
114
111
11»
117
111
111
141
141
141
14J
144
141
141
14T
141
141
1>l
111
111
1IJ
114
111
111
117
III
111
1*1
1(1
1*1
1(9
1(4
1*1
1*1
111
1 *l
1*1
171
»*•
OOOJ
O.OM
1 0.0311
0.031
0.004
000*
1 00311
0.014
0.007
0.00*
0.014
O.OS2
0.021
0.019
0.001
0.000
0.021
0.047
0.017
0.014
0.01*
0.017
0.003
0.001
0.003
0.003
0.004
000«
0.01
0.012
ooia
— m —
*N
- |
•»
"~~*5 I
*»
" 1
i
— il —
*"
*»
*»
— *»
-------
i to f M
_1_
LJL.
(_!_
..!_
_•_
JJ.
"
LiiJ
?•
Ji
.11
ii
?•
ii
-£JL
21
it
>f
»«
it
,ft
ST
t
. 1
1
»
4
I
t
7
. t
f
t
11
»?
«»
14
II
1*
J7
(1
«•
tt
11
'»
tl
•«
II
t«
>'
tt
>•
Tt
ri
M
71
'«
T»
»•
77
T«
*•
It
It
II
»
14
II
••
17
II
If
>•
•1
It
JLJ.
•»
M
M
,
I
•
.
«?
- •
I •
| 5
H__
*
U—
'
*» 1
«
-------
-------
>• IM
_1_
.J
n
tT
i«.
.3.1
11
J?
m
UiJ
01
4 1
41
44
41
44
47
4t
4V
>•
Li
14
I*
LL
1 •
!•
l*
1 1
•a
84
it
IT
4C
7t
1
^
73
'4
71
•
77
•
•
•
1
2
^
«
If
•
17
•
•
•
1
f
0.0*
OM
000
04(3
0 43»
0.12!
0 001
fl
0 004
0.014
0 001
0. 141
0.001
0.004
0 Oil
0 033
0 031
0 321
OMI
0.432
0.347
O.OtJ
0.121
0079
0 1ft]
0171
0.04
0 041
0.043
0 1S1
0.147
01*7
0
o
0
00*2
002
0043
003*
0 14
00*4
2
- *•
»
i
i
i
i
i
-------
s
I
-------
IOWA I
JL
J.
•
J_
11
11
11
U
"
"
u.
If
u
»«
11
If
''
I
»
i;,
»<
1?
11
»•
it
!„',
»•
»•
«•
in
41
11
««
•«»
«•
«'
Af
«•
!1
11
>*
>»
14
1»
14
'»
11
>f
>•
11
LI.
S3.
14
'•
'•
'»
'•
LI
'0
'l
'?
'»
'«
11
'•
TT
±
't
I*
11
'»
l»
l«
If
I*
IT
'•„
'•
'•
''
»
±
ir
B
0 M
e.ia
o.oa
o.oa
0.04
0.01!
O.Oi
O.M
O.I«
O.MV
o.7i
0.541
O.MI
O.MI
0.01'
o.«
o.ai:
O.ttl
0.01
0.01
00*
0.1*
O.lti
O.tM
0.001
(
0.001
0.141
o.on
0.104
0.1«
0.071
O.OM
0.001
«
0.001
O.OOj
0.001
O.OM
0011
0.034
0.003
O.OM
O.OM
0.1*4
0.004
0.004
O.OM
O.OM
0.041
O.OM
o.4oe
0.239
0.4M
O.MI
0.241
0.3M
O.OM
0.171
O.OM
0.141
0.1M
0.13J
0.0*1
0.047
O.OM
0.11
0.211
0.1M
0
o
e
O.OM
0.071
0.03)
0.1M
0061
0001
0
0.001
0.003
0.001
0
0.003
0003
ee —
•
•
5
3 ft
1.4
1.41
4.4
4.C
0.01
o.w
4.01
t.41
0.21
(.21
SOI
2.M
5.75
O.M
3.11
3.M
*.H
0.04
2 IS
2.M
2.M
1.4J
2.M
1.M
O.M
4.M
2 04
2.M
1.M
4.M
S.M
1.41
44 M
3.39
I.M
4 S3
3.39
2.M
3 13
11. 43
2.27
7.M
3.33
1.72
Sit
15 W
2 00
S.M
4.11
4.01
4.21
2.12
3.M
5.24
1M
2.M
1 M
12S
1 M
000
1000
7 JO
1 IS
034
220
ISO
1 20
007
420
3.33
2.22
7.14
447
5.00
4.17
600
tt 0;
10.*
39.01
10.01
11.0'
o.o:
I7.1i
Ta.i:
to.o
72.0.
12*1.01
M.*j
40.7.
13*.*
24.01
Tt.*
10.01
32.04
10.M
10.04
f.1!
17.41
20.fi
Ufi
0 0(
0.01
0.0(
tt(
O.Oi
24.4i
4S 21
10.*4
21 .M
40(
0.0(
1.0J
1.01
O.OC
0.01
3.11
12.M
S.0«
0.41
1S.OC
10 23
7.14
1.03
2.M
5.49
S.ll
22.04
273.39
20 70
78.71
71.11
5444
40.S7
10.04
00.33
34.21
10 f7
1704
2O.t9
0.71
OM
11 04
1§.57
30.03
2403
0.00
0.00
0.00
S.M
1 27
12. Jl
1200
74»
21.33
0.00
0.00
0.00
000
0.00
0.00
0.00
000
fr"n*°6
24 1'
1f.«
17.3!
0.3!
13. f
24.21
07 0'
00 71
00 IH
160J1
SO.*
40.4!
3*2.01
12. li
10004
17 M
24.01
12.fi
20.01
7.M
10. 7!
25.71
10.24
1 4i
0 0(
2.K
17.31
12.41
24.11
110 SI
27.14
21 21
0 M
0 M
1.01
3.39
2M
0.01
2.M
12.M
11.M
13.M
20 M
5.71
1.02
O.M
7.M
7 00
21.11
337.M
24 02
44 M
100.03
45.09
47.71
10.M
03.M
32.M
11.22
16.17
15.03
4 1C
0.71
10 01
1544
52.20
16.27
0.00
0.00
O.M
0.27
2.0)
21.4)
13.71
0.24
17.00
1.43
0.00
111
4.21
1.07
'0.00
2. SO
200
-------
i
£
I-
;
t
I
S
------- |