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i
PREFACE
This report is the final statement on a study of the
nutrients and metals in the sediment of Flathead Lake, Montana.
We initiated this work on June 15, 19 82 with funding from the
U.S. Environmental Protection Agency managed through the Flathead
River Basin Environmental Impact Study. The purpose of this work
was to establish the distribution of phosphorus and the pathways
and mechanisms controlling phosphorus migration. Because the
grainsize, organic content and heavy metal concentrations of the
sediment affect phosphorus migration, we also determined the
sedimentologic and geochemical framework of Flathead Lake
sediments.
Because Flathead Lake is a popular recreation resource and
the drainage is expected to be modified by future mineral,
petroleum, and timber production, it is essential to have
detailed baseline data to monitor future changes. Aesthetically,
Flathead Lake seems completely pristine, and its waters have been
classified A-open-Dl, the highest water quality rating of the
Montana State Department of Health and Environmental Sciences.
But recent aquatic chemistry suggests that the lake lies at the
boundary of the Oligo-mesotrophic (Stanford, et al., 1981). If
this is correct, any changes in the nutrient budget could have
significant effect on the lake biota, chemistry and water quality
and, therefore, recreation potential. The basic goal of this
sedimentation study is to determine the history of sedimentation
in the lake and the relationships between nutrients and metals in
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the sediments. We have developed models that explain nutrient
and metals distribution as well as establishing baseline data on
physical and chemical properties. This data will allow changes
in sedimentation, nutrient input and trace metal concentration to
be monitored and responses of the lake predicted. In the last
chapter of this report I discuss possible future scenarios based
on our present understanding of sediment-nutrient interactions.
The fieldwork and analyses presented here result from two
years of work by faculty, staff and students of the Geology
Department of the University of Montana. We thank all the people
and agencies that aided in these two years of research. The
scientists and staff at the University of Montana Biological
station gave us logistical and analytical support and many hours
of helpful discussion. The secretarial, professional and
computer center staff of the University of Montana helped
throughout data collection and report preparation. Specific
thanks to: J. Bibley, S. Vuke, B. Wall, G. Thompson, L. Hanzel,
T. Stewart, T. Qamar, J. Stanford, B. Ellis and R. Cooper.
Finally, we thank the U. S. Environmental Protection Agency and
especially the Flathead River Basin Environmental Study for
funding this research and supporting us throughout the two years
of work.
2
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TABLE OF CONTENTS
Preface i
Chapter One INTRODUCTION AND SEDIMENTARY FRAMEWORK
Geologic and Environmental Setting I
Suspension Sedimentation 9
Deltaic Sedimentation 21
Summary 26
Fi gures
1. Location Map 2
2. Bathymetric map of Flathead Lake 4
3. Sample locality map 8
4. Clay distribution contour map 10
5. Silt distribution contour map 11
6. Silt and clay histograms 13
7. Photographs of core #4 stratification 15
8. Stratigraphy of cores from central lake 16
9. Seismic profile of lake sediment 18
10. Profile of Flathead delta 22
11. Historic maps of Flathead delta 24
Chapter Two HEAVY METAL DISTRIBUTION
Introduction 28
Methods 31
Results 35
Discussion 47
Figures
1. Index map 29
2. Location of sampling points 32
3. Histograms of sequential extraction results 36
4. Extractable iron contour maps 37
5. Histograms of extractable metal data 39
6. Oxidized/reduced layer ration histograms 40
7. Extractable manganese contour maps 41
8. Extractable zinc contour maps 43
9. Extractable copper contour maps 45
10. Histograms of extractable inorganic phosphorus.. 57
Tables
1. Results of sequential extractions 48
2. Correlation coefficient matrices 49
3. Multivariate linear regression-oxidized 51
4. Multivariate linear regression-reduced 52
5. Partial ocrrelation coefficient matrices 54
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Chapter Three PHOSPHORUS
Introduction 65
Distribution 69
Correlation to other variables 77
Migration and cocentration 88
Figures
1. Extractable phosphorus histograms 70
2. Extractable total phosphorus contour.map 71
3. Extractable inorganic phosphorus contour map 72
4. Extractable organic phosphorus contour maps 74
5. Scatterplot:inorg. phosphorus vs manganese 32
6. Scatterplot:inorg. Phosphorus vs iron 83
7. Scatterplotrinorg. phosphorus vs clay 84
8. Migration status, reduced to oxidized layer 87
9. Phosphorus migration model 93
Tables
1. Variations from reduced to oxidized layer 75
2. Reduced layer correlation coefficients 78
3. Oxidized layer correlation coefficients 79
4. Partial correlation coefficients 80
Chapter Four CONCLUSIONS AND PREDICTIONS 95
Figure 1. Concentration-migration senarios 96
Bibliography 101
Appendix I METHODS Ill
Appendix II RAW DATA 119
Appendix III SCATTERPLOTS 148
End 203
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1
Chapter One
INTRODUCTION AND SEDIMENTARY FRAMEWORK
J.N. Moore
Geologic and Environmental Setting
Flathead Lake is the largest freshwater lake in the United
States west of the Mississippi River and covers an area of 510.2
square kilometers. The lake occupies the southern end of the
Rocky Mountain Trench (Fig. 1), a depression that extends from
British Columbia into northern Montana.
The Rocky Mountain Trench is bounded on both sides by normal
faults that continue into Flathead Lake basin (Stickney, 1980) ,
and Seismic activity around the lake is similar to other areas of
the intermountain Seismic Belt with many small earthquakes and
microearthquake swarms. Although most earthquakes are small, two
recent magnitude five earthquakes occurred in 19 52 and 1975
(Qamar and Breuninger, 1979). Microearthquake swarms have been
located on the southwestern side of the lake (Sbar, et al., 1972;
Stevenson, 1976) and other small earthquakes identified with
faults in the Kalispell Valley to the north (Stickney, 1980).
During the Pleistocene, the Rocky Mountain trench guided
lobes of Pleistocene ice sheets south into the Rocky Mountains,
and multiple glacial events left a complex record of tills,
moraines and lake deposits. During the last advance in Pinedale
time into the Flathead Valley, Poison moraine formed, damming
Flathead Lake. Since that time, approximately 10,000 to 14,000
years ago (Stoffel, 1980), the lake has received sediments from
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Figure 1
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3
2
an extensive drainage (18,378 km ) dominated by the Flathead
River and other less important sources. The level of the lake
lowered from a high immediately following the retreat of the
glacier, to the present low, as the outlet river cut through the
moraine (Johns, 197M. The level is now artificially maintained
by Kerr Dam, constructed in 19 38.
The Flathead watershed encompasses mixed forest and
agricultural lands in northwestern Montana and British Columbia,
drained by six major river systems. The Flathead River is the
major sediment source for the lake (Stanford, et al. 1981)
supplying 90% of the water (Potter, 1978) the bulk of the
suspended sediment and probably most of the bedload sediment
annually.
The bedload is deposited adjacent to the inlet forming a
large deltaic complex extending over 5 km into the lake.
Suspended load is carried into the lake as a sediment plume
during spring runoff in late April to June. The coriolis force
drives the plume against the western shore concentrating
suspension sedimentation there. Rivers and streams entering the
lake supply the bulk of suspended sediment during the maximum
spring runoff. During the remaining months the rivers flow
clear, supplying only a small amount of organic debris.
Flathead Lake contains several distinct bathymetric
provinces (Fig. 2). The eastern part of the lake is underlain by
a deep trough (110m deep) extending the entire length of the
lake. This trough connects to shallower shelf to the west, where
depths range from 24m to 45m. Poison Bay, at the southern end of
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5
the lake, is isolated from the main lake by a narroe inlet. With
depths less than 8m this bay forms the most extensive shallow
area in the lake. At the extreme north end of the lake the
present active delta and an older inactive delta combine to form
a shallow platform with depths from 2m to 5m.
The drainage basin of Flathead Lake encompasses several
major mountain ranges and a complex geologic terrane. Rocks of
the Precambrian Belt Supergroup cover the majority of the basin
(approximately 80-85%, Price 1965; Harrison, 1972). The Belt
terrane is covered locally by a veneer of Tertiary sedimentary
rocks or Pleistocene till which were mostly derived from the Belt
rocks. Paleozoic rocks are exposed in the far eastern, and
Mesozoic rocks in the northern parts of the basin.
The Mesozoic strata of British Columbia contain large
quantities of coal that is slated for development at Cabin Creek
and Sage Creek. This development was the initial impetus for the
Flathead River Basin Environmental Impact Study and remains as
the largest potential contributor to change within the basin as
resources are developed.
One problem that may emerge in the Flathead drainage in
response to natural resource development is the increase of heavy
metals in the environment. Even residential sewage sludge not
containing large amounts of industrial effluents usually contains
enriched amounts of copper, cadmium and zinc which might enter
the environment by leeching as residential development increases
on the shoreline and within the drainage basin of Flathead Lake.
Because of the possible increases in heavy metals, it is
important to understand the sources, pathways and sinks
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6
controlling their distribution. The primary purpose of the heavy
metal study (Chapter 2) is to determine the geochemical factors
controlling distribution of heavy metals in Flathead Lake
sediments and their associations with the limiting nutrient,
phosphous (Chapter 3). This type of study has been used as an
effective tool in determining the levels and sources of heavy
metal pollution in a basin (Forstner, 1979) and should add
considerable baseline data to monitor the condition of the
Flathead River Basin.
The major background source of metals in the Flathead
drainage are the rocks of the Belt Supergroup. All metal
deposits are stratiform and occur as disseminated grains and
blebs in argillite, quartzite and oolitic carbonate (Harrison,
1972; Lange and Moore, 1981). These deposits are a source of
heavy metals and could supply copper, silver, mercury and lead.
However, because they are tightly bound in the lattice of mineral
grains (Harrison and Grimes, 19 70) considerable weathering is
needed to release them in soluble forms. Mining operations
increases leaching of metals from tailings and may significantly
alter the concentrations formed by weathering of undisturbed
rock. In the unaltered state probably only a small amount of
heavy metals in solution is derived from erosion of Belt bedrock,
and it is unlikely that this natural background contributes
significant heavy metals to the biota.
Mining, ore processing, waste disposal, fuel consumption,
and fertilizing can drastically change the normal concentrations
of metals and nutrients within the basin. The large coal mining
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7
operations proposed on the North Fork of the Flathead River offer
a source for soluble metals. Coal use releases heavy metals at
many stages, including mining, cleaning, processing,
transportation and burning. Changing the geochemical environment
of the coal and overburden causes release of metals into surface
and sub-surface waters (U.S. Comm. for Geochem. , 1980). These
chemical changes are most effective in the large volumes of solid
waste produced by strip mining and coal production. For that
reason, the U.S. Committee on Geochemistry (1980) and the
Committee on Accessory Elements (1979) considered solid wastes
the most environmentally hazardous facet of coal use.
Agriculture, including forestry, can also contribute to
heavy metal and nutrient increases by the application of
fertilizers and pesticides. Fertilizers commonly contain
phosphorus and enriched amounts of cadmium, arsenic and uranium
(Forstner, 1979); pesticides may contain significant amounts of
arsenic (Shukla, et al., 1972). Because of the large amount of
agricultural activity in the Kalispell Valley and on the slopes
surrounding Flathead Lake, such inputs are expected.
Domestic sources potentially add significant amounts of
heavy metals and nutrients to drainage systems. In urbanized
areas sewage effuents, storm runoff and refuse disposal supply
most of the leachable metals and phosphorus (Wittman, 1961 ).
Sewage effluents and sludge are often enriched in copper, lead,
zinc and cadmium, mainly from the corrosion of pipes (Preuss and
Kollman, 1974). Storm runoff commonly flushes lead, copper and
zinc into the drainage system (Malmquist, 1975). These sources
may add significant quantities of metals to Flathead Lake as the
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3
Figure 3
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9
shoreline and basin is developed, and urban and suburban disposal
sites contaminate groundwater with copper and zinc and excess
phosphorus (Forstner and Van lierde, 1979),
Suspension Sedimentation
Grab samples and cores of sediment in Flathead Lake (Fig. 3)
show well-oxidized sediment at the sediment-water interface.
This upper, oxidized layer is forms a distinct light-yellowish
brown band from several millimeters to a centimeter thick, at
the top of most cores and grab samples. Beneath the oxidized
layer, the sediment is reduced to light gray and contains streaks
and laminae of black organics. Grain size analyses of both these
layers were performed by seiving (sand fraction) and pipet
analysis (silt and clay fraction). The resulting grain-size
distribution is presented in figures 4 and 5.
The percentage of silt in surface sediments decreases
systematically southward from the mouth of the Flathead River
(Fig.4). Noticable highs in Poison Bay and on the east shore
that deviate from this trend probably result from waves reworking
shoreline sediment. The percent of clay in surface sediments
show opposite trends to the distribution of silt. Clay content
increases away from the source at the Flathead River because silt
settles out first from the spring sediment plume and clays
carried farther. Because of the differential settling within the
plume, sediments in the northern half of the lake are silt rich
(40-80%) and those in the southern half clay rich (greater than
60%) .
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12
Sand and coarser-grained sediment is not controlled by the
sediment plume but instead by river and wave processes. These
processes are limited to shallow water so coarse-grained sediment
accumulates only along the margin of the lake, on the delta and
, , n isolated grains and patches
in shallow bays (eg., Poison Bay;
of sand and gravel are transported into deeper areas at the bases
of steep slopes adjacent to shallow-water areas by gravity
sliding and ice rafting.
The grain-size difference between surface oxidized sediment
and the underlying reduced sediment is minimal (Fig. 6).
However, oxidized sediment contains a slightly higher percent of
silt than reduced sediment. A trace of sand accompanies this
increase, even in localities far removed from a sand source. In
smear slides of the coarse fraction of oxidized samples, volcanic
ash makes up these coarser grains. Ash is absent, however, in
reduced sediment. The ash is identical to that deposited by the
May 1980 Mt. Saint Helens eruption when several millimeters of
ash fell in and around Flathead Lake. The presence of Mt. Saint
Helens ash accounts for the slightly coarser distribution in the
oxidized layer which reprsents the most recent sedimentation.
During normal spring runoff sediment settles out from the
spring plume. By mid-summer all this sediment has reached the
bottom and the yearly algal bloom supplies organic material to
the lake (Stanford, et al., 1981). This alternating
sedimentation results in interlayers of silt-clay and organics.
These laminae are generally less than 1mm thick and form a
distinct rythmic layering that records sediment influx and algal
productivity. The organic and sediment laminae also contain
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13
SILT
CLAY
30
20-
N
IQ-
0
301
20-
N
10-
oxidized
meon 3 36.3
S.D. 3 10.8
N *52
mean=60.2
S.D. 3 I 3.2
N *52
reduced
mtan339.9
S.Q3 19.4
H *101
mean=47.7
Saซ25.6
N *101
On
0 20 40 60 80 100 0 20 40 60 80 100
weight %
Figure 6
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14
detritus washed in from the drainage. This material includes
plant fragments and charcoal.
Unfortunately, the sediments do not continuously record
yearly events because the spring plume often does not cover the
entire lake, is non-existent or very small or may have more than
one pulse. So, eventhough laminae are formed by periodic, annual
processes, they are not proper varves and cannot be used to date
sediment. In general though they record changes through time in
both the lake and the drainage basin.
The thickness of sediment between distinct organic laminae
increases downward in sediment collected by coring in the central
lake (Fig. 7). This thickening is accompanied by an increase in
the thickness of the organic laminae themselves, representing
both a change in organic material and sediment supplied to the
bottom through time.
Thickness and composition of laminae also vary laterally.
Sediment accunmalting on the western shelf, along the main path
of the plume, contains thicker lamiane than sediment on the east
side of the lake. Sediment in the deeper areas on the eastern
side of the lake, where the sediment plume reaches last, also
contain slightly higher concentrations of organics. Sediment
lamiane also increase towards the delta as the grain size
increases
Although suspension sediment in Flathead lake does not
contain true varves they do contain ashes that are correlative
to dated volcanic eruptions in the Cascade Range. in cores from
the central lake, where sedimentation is fairly low, ash from Mt.
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15
Depth (cm) from top of core
225
235
245
Figure 7
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16
Figure 3
Stratigraphy of Cores
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17
Mazama (6600 years before present) was found at 1.8 to 3.3m below
the surface (Fig. 8). The ash was deeper in cores from the
western shelf where sedimentation rate averages 0.5 mm/year over
the last 6600 years. In cores from the eastern trough, the rate
of accumualtion averaged 0.3 mm/year. These differences in
sedimentation rate result from the path of the sediment plume.
Using these average sedimentation rates we can estimate the
age of sediments accumualting under conditions similar to those
in Flathead Lake today. Seismic profiles of Flathead Lake
sediments show an undisturbed package of sediment from 2 to 9m
thick (Fig. 9) overlying an older package of horizontal and/or
disrupted sediment (Kogan, 1981). Assuming 0.3 to 0.5mm/year
sedimentation rate, in most places this drape represents
undisturbed sedimentation for approximately 12,00 0 to 30,000
years. This timing coincides well with the last withdrawl of
Pinedale glaciers from the Flathead Valley (Stoffel, 1980) 12,000
to 14,000 years ago. Because sediments in cores from the drape
have nearly identical characteristics throughout their length,
they must have accumulated under very similar conditions. This
data suggests that Flathead Lake developed it's present
configuration, both chemically and sedimentologically,
approximately 12,000 to 14,000 years ago and has not changed
appreciatively since.
Although the major processes affecting sedimentation have
varied little since the lake formed, sediments recovered by deep
coring reveal changes in relative quantities of organics and
sediment through time. Older organic events (deeper in core)
were larger (thicker organic laminae) and occured less frequently
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^imSmSk
18
Figure 9
Seismic Profile of Stratigraphic units
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19
(greater spacing). More recent deposition shows that more
frequent and less voluminous events supplied organics to the
lake. If the organic lamiane formed entirely from algal blooms
these differences suggest the productivity of the lake has
evolved from fewer, larger blooms to more freqent, smaller
blooms. The same charaacteristics could also be controlled by
sediment influx. If sediment were supplied faster in the past
and decreased more recently, then only the larger blooms would be
preserved as organic laminae becaue the smaller ones would be
mixed with the sediment. However, because the sediment laminae
are thicker and the organic laminae are very distinct it seems
likely that these older sediments record changes in lake
productivity associated with climatic warming since the last
glacial retreat. Suspension sediments also record more detailed
changes as well as these general trends.
Throughout the lake shallow cores contain a distinct horizon
at a depth of from 15 to 20cm below the sediment surface. The
horizon is composed of a pinkish gray mud underlain by brown
clay. Locally, an organic layer is sandwiched between these two
layers. Assuming a sedimentation rate of 0.3 to 0.5mm/year, this
horizon represents an event that occured 400 to 500 years ago,
which correlates to a well established climatic event in
northwestern North America.
The climate of the Rocky Mountain region cooled
approximately 500 years ago and alpine glaciers advanced in their
vallies throughout the Northwest (Stoffel, 1980). This "mini ice
age" lead to more precipitation and erosion and hence more
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20
sediment. Because open lake sedimentation is dominated by
suspension sediment supplied by the Flathead River and other
streams around the lake, these climatic changes were faithfully
preserved in the sediment of Flathead Lake.
In summary, suspension sedimentation in Flathead Lake has
continued since the formation of the present system initiated by
the final retreat of Pinedale glaciers. Sedimentation is
dominated by annual influx of sediment from the Flathead River
and from algal blooms within the lake. These processes have
changed only in relative magnitude over the last 12,000 to 14,000
years because sediment characteristics show no major
modifications, but do record detaild climatic and productivity
changes.
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21
Deltaic Sedimentation
The delta complex formed by the Flahead River as it flows
into the north end of the lake covers over 20 square kilometers
(including submerged portions). To the west of this active delta
older deltaic deposits form an extensive submerged plain
approximately half the size of the present active delta. This
ancient delta formed when the Flathead River flowed into the lake
along the western side of the Flathead graben. The river's shift
to the eastern side of the valley to form the present delta
possibly resulted from the rapid tilting of the graben and
migration of the river until it met bedrock on the east
(Stickney, 1980; Hlebicheck, 1981).
Deposits of the recent delta consist of interlayered fine-
to medium-grained sand and mud. Sand layers are from 2 to 2 5cm
thick with subordinate layers of mud from 1 to 3cm thick.
Lakeward from the delta plain, percentage of mud increases and
mud dominates the delta slope and prodelta sediments (Dobos,
1980). Sand supplied by the Flathead River is reworked by waves
and transported lakeward forming a large, sandy delta plain. At
the edge of this plain a sharp break in slope marks the front of
the delta (Fig. 10). Slumps and turbidity currents carry
sediment down this steep front into the deep eastern trough and
onto the western shelf where it accumulates in a hummocky pile
(Joyce, 1980; Kogan, 1981). The magnitude of this reworking is
unknown but a significant amount of sediment is probably
transported into deeper water by these processes.
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p . w.
DELTA
HIGH SIGNAL
-100 J absorption
-200 J
10342
E,
SHARP TRANSITION FROf1
LAYERED TO CHAOTIC
rv>
ro
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23
Flathead delta forms a large wedge of sediment that
dominates sedimentation in the northern lake, but it has very
few features characteristic of deltas forming in other temperate
lakes. The form of lacustrine deltas is generally controlled by
river processes because sedimentation always overpowers other
lake processes. This results in deltas that fill their inlet
with sediment so that complex channel systems develop on
vegetated deltaic plains. These plains remain emergent
throughout most of the year and flood only during maximum spring
runoff, establishing excellent habitat for waterfowl and other
wildlife. Although Flathead delta once contained all these
characteristics it no longer does.
The vegetated portion of Flathead delta forms only a small
percentage of the delta plain. At high water level (which is
maintained throughout most of the year) a narrow cusp-shaped
peninsula extends into the lake next to the Flathead River
channel. When the lake level is lowered a broad sandy plain
extends for 3 km into the lake away from this upper vegetated
surface. So, the main active delta lobe is subaqueous and not
covered with wildlife habitat. This odd morphology has developed
in the last forty-four years and is not a natural situation for
the lake (Fig. 11) .
When Kerr Dam was built and lake levels controlled in 19 39
the processes affecting the delta changed drastically. Before
1938 (Fig.11) lake levels responded to yearly runoff, staying low
during most of the year and then raising briefly during the
spring runoff. The delta plain formed a large vegetated lobe
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"iir
DEC MAR
1r
JUN
ro
-P.
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25
extending into the lake and flooded only during the spring. Low
lake levels and the forested surface protected the lobe from
destruction by fall and winter storm waves. Since 1938
artificially high lake levels have allowed storm waves to erode
the delta plain. The waves transport sand lakeward, forming the
broad surbmerged sandy delta plain, and mud to the open lake.
These processes have removed up to 1.5 m of sediment vertically
from the delta plain and reduced the vegetated area from 10 to
less than 2 square kilometers. This erosion has significantly
reduced the wildlife habitat on the delta since the construction
of Kerr Dam and in the last three years has destroyed at least
two osprey and one bald eagle nesting sites as well as many goose
and duck nesting. Skeletons of tree stumps are the only remains
of this once extensive habitat.
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26
Summary
We can make several generalities based on the data collected
from grab samples and cores of Flathead Lake sediment:
1) Sedimentation in the lake is dominated by suspension sediment
supplied by the spring sediment plume.
2) Sediment at the sediment-water interface is oxidized, that
below reduced.
3) Sedimentation rates average from 0.3 to 0.5 mm/year with
higher rates of accumulation on the western side of the lake.
4) Similar processes have acted in the lake for the last 12,000
to 14,000 years, since the last retreat of Pinedale glaciers.
5) Since the formation of the present lake system, input of
organic sediment has become more regular and shorter lived,
presumeably the result in changes of productivity.
6) Erosion of the delta results from artificially high lake
levels which has drastically decreased the habitat available for
wildlife.
7) Some unknown amount of sediment is reworked by wave action on
the delta plain and along the shoreline.
Within this system heavy metals and nutrients are collecting
along with sediment and orgnaics. Grain size distribution and
sediment composition affect the storage and migration of metals
and nutrients within the sediments, so the sedimentary framework
presented in this chapter is important in considering the metals
and nutrient models considered in subsequent chapters.
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27
Chapter Two
HEAVY METAL DISTRIBUTION IN THE SEDIMENTS
OF FLATHEAD LAKE, MONTANA
by
Christopher J. Murray
Presented in partial fulfillment of the requirements for the deqree of
Master of Science in Geology
UNIVERSITY OF MONTANA
1982
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28
INTRODUCTION
Flathead Lake is a large freshwater lake, covering 462.3 sq. km.
in the Rocky Mountains of northwestern Montana (Potter, 1978). The
drainage basin of the lake occupies 18,400 sq. km. (Potter, 1978) in
Montana and southeastern British Columbia (Fig. 1). Argillites,
quartzites, and carbonates of the Proterozoic Belt Supergroup dominate
the bedrock geology of the drainage basin. Cultural development of the
basin has been slow, with a small population, and an economy based on
logging, farming, and catering to the tourist industries. Flathead
Lake is the largest natural freshwater lake west of the Mississippi
River (Joyce, 1930). Considering its size and long history of use, the
lake remains largely unpolluted.
Recently, however, development in the drainage basin has increas-
ed dramatically. Exploration for coal, oil and gas are underway
throughout this part of the Rocky Mountain Overthrust belt.
Development of known energy resources has either begun, cr is in the
planning stage. For example, Rio Algom Ltd. has applied for permission
to begin strip mining coal at its Cabin Creek property on a tributary
of the Flathead River in British Columbia. Minerals companies have
been exploring the drainage basin for base and precious metals,
economic deposits of which have been found in the sedimentary rocks of
the Belt Supergroup west of the Flathead Lake drainage basin. These
activities, along with the general trend of population growth in the
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29
Fig. 1. Location of watershed draining into Flathead Lake.
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30
Rocky Mountains, have increased residential pressure on the area, with
concomitant increases in sewage, automotive pollution, and erosion
(Potter, 1978).
The study of sediment metal contents has been used previously to
monitor the environmental health of aquatic systems (Forstner, 1982b;
Crecelius et al., 1975; Goldberg et al., 1981). The study of
extractable metals is particularly applicable. Extractable metals
reflect the metal content of the sediment that is readily available to
the biota. The purpose of this study was to document the present
levels of extractable Fe, Mn, Cu and Zn in the lake sediments, and to
interpret the geochemical factors controlling their distribution. That
knowledge may be useful to future researchers in studies of Flathead
Lake and its drainage basin, and in monitoring the effects of present
and future development.
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31
METHODS
Sampling and Preparation
Sampling was performed at 110 sites during the summers of 1980
and 1981 (Fig. 2). Surface sediment samples were taken with a Peterson
clamshell dredge. Wherever possible, subsamples were taken from the
upper oxidized sediment layer, and the lower reduced layer. These
layers were recognized by a distinctive color change from gray in the
reduced layer to a rust brown color in the oxidized layer (Price,
1976; Berner, 1981). The separation of these subsamples was usually
not possible in coarser, sandy areas, such as the Flathead River
delta. The samples were stored in clean polyethylene containers, and
refrigerated at approximately 4ฐ C.
Extraction
After drying, the samples were extracted with a solution of 20%
acetic acid. The metals released by this extraction are weakly bound
to the sediment, for example, in pore water, cation exchange sites and
carbonates, and physically adsorbed to mineral and organic sediment.
The metals bound in this fashion are assumed to be readily available
to the bicta if the chemical environment of the sediment changes (Skei
and Paus, 1979)'. The extraction was performed by placing one gram of
sediment with 25 ml of 20% acetic acid in a Nalgene Screw-Cap test
tube, which was then placed on a mechanical shaker for 12 hours. After
centrifuging, the supernatant was decanted into Nalgene bottles, which
were kept at 4ฐ C until the samples were analyzed.
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32
SOBERS
BA Y
'
sc
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J
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33
Sequential Extraction
A small number of the samples (Fig 2) were selected for a sequen-
tial extraction (Chester and Hughes, 1967; Gupta and Chen, 1975; and
Forstner, 1981). The extraction scheme used in this study was a
simple, two step extraction.
The first step was identical to the acetic acid extraction pre-
viously described. After the sample was centrifuged, the residue was
washed and dried, and a 0.25 gm. subsample was taken. The subsample
was fused with 1.25 gm. of sodium carbonate in a platinum crucible at
1100ฐ C for 15 minutes, and then dissolved with 5.0 ml. of concen-
trated nitric acid and deionized water. The resulting solution was
then diluted to 50.0 ml. (Jeffery, 1975).
The second step of the extraction process removes residual metals
that are more tightly bound to the sediment than the metals removed in
the acetic acid extraction. These residual metals include metals bound
in silicate lattices, coprecipitated in oxide phases that are not
readily reducible, and metals that are tightly bound to organic
materials. The metals bound in this fraction should not be available
to the biota, under most conditions.
Analysis
Solutions were analyzed for Fe, Mn, Zn, and Cu using a Perkin-
-Elmer 5000 atomic absorption spectrophotometer in flame mode, using
the standard analytical conditions for that machine (Perkin-Elmer,
-------
34
1976). Reagent blanks were prepared and duplicates or spikes of every
fifth sample were analyzed. Standard solutions were made up with
compositions that duplicated those in the sample solutions. Reagent
grade materials were used throughout.
Other Analyses
Besides the metals analysis, samples were analyzed for extract-
able and total phosphorus (both organic and inorganic), total carbon,
nitrogen, hydrogen, and grain size, and for the mineralogy of the
sand, silt, and clay size fractions. Statistical analysis of the data
was performed using the SCSS software package (Nie et al., 1980).
-------
35
RESULTS
Iron
Extractable Fe in the oxidized sediment layer has a mean of 3820
ppm (S.D.=1200, N=7Q). In the reduced layer the mean is 3430 ppm
(S.D.=1530, N=110). Results of the sequential step extraction indicate
that only a small percentage of the total Fe is extractable (Fig. 3).
In the oxidized layer an average of 7.7% is extractable, and in the
reduced layer, 7.3%.
The average total Fe in the sediment samples that were
sequentially extracted (Fig. 3) is very close to the average recent
lake sediment value (43,000 ppm), and to the global shale standard
(46,700 ppm) (Forstner, 1981a, p. 136).
Contour maps of the distribution of extractable Fe data for oxi-
dized and reduced layers show that the highest concentrations of
extractable Fe occur in four different areas (Fig. 4). In two of these
areas (northeast and southwest areas of Big Arm Bay) we found crusts
of nodular Fe similar to those found by Cronan and Thomas (1972) in
the Great Lakes, and to cases reported by Calvert and Price (1977).
These crusts form a hard pavement at the sediment-water interface. A
Peterson dredge with attached lead plates, weighing nearly sixty
pounds, had difficulty penetrating the crust. The crusts appear to
have a lateral extent of about 20 square meters. They grade into areas
-------
36
100-i
75-
44200 3550 175 240
relative % 50-
25-
KHV-
extractabto
100-,
relative %
Fe Mn Zn Cu
a) OXIDIZED LAYER
43400 TIOO 160 175
Fe Mn Zn Cu
b) REDUCED LAYER
tho'deP'ic^'i"9 results of the sequential extractions for
the oxidized and reduced layers. At the too of each bar, the average
total amount of each metal is posted, in parts per million.
-------
n>
Q.iQ
c ป
n
n> r.
p> n
O
pป ft
3 ฐ
O-c
o
x =1
ฆj* a
5:S
M <*
rt>
o. o
~h
Qป
*<
Ci-
(/i
rfr
1
OCT
O C
3 ci-
rt -*
o o
C 3
-1
rt
m K
-i 1
< It
oป ^
n
*ป rt
t/> W
O
ro rt>
o
O-O
(P
*o
?-:t
"t"
IT
<1)
-------
0 0
j u
where smaller discontinuous nodules (down to sand size) are present.
Pieces of the crust react violently when treated with hydrogen
peroxide, indicating that they may be bound by an organic matrix.
In the other two areas where high Fe concentrations were found
(in southeastern Big Arm Bay and the area along the southeast
shoreline extending into Skidoo Bay) no Fe nodules or crusts have been
located.
Manganese
Extractable Mn is enriched in the oxidized layer of the surface
sediments (Fig. 5). The average Mn content of the oxidized layer is
1590 ppm (S.D.=1000), while that of the reduced layer is 310 ppm
(S.D.=780). A more detailed comparison of the extractaDle Mn in the
oxidized layer versus that in the reduced layer was made on 70 samples
for which both oxidized and reduced subsamples were available. In
these samples, 83% of the oxidized layers contain at least 10% more
extractable Mn than the reduced layers (Fig. 6).
The sequential extraction shows that a much higher proportion of
the total Mn is extractable, relative to Fe (Fig. 3). The mean for the
oxidized layer is 43.5%, while in the reduced layer an average of
57.3% of the total Mn is extractable.
-------
39
w*
b) REDUCED LAYER
Fig. 5. Histograms of the acetic acid extractable metal concentrations
in the oxidized and reduced sediment layers.
-------
40
Fig. 6. Histograms portraying comparisons of the amount of extractable
material in the oxidized layer to that in the reduced layer, where
both subsamples were available at the same sampling site. The relative
% was calculated as follows: (Concentration of extractable element in
the oxidized layer divided by concentration of extractable element in
the reduced layer) x 100%.
-------
-j ~n
at
G-ta
c
o
s.^
aป <ป
^-o
3
fiป rt
3 ฐ
Q-C
O **
*3
a.ป
-t. t3
M W
a>
a. o
rr
no
oป
*< (X
(V -I.
n w
lA rt
1
J.
o a*
o c
3 rt-
rt- ป
0 O
C 3
1
sฐ
ri-
ot n>
i *
< 2
oi -t
oซ
n
rf
IA 01
cr
o> *
o ซD
O
"O 3
"O
rt
U"
ro
-------
42
Comparison of the total Mn measured in the sequential extractions
(Fig. 3) with other recent lake sediments (Forstner, 1981a) indicates
that Mn in Flathead Lake sediments exceeds both the average values
(750 ppm) and the range (100-1800 ppm). Forstner (1981a) states,
however, that Mn has a wider variation in values than most elements,
due to its diagenetic mobility, so high values of Mn are not
surprising.
Zinc
Extractable Zn in the oxidized layer averages 15.1 ppm
(S.D.=7.7). In the reduced layer, the mean is 15.9 ppm (S.D.=6.9). A
detailed comparison of oxidized and reduced layers from the same
samples reveals a systematic enrichment of Zn in the reduced layer.
61A% of the samples contain at least 10% less extractable Zn in the
oxidized layer than in the reduced layer.
The extractable portion of the total Zn present was low (Fig. 3),
averaging 10.1% in the oxidized layer, and 9.6% in the reduced layer.
The total Zn recoverable in the sequential extraction fell within the
range of 87 recent lake values reported by Forstner (1981a).
The area with the highest concentration of Zn is in Somers Bay
(Fig. 8), where the concentrations of extractable Zn are 3-5 times
higher than the average concentrations. Most of the other locations
containing higher than average Zn values are also near developed sec-
-------
~i ~n
(0 -*
OlO
C
O
S.CP
Qt O
^ O
3
Of <-t
3 ฐ
o-c
o"1
2. a
Q. Dl
ซj.XJ
N ซ*
fP
O- O
-ti
0>
(U
ซ< O-
IP
-s t/>
i/i rt
"I
o cr
o t:
3 c+
r+ -*ฆ
O O
C 3
"1
3
r+
* Q*
o
* rt
O*
O fl>
*o
H
M
13
a
3*
(D
O & Milts
. S ป ป ป <
O 4 AK(t
-------
44
ticns of the shoreline. The exception is the deep southern arsa of the
lake, west of Blue Bay, which also has nigher than average Zn
concentrations in the reduced layer.
Copper
Extractabla Cu in the oxidized layer has a mean cf 3.0 ppm
(S.D.=3.4). Comparisons of oxidized and reduced layers from the same
samples show that 84% of the reduced subsamples contain at least 10ฐi
more extractable Zn than the oxidized layer (Fig. 6).
In the sequential extraction, only 4.1'i of the total Cu is
extractable in the oxidized layer, and 5.8% in the reduced layer (Fig.
3). The total amount of Cu in the sediments is high relative to the
mean and high values for 37 recent lakes (Forstner, 1981a), which
clustered around a mean of 45 ppm. The total Cu in the samples from
Flathead Lake averages 238.0 ppm in the oxidized layer, and ranges
from a low of 85.4 to a high of 833.0 ppm. In the reduced layer, the
mean is 176.0 ppm, with the total concentrations varying from 67.2 to
428.0 ppm.
The areal distribution of extractable Cu in the reduced tayer
closely mimics the distribution of Fe in the reduced layer (see Figs.
4a and 9a), but this close correlation is not found in the oxidized
layer. However, two of the areas which have high Cu values in the
ฆ educed layer also have high values "in the oxidized layer, the south
-------
-------
46
eastern area of Big Arm Bay, and the northeast part of Big Arm Bay,
where the nodular Fe crusts were located.
-------
47
DISCUSSION
Tables I la and lib show the correlation coefficients of the mea-
sured variables for the oxidized and reduced layers. Tables III and IV
contain the multiple linear regression statistics for the oxidized and
reduced layers.
Manganese Pi agenesis
The distribution of extractable Mn in the oxidized layer corre-
lates best with the distribution of extractable Fe (Table Ila), indi-
cating that Fe oxides and hydroxides may adsorb and coprecipitate some
of the extractable Mn. Probably some extractable Mn is also leached
from discrete Mn oxides (Forstner, 1981b; Hem, 1981). In the reduced
layer, the major factors correlating with the distribution of extract-
able Mn are extractable inorganic phosphorus and extractable Fe
(Tables lib and IV).
As previously mentioned, extractable Mn shows a distinct enrich-
ment in the oxidized layer, averaging 90%. This suggests that Mn may
be moving as the result of diagenetic processes in the sediment
column, a phenomenon frequently cited in the literature (Lynn and
Bonatti, 1965; Robbins and Callender, 1975; and Klinkhammer, 1980).
Klinkhammer (1980) mentions that the simplest way to oxidize Mn"1"'"
is by the reaction:
-------
Ext. |
Res. |
Ext. |
Res. |
Ext. |
Res.
I
Ext. |
Res.
Sample
I Layer j
Fe j
Fe |
Mn |
Mn |
Zn |
Zn
1
Cu j
Cu
34
I Red. |
1040 |
27500 j
37.6 |
170 j
T4'.6~T
21b
|
T2T.2T
4T6
60
1 Ox. |
1900 j
25100 j
115 |
172 |
15.5 |
208
I
5.8 |
283
60
I Red. j
1860 |
30300 |
54.4 I
173 |
10.2 |
246
|
9.8 |
123
75
1 Ox. |
1610 |
36700 |
1060 |
493 |
7-6 |
214
|
3.4 |
82
75
j Red. |
4540 |
33900 |
932 |
328 |
8.4 |
148
I
8.2 |
139
86
1 Ox. |
4540 j
34700 I
1370 |
4410 |
10.9 |
226
|
7.4 |
190
86
I Red. j
5030 |
31500 j
1600 j
359 |
14.3 |
268
|
11.8 |
98
94
1 Ox. |
3400 |
49200 I
87.1 |
9280 j
9.3 |
226
|
4.2 |
829
94
j Red. j
4590 |
52000 |
1690 |
486 |
17.3 |
108
|
9.4 |
348
123
I Ox. |
4540 |
46800 |
2080 j
3380 |
10.0 j
62
1 |
11.0 |
78
123
I Red. j
2790 |
47600 |
1960 |
624 |
10.7 |
110
|
7.4 |
110
136
1 Ox. |
3200 j
54000 |
1040 j
1680 |
8.0 |
131
|
5.0 |
145
136
I Red. j
3400 |
46400 |
683 |
298 |
14.1 |
85.
o 1
8.2 |
59
145
1 Ox. j
3690 |
41900 |
1900 |
677 |
8.7 |
102
|
6.2 |
167
145
1 Red. |
3570 |
60800 j
679 |
323 j
8.8 |
113
|
7.8 |
120
154
1 Red. j
1330 1
35100 |
111 |
168 |
2.0 |
65.
5 1
1.8 |
129
160
1 Ox. |
4060 |
38300 |
442 |
242 |
54.7 |
105
|
3.0 j
84
160
I Red. j
3240 |
37500 |
148 |
182 |
42.6 |
106
1
4.6 j
142
Table I Results of the sequential extractions, in ppm. Results given
tor oxidized and reduced subsamples, where available. Two figures
given for each element - extractable and residual. Extractable Zn
e.g., was leached from the sediment sample by 20% acetic acid!
Residual Zn was only released from the sediment by complete
dissolution. K
-P*
00
-------
4S
Mn
-.051
Fe
.294
.514
Cu
.119
.347
. 406
Inor. P
-.032
.409
.652
.406
Carbon
. 546
-.107
.359
.308
.359
Sand
.018
-.250
-.234
-.233
-.265
.050
Silt
-.499
-.182
-.256
-.402
-.167
.094
-.274
Clay
.414
.356
.407
.532
.355
-.094
-.563
Zn
Mn
Fe
Cu
Inor .P
Carbon
Sand
a) Oxidized layer
Mn
.327
Fe
.531
.743
Cu
. 465
.525
.696
Inor. P
.377
.771
.738
.396
Carbon
-.029
-.350
-.280
.038
-.417
Sand
-.526
-.345
-.650
-.712
-.376
.218
Silt
-.098
- 3QG
ป -J w
-.227
.089
-.285
.581
-. 255
CI ay
.580
.641
.807
.637
.586
-.293
- ] 702
Zn
Mn
Fe
Cu
Incr.P
Carbon
Sand
b) Reduced layer
Table II. Correlation coefficients between measured parameters in the
oxidized (a) and reduced (b) layers..
-------
Mn++ + \ 02 = Mn02 + 2H+
However, he states that there is the possibility, shown by Morgan
(1967) and K1inkhammer and Bender (1980), that hausmannite (Mn^O^), a
less oxidized Mn(III) phase, actually forms during oxidation and pre-
cipitation. This suggestion has recently been corroborated by Hem
(1981), who determined experimentally that, at temperatures between
0.5ฐ C. and 37.4ฐ C., oxidation of Mn+ leads to the formation of
mixtures of hausmannite and feitknechtite by the following reactions:
3Mn++ + \ 0^ + 3 H^O = Mn^ + 6H' (hausmannite)
2Mn + + \ 0^ + 3H^u = 2Mn00H + 4Hr (feitknechtite)
With aging and further oxidation the
recrystallize to various forms of
todorokite (K1inkhammer, 1980).
hausmannite and feitknechtite may
MnO^, including birnessite and
Below the oxidized zone is a neutral zone, in which Mn compounds
are neither dissolved nor precipitated. In this zone, Mn++ moves by
diffusion (Robbins and Callender, 1975). A zone of dissolution
underlies the neutral zone. In that zone, the Mn oxides and hydroxides
formed at the sediment-water interface dissolve by oxidation-reduction
reactions (Robbins and Callender, 1975). The metabolic reactions of
bacteria probably control the reduction of Mn compounds by the gener-
alized reaction (Berner, 1980):
-------
51
DEPENDENT: FEEX 2 VARIABLES IN. LAST IN: CLAY
MULTIPLE R =ฆ
F CHG ป
SIGNIF F
EM EQUATION
VARIABLE
MNEX
* CLAY
(CONSTANT)
.56720
1.10-197
.08020
3
.51038
23.46219
1603.90607
R SQUARE = .32172
SIGNIF F CHG = .31233
3ETA
.42237
.25695
R SQUARE CHG * .05765
F * 3.08302
F SIGF
2.986 .108
1.105 .312
1.579 .231
CORR
.514
.407
PART PRTL
.395 .432
.240 .280
OEPENDENT: CUEX 2 VARIABLES IN. LAST IN: FEEX
MULTIPLE R ป
F CHG *
SIGNIF F *
IN EQUATION
VARIABLE
CLAY
* FEEX
(CONSTANT)
.60250
1.64096
.05332
R SQUARE ป
SIGNIF F CHG
.36301
.22257
R SQUARE CHG
F *
B BETA F SIGF
.07552 .40512 2.794 .119
6.339-04 .31049 1.641 .223
1.02901 .151 .704
CORR
.532
.476
.08041
3.70425
PART PRTL
.370 .421
.284 .335
Table III. Results of multiple linear regression analysis for the
oxidized layer. FEEX stands for extractable Fe, INPEX for extractable
inorganic phosphorus, etc.
-------
DEPENDENT: FESX 2 VARIABLES IN. LAST :N: ;NPEX
VIUL71PLH a "
- :hg
IGMf P
M EQUATION
/-31 ABLE
CLAV
*:mpe:<
CONSTANT)
370S9
19.50910
3000a
3
34.43133
1.17435
37.53230
-5 SQUARE ,"5732
SIGNIF ? CHG - 00008
3ETA
56933
40447
F
33.662
19.509
369
SIGr
300
ooo
.793
DEPENDENT. MNEX 2 VARIABLES IN
MULTIPLE fl - 31301
F CHG 3.61109
SIGNIF P .30000
IN EQUATION
V AH I ABLE 3 3 ETA
INPEX 72S27 43909
===:< 19508 .38195
CCNSTANT) -305.27396
, LAST IN: FESX
R SQUARE
SIGNIF P CHG -
f
14.119
3.611
20.332
DEPENDENT: CUEX 3 VARIABLES IN. LAST IN: CLAY
multiple a - 73224 a square
P CHG 5.31572 SIGN IP F CHG ฆ
SIGNIF F .30000
N EQUATION
7ARIA8L2 3 3STA ?
*ซEX 9.22304 .40908 5.227
SILT .06823 .37235 12^52
CLAY .08234 .48093 5.318
(CONSTANT) 1.38940 1.217
56098
00523
SIGF
301
305
.300
51190
.01181
SIGF
018
301
.312
27a
CEPENOENT: INPEX 2 VARIABLES IN. LAST IN: FSEX
MULTIPLE R
P CHG
SIGNIF P
IN EQUATION
VARIASLs
VINEX
PSEX
; CONSTANT)
30973
7.30409
30000
3
.33498
12719
734.21668
P SQUARE
SIGNIF P CHG
55570
30769
3ETA
.19671
.38928
14.119
7 304
26.037
SIGF
301
.308
.300
R SQUARE CHG -
CORR
307
738
PART
481
223
R SQUARE CHG
QTZ3
68.38006
3RTL
;34
.534
.C6635
4239253
CORR
.771
.743
PART
230
253
3RTL
493
.405
3 SCUARE CHG 36242
? 22.59891
CORR
.396
389
337
PART
.237
233
.250
3 SQUARE CHG
PRTL
256
.471
372
38107
41.39714
CORR
.771
.733
PART
332
.247
BSTw
493
.288
Table IV. Results of multiple linear regression analysis for the
duced layer.
-------
CH20 + 2Mn02 + 3C02 = 2Mn++ + 4HC03
Below the zone of dissolution Mn++ equilibrates with authigenic Mn
phases (Robbins and Callender, 1975). According to Berner (1980), the
most common reduced phase is rhodochrosite (MnCO^), but other possible
phases include reddingite [Mn^PO^^SHgO], and several forms of Mn
sulfide.
The reduced sediment layer of Flathead Lake may contain some
rhodochrosite, but in view of the small amount of carbonate in the
sediment (Decker, 1968) the amount of rhodochrosite is probably low.
The Mn phosphate reddingite may form a more important reduced Mn
phase, based on the high concentrations of extractable phosphorus,
which suggest that phosphates may be stable. Statistical analysis of
the data for the reduced layer indicates that extractable inorganic
phosphorus correlates with both extractable Mn and extractable Fe
(Table lib). An examination of the partial correlation coefficients
seems to show that the correlation of extractable Mn and phosphorus
remains independent of the correlation cf extractable Fe and phos-
phorus (Table V). The presence of a second phase containing Mn and
phosphorus probably causes the correlation of extractable Mn and phos-
phorus, which may be the Mn phosphate, reddingite.
One difficulty in this, and other studies, has been the identifi-
cation of postulated mineral species (Emerson and Widmer, 1978; Klink-
-------
54
Fi rst
Order Partials
Control: Fe
Mn
-.119
Cu
.156
.016
I nor. P
-.026
.493
-.245
Carbon
.147
-.222
.338
-.325
Sand
-.281
.271
-.476
.203
-.549
Silt
.028
-.348
.354
-.179
.553
-.679
CI ay
.303
.104
.178
-.023
-.119
-.395
-.399
Zn
Mn
Cu
Inor.?
Carbon
Sand
Silt
First
Order Partials
Control: Mn
Fe
.455
Cu
.364
.537
Inor. P
.208
.388
-.017
Carbon
.097
-.031
.279
-.246
Sand
-.466
-.627
-.665
-.184
-.386
Silt
.037
.109
.380
.514
-.570
Clay
.511
.543
.460
.189
-.096
-.667
-.226
Zn
Fe
Cu
Inor.P
Carbon
Sand
Silt
First
Order Par
ti als
Control: Clay
Mn
-.071
Fe
.131
.499
Cu
.151
.198
.400
Inor. P
.056
.636
.554
.035
Carbon
.182
-.222
-.076
.305
-.316
Sand
-.205
.191
-.200
-.483
.062
-.623
Silt
.191
-.187
.197
.502
-.058
.528
-.993
Zn
Mn
Fe
Cu
Inor.P
Carbon
Sand
Table V. First-order partial correlation coefficients ior <.he reduced
1ayer.
-------
55
hammer, 1975), particularly by x-ray diffraction methods. One reason
for this difficulty is the relatively low volumetric importance of the
phases being sought, which makes them difficult to separate and
concentrate. Also, since x-ray diffraction cannot identify amorphous
phases, the amorphous nature of many authigenie compounds may
constitute the most important reason for the difficulty encountered in
identification of these authigenic minerals (Emerson and Widmer,
1973).
Iron and Phosphorus Pi agenesis
Extractable Mn content and the percent clay size fraction corre-
late best with the distribution of extractable Fe in the oxidized
layer (Tables I la and III). The extractable Fe probably exists in
three forms: as hematite; adsorbed and coprecipitated by the Mn oxides
mentioned above; and adsorbed by clay minerals. Hematite occurs in the
surface sediments of Flathead Lake as films that coat clay grains and
other minerals, and as discrete grains (Decker, 1968). Mn oxides
readily adsorb and/or coprecipitate Fe, because of the chemical simi-
larity between Fe and Mn (Krauskopf, 1979). Clay minerals efficiently
adsorb Fe, especially in the form of Fe(0H)3 colloids (Forstner,
1981b). Extractable inorganic phosphorus in the oxidized layer
correlates with extractable Fe, and to a lesser extent, with
extractable Mn (Tables Ila and III). Fe and Mn oxides and hydroxides
efficiently adsorb aqueous phosphorus (Wetzel, 1975). Multiple linear
regression and partial correlation coefficients revealed no appreci-
-------
56
able correlation of inorganic phosphorus with grain size, independent
of Fe and Mn content (Tables III and V). This may indicate that the Fe
and Mn oxides adsorb phosphorus so efficiently that adsorption by clay
minerals plays a minor role in controlling the distribution of
phosphorus.
In the reduced layer, grain size and extractable inorganic phos-
phorus correlate with the distribution of extractable Fe (Tables lib
and IV). As indicated above in the section on Mn diagenesis, both
extractable Mn and extractable Fe correlate with the distribution of
inorganic phosphorus, seemingly independent of one another.
A diagenetic modal for the behavior of extractable Fe proposed
i
for Flathead Lake is similar to the model proposed for Mn diagenesis.
The apparent immobility of Fe in the surface sediments (Figs. 5 and 5)
constitutes the major difference between the two models. Krauskopf
(1979) and Mortimer (1971) have previously dealt with sediment systems
undergoing oxidation-reduction and found that Mn often becomes mobile
before Fe, because of Mn's greater sensitivity to changes in redox
conditions. Inorganic phosphorus may be mobile in the sediments, since
the oxidized layer does contain an average of 23% more extractable
phosphorus than the reduced layer, with 54% of the samples having an
enrichment of more than 10% in the oxidized layer (Figs. 6 and 10). in
view of the agricultural activity and increased population in the
Kalispell valley, input of cultural phosphorus probably occurs, which
may enhance the enrichment of phosphorus in the oxidized layer.
-------
Inorganic P
pHim.
OXIDIZED LAYER
p^xm.
REDUCED LAYER
Fig. 10. Histograms of the extractable inorganic phosphorus
oxidized and reduced sediment layers.
-------
A possible diagenetic model for explaining the distribution of
extractable Fe in the sediments of Flathead Lake involves the burial
of initially oxidized sediments containing hematite and ferric hydrox-
ides, together with adsorbed inorganic phosphorus. Decomposition of
organic matter by bacteria causes the sediments to become reducing.
After the bacteria have utilized other, more energy efficient
oxidants, such as oxygen, nitrate, and Mn oxides (Serner, 1980), the
reduction of Fe begins. The metabolic reactions are of the form
(Berner, 1980):
4Fe(0H)3 + CH20 + 7C02 = 4Fe+" + SHC03" + 3H?0
This reaction would release Fe++ and phosphorus into the pore water.
Eventually, as the activity of Fe+i" increased, the ion activity pro-
duct would exceed the solubility product of one of the reduced authi-
genic Fe minerals, and precipitation would ensue. Based on the low
sulfate content of fresh water, the small amount of organic material
and carbonate in the sediments of Flathead Lake, and the large amounts
of extractable inorganic phosphorus present, the Fe phase that preci-
pitates probably consists of an Fe phosphate, vivianite (Fe^PO^*-
8^0). Small nodules of vivianite which have been discovered in two
previous studies of Flathead Lake sediments (Joyce, 1980; Potter,
1978) support this hypothesis. Emerson and Widmer (1978) in a study of
the Greifensee, a Swiss lake, reported similar results.
-------
59
Geochemical Classification of Flathead Lake Sediments
Recently, Berner (1981) proposed a geochemical classification of
sediments based on the concentrations of 0^> H^S, and more impor-
tantly, on the identification of the Mn and Fe mineral phases that are
present. Based on the Fe minerals that are known to be present,
hematite and vivianite, on the suspected presence of Mn oxides, hy-
droxides, and phosphates, and, especially, on the lack of any sulfide
minerals, the sediments in Flathead Lake appear to fit into the non-
-sulfidic continuum of Berner's (1981) classification scheme.
Specifically, this involves the presence of an oxic layer, demon-
strated by the presence of hematite, and the assumed presence of Mn
oxides. Below this oxic layer, the sediments enter the post-oxic (non-
-sulfidic) phase, identified by the presence of vivianite, and the
assumed presence of reddingite and other reduced Mn phases, and by the
lack of sulfide minerals. Because of the small amount of organic
matter deposited in the sediments and the presence of a year round
oxidizing environment at the sediment water interface, only a small
amount of decomposable organic matter is present in the sediments upon
burial. The lack of sufficient organic matter probably prevents the
sediments from attaining the strongly reducing conditions necessary
for the formation of the methanic phase, Berner's (1981) designation
for the most reducing non-sulfidic environment.
Sources of Zinc
The distribution, of Zn in the oxidized layer correlates with the
amount of carbon present and with grain size (Table I la). In the
-------
60
reduced layer, the major correlation is with grain size (Table lib).
Partial correlation coefficients and multiple linear regression sta-
tistics indicate that the correlation of Zn with Fe in the reduced
layer (Tables IV and V) results from the correlation of Zn with clay
size fraction and of Fe with clay size fraction, and that no direct
link between extractable Zn and =xLractable Fe actually exists. The
lack of correlation between carbon and Zn in the reduced layer proba-
bly arises because of the destruction of organic matter by microor-
ganisms .
Another factor that seems to control the distribution of extract-
able Zn in the sediments is geographic location. As shown in Fig. 3,
the highest Zn values are found in Somers Bay. in both the oxidized
and reduced layers. This location has extractable Zn that is 3-5 times
higher than average extractable concentrations. In addition, the
amount of extractable Zn as a percent of total Zn is 2 times higher
than the mean, indicating that more of the Zn in that location is
readily available in aqueous form.
The high amount of Zn near a populated area suggests cultural
input of Zn to the lake sediments. The long history of industrial
activity in Somers, as well as its continuation as a population center
for over 80 years, lend support to that idea. Over the years, Somers
has had a steamship port, a sawmill, a mill pond, scrap metal yards, a
railroad tie factory, a tannery, and other industry. In Somers, as in
most small towns, septic systems dispose of household sewage. Domestic
-------
51
effluents are a common source of Zn in aquatic systems (Wittmann,
1981). A study by Konizeski and others (1963), found that during the
months of August through March, when the water level of Flathead Lake
is lowered, ground water flows through the sandy floodplain aquifer of
the Flathead River directly beneath the town of Somers and into
Flathead Lake. This ground water flow may transport Zn into the lake,
and ultimately, into the sediments in Somers Bay.
The majority of the other areas that show high extractable Zn
values also occur near populated sections of the shoreline. The possi-
bility that ground water flow from communities surrounding the lake
contributes Zn to the lake, together with the fact that some of the
areas of highest extractable Fe and Cu concentrations are near the
shoreline, all point to the need for greater study of the groundwater
and sediment porewater chemistry.
The southern portion of the lake comprises the main area of high
Zn concentrations not located near the shoreline (Fig. 8). This area
also tends to have high percentages of clay size material, because of
the great distance from the Flathead River delta. The Flathead River
contributes most of the sediment to Flathead Lake. Considering the
good correlation of extractable Zn with the clay size fraction (Table
II), higher than average values of Zn in this area are not surprising.
Sources of Copper
Grain size, and to a lesser extent, extractable Fe, correlate
with the distribution of extractable Cu in the oxidized layer (Table
-------
62
11 a). In the oxidized layer, clay minerals probably adsorb Cu, while
Fe oxides and hydroxides both adsorb and coprecipitate it (Forstner,
1981b). Examination of the correlation coefficients and of the
multiple linear regression statistics for the reduced layer (Tables
lib and IV) indicates that extractable Fe and grain size correlate
with the distribution of extractable Cu. Comparison of the contour
maps of Fe and Cu in the reduced layer also shows the correlation
between the two elements (Figs. 4a and 9a). However, while Cu
correlates with percent clay in the reduced layer (Table lib),
multiple linear regression reveals that extractable Cu also correlates
with percent silt (Table IV). This is the only case where a positive
correlation of any of the extractable metals appears with coarser
grained sediments. As a general rule, extractable metals usually
correlate with finer grained sediments, because of surface area
effects (Forstner, 1981b).
The positive correlation of extractable Cu with the silt size
fraction in the reduced layer, taken together with the extremely high
values of total Cu, almost all of which resides in the residual frac-
tion, suggests two sources for the extractable Cu. One source consists
of Cu bound loosely by extractable Fe compounds and by clay minerals.
The other source consists of detrital Cu minerals.
The presence of detrital Cu minerals would explain the high con-
centrations of residual Cu in the sediments. Because it is tightly
bound to the sediment, the large amounts of Cu should not be available
-------
63
to the biota, under normal conditions. Any detrital Cu minerals
present in the sediment have presumably been altered from their
original sulfide mineralogy, due to weathering at the outcrop, during
transport, and in the oxidized layer of the sediments. Possible Cu
phases now present may include tenorite, cuprite, malachite, and
azurite.
Rocks of the Belt Supergroup are a likely source for detrital Cu
minerals. They contain ore-grade Cu mineralization, with Cu contents
varying from background levels of 20 ppm to highs of at least 20,000
ppm (Harrison, 1972; Harrison and Grimes, 1970). Cu minerals include
chalcopyrite, chalcocite, digenite, bornite, and covellite (Harrison,
1972). Several types of Cu deposits are known, and are found in almost
every stratigraphic unit, and every geographic area of the Selt basin
(Harrison, 1972). Mineral companies are actively exploring the Belt
basin for these Cu deposits. Besides Cu, the deposits also provide
sources of Pb, Ag, and Hb (Clark, 1971; Lange and Moore, 1981).
Remobilization of Extractable Material
The concentrations of extractable metals and nutrients measured
in the surface sediments exceed the levels in the waters of Flathead
Lake by at least an order of magnitude (Stuart and Stanford, 1981).
This reservoir of extractable material may be released if the chemical
environment of the sediments changes sufficiently. The release of
phosphorus to the lake waters would be particularly important because
of the role of phosphorus as the limiting nutrient in the Flathead
Lake ecosystem (Stuart and Stanford, 1981).
-------
64
The distribution of extractable In indicates that some pollution
or the lake may be occurring near peculated areas. Stanford (personal
comm., 1982) recently discovered hicner levels of primary productivity
in the waters of some of the bays with populated shorelines, which
tends to support that idea. Increased pollution levels could lead to a
situation in which the bottom waters of Flathead Lake are no longer
oxidizing. If that occurred, the seaiments of Flathead Lake might
become a source of both nutrients and metals (Wetzel, 1975; Lei and et
al., 1973), which would tend to aggravate any developing pollution
problem. The high economic, recreational, and ecological value placed
on the lake by its many users suggest the need for continued
monitoring of the waters and sediments of Flathead Lake.
-------
65
Chapter Three
PHOSPHORUS
Jaswant Singh Jiwan
Johnnie N. Moore
Introduction
In all parts of the world, increasing industrial and
domestic waste discharge, agricultural runoff and input from
catchment basins subject lakes to pollution. These effluents
usually contain an abundance of nutrients which can cause
unrestricted growth of aquatic vegetation (Hwang et al., 1975).
In recent years, the environmental challenge has been to protect
unpolluted lakes and restore those already in various stages of
eutrophication. Among the growth promoting nutrients, phosphorus
has been implicated as a major factor in the deleterious
fertilization of lakes (Hwang et al., 1975). Increasing
population density, the intensive use of fertilizers in
agriculture and the widespread application of domestic and
industrial detergents has raised the concentrations of phosphate
and nitrate in many lakes resulting in eutrophication.
In more than 80% of the 200 north temperate lakes studied in
the International Eut Dphication Programme of the Organization
for Economic Cooperation and Development, the availability of
phosphorus controlled the process of eutrophication. Posphorus
concentration is considered the most important factor affecting
-------
66
primary productivity, algal standing crops, fish population and
water clarity and quality (Vollenweider, 1971; Ostrofsky and
Duthie, 1975, 1980; Wetzel, 1975; Oglesby, 1977; Schindier , 1977;
Kalff and Knochel, 1978; Lee, Jones and Rast, 1980).
Limnological investigations of Flathead Lake began towards
the end of the nineteenth century (Forbes, 1893), but this early
work only established the structure of the ecosystem and did not
address aquatic chemistry or productivity. More recent work
(Stanford et al., 1981 ) is establishing the aquatic
chemistry and biology of the entire drainage system. All previous
limnological work alluded to the oligotrophic status of Flathead
Lake (Seastedt and Tibbs, 1974; Tibbs, Gaufin and Prescott, 1976;
Potter, 1978). Stanford and Potter (1976) suggested that the
nutrient balance in the lake is maintained by interaction of
sediment from the spring turbidity plume and other ecologi al
factors. In their hypothesis, clay particles introduced by
spring runoff causes floculation of phytoplanton and organic
detritus and concommittant adsorption of inorganic phosphorus.
These clay-detritus floes then settle to the lake bottom. The
sediment both supplies and removes phosphorus from the water
column and thus aids or inhibits primary productivity. The most
recent work on the trophic system of the lake has modified this
hypothesis (Standford, et al., 1981 ) but phosphorus
concentration is still assumed to control the trophic state of
the lake, and originates mostly from sediment input.
In most northern-temperate oligotrophic lakes, wind and
rivers supply the majority of phosphous. Once phosphous reaches
the lake, a variety of dynamic interactions occur between
-------
67
sediment, biota and nutrients. Syers et al., (1973) summarized
work on phosphorus in lake sediments and discussed the
relationship between amounts and forms of phosphous and
composition and textural properties of sediment. He also
discussed chemical mobility and availability of phosphorus to the
biota from sedinents. In general, lake sediments store
phosphorus under certain chemical conditions and release it under
others.
Phosphorus cycling, in relation to the input of phosphorus
from external sources, governs the biological productivity of a
great number of lakes (Wetzel, 1975). Therfore, it has become
very important to understand the characteristics of sediments
that affect the overlying water quality through chemical,
biological and mechanical exchanges. The exchange of phosphorus
between the sediments and overlying water is a major component of
the phosphorus cycle in natural waters (Drever, 1982). Its
importance rests in an apparent net accumulation and upward
migration of phosphosus in lake sediments.
Because phosphorus migrates and concentrates at the surface
after deposition (Berner, 1978), there is little correlation
between the amount of phosphous in lake sediments and the
overlying water (Wetzel, 1975). Phosphorus content in lake
sediment can be several orders of magnitude greater than that in
overlying water. The ability of the sediment to concentrate and
return phosphorus depends on the pH, Eh and major ion centrations
of the sediment and the lake bottom water. Both inorganic and
biologic processes alter exchange equilibria and affect
-------
68
phosphorus migration from sediment into the water.
Because phosphorus concentration controls the trophic srate
of Flathead Lake, previous workers have attempted to calculate
the phosphorus budget (Seastedt and Tibbs, 1974; Tibbs, Gaufin and
Standford, 1975; Nunallee, 1976; E.P.A., 1976). However, none of
these studies have considered the contribution or the potential
contribution of the sediments filling the lake. The data and
interpretation presented here discusses the physical and chemical
framework of Flathead Lake sediment that control phosphorus
distribution and migration and thus may affect the water quality
of the lake.
-------
69
Distribution
Extractable total-, inorganic- and organic- phosphorus as
3-
PO was determined for oxidized and reduced sediment recovered
4
by grab sampling (App. I). Values in the oxidized layer range
from 1137 to 3617 ppm (mean=2311 ppm, S.D.=484, N=70), 800 to
3225 ppm (mean=1983ppm, S.D.=531) and 53 to 594 ppm (mean=327
ppm, S.D.= 163) respectively (Fig. 1). Concentrations in the
reduced sediment range from 617 to 3346 ppm (mean=1765 ppm,
S.D.=583, N=110), 387 to 2990 ppm (mean=1441 ppm, S.D.=527) and
27 to 813 ppm (mean=315 ppm, S.D.=171) respectively (Fig. 1). In
both the oxidized and reduced sediment, inorganic phosphorus
dominates extractable phosphorus and organic phosphorus never
exceeds inorganic concentrations.
Inorganic and total phosphorus, in both the oxidized and
reduced layers, have very similar lateral distributions (Figs, 2
and 3). Values higher than the mean concentrate in the southern
portions of the main lake with isolated higher values along the
east shore north of Yellow Bay, in Woods Bay, in Blue Bay and
along the southwestern edge of Big Arm Bay. Although the mean
values of both total- and inorganic-extractable phosphorus
increase from the reduced layer to the oxidized layer, both types
of sediment and both types of phosphorus show the same
distribution patterns. Oragnic-extractable phosphorus shows a
completely different distribution, unrelated to that of total or
inorganic phosphorus.
Organic phosphorus has accumulated in the sediments in
concentrations greater than the mean throughout the southern half
-------
Total P
M 23||
8 O 484
in
c
-s
a>
10 20
0
ซ
S I ฎ "i
L
II
A
E
3
C
I 9-
400 1040 1600 2920 2960 8*00
ppm
a OXIDIZED LAYER
Inorganic P
M
6 D
1983
531
/ 7
~
*
/
950 l|00 170023002900
ppm
520
i
fl
0 16
vt-
0
L
0
u
E
3
C
1 o
M
S O
1760
563
I
4W
400 1040 1600 2320 2960
ppm
b REDUCED LAYER
a
d *0
ta
s
<*-
0
L
0
ja
E
3
c
19
10
M
S D
1441
527
lHp
380 1100 1700 2300 2900
ppm
Organic P
ppm
IVI
8 D
315
171
m
EL
0 100 360 000 700 900
PPm
-------
-------
-------
73
of the lake including Big Arm BaytFig 4). Isolated higher values
occur in eastern Big Arm Bay, Indian Bay and in the open lake
near Yellow Bay. Although the general pattern is similar to
total phosphorus, none of the isolated high areas are similarly
located, suggesting that organic-extractable phosphorus is
unrelated to the distribution of total- and inorganic-extractable
phosphorus.
The mean concentration of both total- and inorganic-
extractable phosphorus is greater in the sediments of the upper
oxidized layer than in the underlying reduced sediments. The mean
total-extractable phosphorus increases by 30% and inorganic-
extractable phosphorus by 38%. Organic-extractable phosphorus
means are nearly identicle showing no average incease from the
reduced to the oxidized sediment. These average increases may not
mean that at any particular site there is an increase upwards in
the concentration of phosphorus. However, the percent change from
the reduced to the oxidized layer at individual sites show a mean
increase of 18% of total-extactable phosphorus and 2 3% for
inorganic-extractable phosphorus (Table 1) suggesting that there
is a net increase. Organic phosphorus shows no significant
change, with values ranging from large decreases to large
increases.
In summary, the distribution of extractable phosphorus in
the surface sediments show that total phsophorus and inorganic
phosphorus follow simlar trends and organic phosphorus is
unrelated to either. Distributions in the reduced and oxidized
sediment is similar but there is a net increase in both total and
-------
-pa
-------
VARIATIONS FROM REDUCED LAYER TO OXIDIZED LAYER
(DATA IN PPM)
ZnEX MnEX FeEX CuEX TOPEX INPEX OPEX
Min
7
164
675
3
1137
800
53
Mean
15
1592
3820
8
2311
1983
327
OXIDIZED
Max
72
7030
6335
16
3617
3225
934
SD
8
997
f
1205
2-4
4f
V
'.4
531
t
163
1
Min
3
1
26
408
1
4'
7
1
387
3
27
Mean
16
808
3427
10
1765
1441
315
REDUCED
Max
52
3172
6752
16
3346
2990
813
SD
7
781
1530
3-4
583
527
171
en
Table 1
-------
76
inorganic phosphorus upwards. Organic phosphorus shows a wide
range of change and neither average increase or decrease can be
documented. Sediments in the southern lake contain more than the
average concentration of phosphorus throughout the lake, with
total- and inorganic-extractable phsophorus concentrated in
higher amounts in areas on the east side and in southwestern Big
Arm Bay and organic concentrated in Big Arm Bay and in the
southern open lake. Anomolously hgih concentrations of total-
and inorganic-extractable phosphorus occurs near highly developed
shoreline and cherry orchards along the east shore. Very high
values occur in isolated bays (Woods, Yellow and Blue Bays)
suggesting that these concentrations associate with proximity to
developed areas. Concentrations of organic phosphorus appears to
be related to areas of high productivity where sedimentation rate
is slow in Big Arm Bay and central lake.
-------
77
Correlations With Other Variables
Phosphorus in sediments is commonly associated with clays,
metal oxide-hydroxides and organic compounds (Forstner and
Wittman. ,1981; Drever, 1982). Because of these associations the
correlations between metal concentration, grain size and organic
content often identifies modes of occurence of phosphorus in
sediments. We have used this statistical technique of
correlation of varialbes (Drever, 1982) to analyze data collected
on Flathead Lake sediment to determine the mechanisms controlling
phosphorus fixation. Correlation coefficients are presented in
Tables 2 and 3 and partial correlation coeffients in Table 4.
The associations detailed in these tables establish a model of
phosphorus fixation and migration that is consistent with
theroetical and experimental models developed to explain
sediment-water interactions (Drever, 19 82; Forstner and
Wittman, 1981) .
The most striking correlation is between total-extractable
phsophorus and inorganic-extractable phsophorus (Tables 2,3, and
4). In both the oxidized and reduced sediment the correlation
coeffiecient is greater than 0.95 and even with controls the
partial correlation coeficient never falls below 0.88. When
considered with the similar distribution (Distribution section),
these statistics suggest that inorganic phosphorus dominates
extractable phosphorus. Poor correlation between organic-
extractable phosphorus and total-extractable phosphorus shows
that there is no distiguishable relationship between these two
types of phosphorus, as is suggested in the distribution maps
(Figs. 1/2 and3). Inorganic phosphorus dominates the extractable
-------
CORRELATION COEFFICIENTS
MNEX
.327
ORPEX
.448
.101
INPEX
.377
.771
.161
FEEX
.531
.743
.231
.738
TOPEX
.491
.741
.435
.950
.748
CUPEX
.465
.525
.227
.396
.696
CARTO
-.029
-.350
.021
-.417
1
ro
CO
o
SAND
-.526
-.345
-.363
-.376
-.650
SILT
-.098
-.395
-.138
-.285
-.227
CLAY
.580
.641
.454
.586
.807
ZNEX
MNEX
ORPEX
INPEX
FEEX
Table 2
Reduced Layer
.437
-.372
.038
-.444
-.712
-.218
1
CO
o
.089
.581
-.355
.668
.637
-.293
-.702
TOPEX
CUPEX
CARTO
SAND
-------
CORRELATION COEFFICIENTS OXIDIZED LAYER
MNEX
-.051
ORPEX
.233
.044
INPEX
-.032
.409
-.430
FEEX
.294
.514
-.103
.628
TOPEX
.042
.461
-.137
.952
.652
CUPEX
.119
.347
.162
.406
.476
.497
CARTO
.546
-.107
-.035
.359
.350
.424
.308
SAND
.018
-.250
-.209
-.265
-.234
-.379
-.233
.050
SILT
-.499
-.182
-.084
-.167
-.256
-.221
CM
O
1
.094
-.274
CLAY
.414
.356
.238
.355
.407
.493
.532
-.094
-.563
ZNEX
MNEX
ORPEX
INPEX
FEEX
TOPEX
CUPEX
CARTO
SAND
-.640
SILT
Table 3
-------
PARTIAL CORRELATION CO-EFFICIENTS
REDUCED LAYER
OXIDIZED LAYER
Control r
Correlation I
Between
CLAY
TOPEX MnEX
TOPEX FeEX
TOPEX INPEX
TOPEX CLAY
INPEX MnEX
INPEX FeEX
INPEX CLAY
FeEX MnEX
FeEX CLAY
CuEX SAND
CuEX SILT
.547
(.741)
.476
(.748
.926
(.950)
.636
(.771)
.554
(.738)
.499
(.743)
- .483
- .712
- .502
(.089)
FeEX
MnEX
.416
.889
.164
(.668)
.439
ฆ .023
(.586)
.476
.354
.439
.886
.375
.388
.189
.643
(.807)
- . 665
.460
Table 4
CLAY
.351
(.461)
.568
(.652)
.956
(.952)
.323
(.409)
.566
(.628)
.432
(.514)
- .094
(- .233)
- .094
(- .402)
FeEX
. 1 y3
.920
.328
(.493)
.129
.139
(.355)
- .143
- .329
MnEX
.545
.943
.396
.534
.245
.280
(.407)
- .162
- .362
CO
o
-------
81
phosphorus in the sediment and so correlations with other
variables will show only slight modifications by organic
phosphorus.
Correlations between phsophorus and other variables differ
in the oxidized layer and the reduced sediment below. All
correlation coeffients decrease, some only slightly others
dramatically, from reduced to oxidized sediment (Table 4). In
the oxidized layer,, total- and inorganic-extractable phosphorus
show good correlation with extractable manganese and iron and
clay (Tables 2 and 3; Figs. 5,6 and 7). These correlation
coefficients decrease in the oxidized layer, especially with
manganese and clay. Likewise, in the reduced layer extractable
iron and manganese in the reduced layer correlate strongly with
clay but weaken in the oxidized layer. Using iron manganese and
clay as controls illuminates these associations (Table 4).
In reduced sediment, the correlation of total- and
inorganic-extractable phosphorus with clay decreases
significantly when iron and manganese are used as controls(Table
4). These relationships suggest that phosphorus is associated
with iron and/or manganese and not with clays. The good
correlation with clay is controlled by the correlations of clay
with iron and manganese. This association is supported by the
correlation between iron and phosphorus staying strong when
manganese and clays are used as controls (Table 4). Because the
correlations decrease slightly with both, it appears they have
some association. Similarly, correlation with manganese decreases
when iron is used as the control and only very slightly when clay
-------
^'5225
t
"2369
O
SI
-------
83
OXIDIZED
EXTRACTA3LE IRON
3225
cc
o
s:
oo
O
a. 2390
o
i 1723
o
a 1055
<
387
J.
R=0.623
R2=0.394
ppm 409
3580
6752
REDUCED
3225
ac
O
X
Q.
CO
o
= 2390
ซc
o
ce.
o
as
<
t
o
1723
1055
387
EXTRACTABLE IRON
R=0.738
R =0.545
ซ
#ป
#
ppm
409
3580
Figure 5
5752
-------
~ 2390
rv 170^
1/ C j
9 105
is:
X
387
ppm
ซ
.< ป :
ซ.
i *
:
R=0.355
R2=0.126
41
32
REDUCED
U1
a.
OO
O
3225
0.
o 2390
s
-V
c
S3
<
1723
1055
387
ppm
CLAY
<
R=0.586
R2=0.344
*
#
# ซ~
4* !
# *
~
41
32
Figure 7
-------
85
is used. These partial correlation coeffients suggest that
total- and inorganic-extractable phosphorus is controlled by
extractable iron and manganese, both of which are associated with
clay (see Chapter Two).
The same variables in the oxidized layer show different
associations than those in the reduced sediment. In the oxidized
layer the same correlations exist but they are weaker. With
clay, manganese and iron as controls the only correlation that
remains strong is phosphorus with iron (Table 4). This suggests
that total- and inorganic-extractable phosphorus are associated
with iron alone in the oxidized layer and not with both iron and
manganese as in the reduced sediment.
Organic-extractable phosphorus does not show any strong
correlation with any other variables in either the oxidized layer
or reduced sediment. However the correlation coefficients differ
for each type of sediment (Tables 2 and 3). In the reduced
sediment organic phosphorus shows a very weak association with
clay and a negative correlation with sand. This suggests that
there is some, but probably minor, control by grain size, with
organic phosphorus correlated with finer-grained sediment. Total-
extractable phosphorus also shows a very weak correlation with
organic-extractable phosphorus. All these poor associations
change in the oxidized layer.
Organic-extractable phosphorus in the oxidized layer shows
no correlation to grain size. All the correlation coefficients
are insignificant except for (possibly) a negative correlation
with inorganic-extractable phosphorus. The change from a poor
correlation with total phosphorus and clay in the reduced
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86
sediment to poor negative correlation with inorganic phosphorus
in the oxidized zone may suggest that clay-sized organic
phosphorus is altering to inorganic phsophorus in the oxidized
zone. This would explain the relative decrease in the relative
percentage of organic phosphorus in the oxidized layer compared
to reduced sediment (Table 5).
Correlation coefficients and partial-correlation
coefficients show several general relationships between
extractable phosphorus and metals and grain size. The most
striking of these is the dominance of phosphorus by inorganic
forms. Phosphorus is strongly associated with manganese and iron
in reduced sediment and iron in the oxidized layer. Organic
phsophorus is unrelated to those variables controlling total and
inorganic phosphorus but is slihgtly controlld by grain size and
inorganic phosphorus.
-------
MIGRATION STATUS
(Change in oxidized layer as % of Reduced layer)
ZnEX MnEX FeEX CuEX TOPEX INPEX OPEX
Mean
88
192
99
75
118
123
112
Minimum
40
26
35
39
90
68
20
Maximum
144
481
218
151
231
265
415
Range
104
455
183
112
141
197
395
S.D.
20.8
99.2
26.8
17.85
20.4
28.1
72.96
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88
Migration and Concentration
The increase in extractable phosphorus from reduced
sediments to the oxidized zone at the sediment-water interface
can be explained by migration of phosphorus upwards, or increased
input in recent times. The vertical distribution of metals in
Flathead Lake sediments suggest that differences in phosphorus
concentration result from migration associated with iron and
manganese compounds.
Suspension sediments in most lakes contain phosphorus
completed with and attached to many different types of material
(Hesse, 1973). Tipping, Woof and Cooke (1981) found amorphous
iron-oxide particles that contained from 1.1 to 2.8% phosphorus
in a seasonally anoxic lake in Great Britain and many workers
have established that humic complexes of iron and aluminium bind
phosphorus. Jackson (1975) demonstrated the ability of humic
chelate complexes of iron and aluminum to bind orthophosphorus.
Clays adsorb phosphorus (Van Olphen, 1963; Sfuntm and Morgan, 1970)
and iron and manganese oxides, hydroxides, phosphates, sulfides
and carbonates incorporate phosphorus during their formation in
lake and marine sediments (Forstner and Wittman, 19 81; Drever,
1982). Phosphorus also complexes with metal ions, specifically
iron and manganese oxides and hydroxides (Forstner and
WiLLuian, 1981) . The extent of complexing between various
phosphates and metal ions depends on the relative concentration
of phosphate and metal ions, pH, Eh and the presence of other
ligands such as sulfate, carbonate, fluoride and organic species
(Emsley and Hall, 1976).
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89
Phosphorus used by organisms as a nutrient accumulates on
the lake bottom as algae bloom and die (Halman and Stiller, 1974;
Lean, 1973). In many lakes (eg., Flathead Lake) productivity is
limited by phosphorus (Halmann, 1972; Stanford, et al., 1981) and
lake water contains very small amounts of phsophorus compared to
that in lake sediments. Even in oligotrophic lakes phosphorus
accumulates in the sediment as iron, manganese and organic
compounds settle to the bottom. Under oxidizting conditions
these compounds are stable, but when reduced, phosphorus migrates
along with other elements (Williams et al., 1976; Drever, 1982).
Because Flathead Lake sediments are dominated by clay, poor in
carbonate, and show no evidence of sulfides or fluorides, we
assume that phosphorous may be associated with such oxides,
hydroxides and/or organic compounds. Such an inorganic dominated
system was described by Williams et al. ,(1976).
The distribution of extractable phsophorus and extractable iron
and manganese, and their correlations to one another (Tables 2,3
and 4), suggest that iron and manganese constitute the major
controls on phosphorus migration and concentration. Because iron
and manganese correlates strongly with clay, it seems reasonable
to assume phosphorus is controlled by iron and manganese
oxides/hydroxides/phosphates attached to clay-sized sediment. In
reduced sediment both iron and manganese compounds control
phosphorus concentration probably as manganese and iron
phsophates adsorbed to clays. Migration from reduced sediment
into the oxidized layer concentrates phosphorus along with
manganese (Chapter Two), so that through time there is a net
accumulation of nutrients and some metals in the surface
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90
sediments. Such processes are well established in the literature
(Drever, 1982; Forstner and wittman, 1981; Jonasson, 1977; Theis
and Singer, 1973). These processes are explained by a model
involving input of phosphorus adsorbed/complexed with clays and
oxides in the oxidizing environment of the lake water and then
mobilized by the reducing environment of the sediment (Theis and
Singer, 1973; Martens and Goldhaber, 1978; Froelich et al.,
1979) .
Phosphorus is transported into the lake adsorbed to iron and
manganese oxides attached to clays or floating free in the water
collumn with suspension sediments. A smaller amount is introduced
by biologic production within the lake. As these sediments
settle through the water column disssolved phosphorus may also be
added by adsorption to iron and manganese colloids, organics and
clays. The phosphorus remains stable in these forms in the
oxidizing lake water and accumulates on the bottom along with
organic material. As this oxidized sediment accumulates,
organics in the sediment decay and bacterial action reduces the
sediment just below the surface, out of reach of the oxidizing
lake water. Within this reducing environment, phosphate adsorbed
to clay and incorporated in more stable organic and iron
phosphate compounds, resists breakdown by bacteria (Emsley and
Hall, 19 76), but organic decay liberates CO and the sediments
2
become more reducing. Phosphorus is liberated as manganese is
reduced by bacterial metabolism (Chapter Two). Krauskopf (1979)
and Mortimer (1971) found that in sediments undergoing such Eh-pH
changes manganese becomes mobile before iron because of it's
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91
greater solubility.
After utilizing the more energy efficient oxygen compounds,
reduction of iron begins (Berner, 1980) following the reaction:
2 +
4 Fe(OH) +CH 0+7C0 =4Fe +8HC0 +3H 0.
3 2 2 3 2
2+
This reaction would release Fe and phosphorus into the pore
water. As concentrations increase manganese, iron and phosphorus
minerals precipitate when the ionic activation product exceeds
the solubility. In Flathead Lake sediments the presence of large
amounts of inorganic-extractable phsophorus correlated separately
to both iron and manganese concentration, and the low amounts of
carboante and organics (Joyce, 1980; App. I) indicate that
phosphorus is tied up in phosphates of iron and manganese. This
is supported by the discovery of the iron phosphate vivianite in
cores taken by Joyce (1980) and Potter(1978) and the work by
Murray (1982, Chapter Two).
As sediment accumulates and compacts, porosity decreases,
expelling pore water. The pore water migrates upward into less
compacted sediments (more porus) carrying manganese and
phosphorus in the reduced state. When they encounter the
overlying oxidizing environment, manganese precipitates as oxides
(probably attached to clays) and phosphorus
coprecipitates/adsorbes to ferric oxides and hydroxides. Ferrous
iron released in the reduced sediment always exceeeds phosphorus
and when oxidized it precipitates much of the phosphorus
(Wetzel, 1975; Forstner and Whittman, 1981). Some ferric
phosphate may form, but will hydrolize slowly and return some
phosphorus to the pore water (Hutchinson, 1957). If enough
organic compounds are present some iron will form humate
-------
92
complexes at the sediment-water interface. These compounds
accumulate as a flocculent and strongly adsorb phosphate
(Tipping, Woof and Cooke, 1981). The redox gradient controlling
these processes is maintained by bacterial motabolism within the
sediment. Changes in oxidation state and upward flow of pore
water concentrate phosphorus in the surface oxidized zone (Fig.
8) .
In summary, the distribution and migration of phosphorus in
Flathead Lake sediments reflects the mobility of iron and
manganese. Iron oxides/hydroxides and manganese oxides
containing adsorbed and coprecipitated phosphorus accumulate in
the oxidizing environment at the sediment-water interface.
Burial of sediments and decaying organic matter results in
a reducing environment which causes the reduction of iron and
manganese oxides/hydroxides releasing iron, manganese and
phosphorus to the pore water. Manganese reduces first and
migrates to the upper surface powered by pore-water flow. Iron,
manganese and phosphorus probably reach equilibrium in the
reduced sediment forming manganese and iron phosphates.
Phosphorus accumulates in the oxidized layer adsorbed to iron
oxides/hydroxides and/or humates/chelates separate from manganese
oxides. Because the stability of phosphorus is maintained by
oxidizing bottom water, a potentially large source of nutrients
exists if the bottom-water chemistry of Flathead lake were to
change. Locally, sediments contain over 3000 ppm phosphorus (as
3-
PO ) greater than values in much less pristine lakes (eg., Lake
Champlain, Hunt, 19 71). This phosphorus, in the highly soluble
-------
93
Mn oxides p_ Fe oxides
V I /
Cu-
CLAY
]-Zn-[
hP
I
organics
+ Cu cmpds
dissolved
Oa
SUSPENSION SEDIMENTS
EQUILIBRIUM
Mn-
P
-Fe
clays
PORE
WATER
Fi gure 8
FLOW
-------
94
complexes of iron and manganese, would be available if the
present oxidation-reduction system of the lake changes in the
future -
-------
95
Chapter Four
CONCLUSIONS AND PREDICTIONS
Johnnie N. Moore
Jaswant Singh Jiwan
The present Flathead Lake system has been extant for
approximately 12,000 to 14,000 years. During that time sediment
has accumulated under conditions very similar to those of today.
Suspension sedimentation dominates the lake and nutrients are
carried into the lake and deposited along with these sediments.
The geochemical framework of sediments concentrates phosphorus in
the upper layers of the sediment creating a large potential
source which could significantly change the nutrient budget of
Flathead Lake. This vast accumulation of nutrients remains
securely locked away in iron and manganese compounds as long as
the bottom waters remain oxygen-rich. If the bottom water
becomes annoxic, even locally, the sediments will release their
stores of phosphorus, dramatically changing the nutrient budget
of the lake.
In the sediment-water geochemical system acting in the lake
(Chapters Two and Three) there are three possiblities for
nutrient-sediment interactions (Fig.l). Because the redox
gradient that controls nutrient and metals migration is
ultimately powered by organic matter in the sediments, it is
-------
OX-RED interface abive SED-WATER interface
OXIDIZING
REDUCING
C
-------
97
convenient to discuss possible senarios based on the amount of
organic material in the sediment. However, the processes could
also be modified if major changes occured in the concentrations
of phosphorus or metals supplied to the lake.
The production of organic matter in lakes is controlled by
phosphate and nitrate (Wetzel, 1975; Drever, 1982).
Subsequently, productivity determines the amount of organic
material collecting in the sediment which controls the oxidation
state. Under sediment and bottom water reducing conditions,
nutrients and metals are pumped into the lake water; under
oxidizing conditions they are trapped at the sediment-water
interface. In Flathead Lake, and other large oligotrophic lakes,
this system can be described by three possible situations. Each
situation is defined by the amount of organic matter accumulating
in the sediment.
Situation One:
Small amounts of organics accumulating in sediment would
provide limited food for bacterial metabolism. Oxidizing water
from the lake would permeate into the sediment forming a discrete
layer of oxidized sediment. The thickness of this layer would
depend on the amount of reduction, the permeability of the
sediments and the oxygen content of the water. This situation
exists in oligotrophic lakes forming a distinctive orangish
oxidized zone at the sediment-water interface. As manganese and
phosphorus migrate upwards in this situation, they accumulate in
the oxidized layer of the sediment (Fig.l. lower).
-------
98
Situation Two:
If under the same lake water conditions organic material
were increased so that more accumualted in the sediment, the
phosphorus situation would adjust. Higher amounts of organics
would lead to more algal motabolism and the reducing pore water
could extend farther upward. With just the proper amount of
organic material the oxidation-reduction interface would move
upwards to the sediment-water interface. Under such conditions
iron and manganese crusts would form at the surface, fixing
phosphorus in relatively sediment-free oxides and hydroxides
(Fig.l, middle).
Situation Three:
If the organic content increased even more, nutrients would
not be trapped in the sediments but released to the water column.
Very high bacterial production would push the reducing-oxidizing
interface into the bottom water. This situation would pump
phosphorus into the water column along with iron and manganese
(Fig.l, upper). Such a system would be self-feeding. As
phosphorus was pumped into the lake water productivity would
increase. Higher productivity would supply more organics to the
sediment to power the phosphorus pump. Such a cycle would not
easily change unless primary productivity was nearly completely
eliminated. This cycling process makes it very difficult to
reverse lake eutrophication because of the large storehouse of
nutrients in the sediments (Drever, 1982; Williams et al., 1976).
Obviously the affect of situation three would depend on the
change of nutrient concentration in the lake water. Even with a
large amount of phosphorus released, if the total concentration
-------
99
did not change enough to affect the trophic state of the lake the
situation would last only briefly. Because eutrophication
rarely, if ever, throughout an entire lake but begins in
restricted bays, such affects would probably first occur in
isolated areas.
Flathead Lake bays, in general, support higher productivity
than the open lake and sediment accumulation in those bays is
richer in organics and contains higher concentrations of
phosphorus. If we assume all the phosphorus was released from
the upper one centimeter of sediment (essentially, the oxidized
layer) how would such an input change the trophic state of some
particular bays. It turns out, significantly!
Vollenweider (1975, 1976) calcualted that phosphorus
concentrations of 10 micrograms/liter is the critical value for
eutrophication in temperate lakes. Flathead lake lies at the
oligotrophic-mesotrophic boundary with average concentrations of
7.5 micrograms/liter of phosphorus. If phosphorus released from
sediment under isolated, short-term events increased
concentrations above the critical value the affect would be
selfsustaining. Specific examples suggest that such a system
could easily develop.
Woods Bay, the largest developed bay on the east side of
11
Flathead Lake, contains approximately 1.7x10 liters of water. If
all the extractable phosphorus was released from the upper 1
13
centimeter of sediment, 6.8x10 micrograms of phosphorus would
be supplied to the water column. Such an influx would change the
concentration to 400 micrograms/liter, forty times the amounts
-------
100
needed for eutrophication.
Yellow Bay would suffer even worse increases. With a volume
9 * 12
of 3.5x10 liters and 4.8x10 micrograms of phosphorus, the
concentration would climb to 1300 micrograms/liter if only the
upper 1 centimeter released it's phosphorus. Such a
concentration would be 130 times the critical value for
eutrophication. Larger bays fare no better. Sommer's Bay, the
largest, open bay on the northern shore, would contain 10 0 times
the phosphorus needed for eutrophication.
Even if only 10% of the available phosphorus was released in
these senarios the concetrations would be from 4 to 13 times that
need for eutrophication. So, the reservoir of phosphorus is very
significant and must be considered a potential source for drastic
change in the trophic status of Flathead Lkae.
-------
BIBLIOGRAPHY
Alden, W.C., 1953, Physiography and glacial geology of western
Montana: U.S. Geol. Sur. Prof. Paper 231, 190 pp.
Allison, L.E., 1935, Organic soil carbon by reduction of chromic
acid: Soil Science, v. 40, pp. 311-320.
Analytical Methods for Atomic Absorption Spectrophotometry, 1976,
Perkin Elmer Cookbook.
Anderson,G., and Arlidge, E.Z., 1962, The absorption of inositol
phosphates and glycerophosphate by soil clays, clay minerals
and hydrated sesquioxides in acid media. J. Soil. Sei. 13,
pp. 216-224.
APHA, 1975, Standard methods for the examination of water an <
waste water. 14th ed., Am. Pub. Health Assn., New York, p.
607.
Association of Official Agricultural Chemists, 1965: Official
' fethods of Analysis of the Association of Official
Agricultural Chemists. 10th ed., Sec. 2.023-2.025.
Berner, R.A., 1978, Rate of control of mineral dissolution under
earth surface conditions. Am. J. Sci. 278 pp. 1235-1252.
Berner, ' LA. , 1980, Early Diagenesis: A Theoretical Approach,
241 pp., Princeton Univ. Press.
Berner, R.A., 1981, A new geochemical classification of
sedimentary environments. J.Sed. Petrol. 51, 359-365.
Bennett, H. and Hawley, W.G., 1965, Methods of silicate analysis,
2nd ed., Acad. Press, London, 350 pp.
Bortleson, G.C., 1971, The chemical investigation of recent lake
sediments from Wisconsin lakes and their interpretation.
Wat. Pollut. > fontrol Res., Sec. 16010 EHR 03/71.
Calvert, S.E. and Price, N.B., 1977, Shallow water, continental
margin and lacustrine nodules: Distribution and
geochemistry. In Marine Manganese Deposits (ed.
G.P.Glasby), pp. 45-86. Elsevir.
Caroll,D., 1959, Ion exchange in clays and other minerals. Bull.
Geol. Soc. Am., v. 70, pp. 749-780.
Chester, ' I. and Hughes, M.J., 1967, A chemical technique for the
separation of ferro-manganese minerals, carnbonate minerals,
and adsorbed bed trace elements from pelagic sediments.
Chem. Geol. 2 ,245-262.
-------
102
Clark, A.L., 1971, Stratabound copper sulfides in the Precambrian
Belt Supergroup, northern Idaho and northwestern Montana,
U.S.A.: Soc. Mining Geologists of Japan Spec. Issue no. 3,
pp. 261-267.
Columbo, A. and Vivian R., 1973, Determination of carbon,
hydrogen and nitrogen in inorganic compounds by means of an
automatic organic elemental microanalyzer. Microchem J., v.
18, pp. 589-595.
Corliss, B.H. and Hunt , A.S., 1973, The distribution of
phosphorus in the sediment of St. Albans Bay, Lake
Champlain. Champlain Research Report, issue no. 4, p. 8.
Crecelius, E.A., Bothner, M.H., and Carpenter, R., 1975,
Geochemistries of arsenic, antimony, mercury and related
elements in sediments of Puget Sound, Environ. Sci. Technol.
9, 325-333.
Cronan, D.S. and Thomas, R.L., 1972, Geochemistry of
ferromanganese oxide concretions and associated deposits in
Lake Ontario. Geol. Soc. Am. Bull. 83, 1493-1502.
Dean, W.E., 1974, Determination of carbonate and organic matter
in calcareous sediments and sedimentary rocks. J.S.P., v.
44, no. 1, pp. 242-248.
Decker, G.L., 1968, Preliminary report on the geology,
geochemistry, and sedimentology of Flathead Lake,
northwestern Montana, unpub. M.S. thesis, Univ. of Mont.,
Missoula, p. 91.
Din, V.K. and Jones, G.C., 1978 7Determination of total carbon
and comined water in silicates using a C, H, N elemental
analyzer: Chem. Geol., v. 23, pp. 347-352.
Dobos, S., 1980, Sedimentological analysis of sediment aggregates
from the Flathead River delta, unpub. senior thesis. Univ.
of Mont., Missoula, MT, p. 15 and appendices.
Drever, J.I., 1982, The Geochemistry of Natural Waters, Prentice-
Hall, Inc., Englewood Cliffs, N.J., 388 pp.
Emerson, S. and Widmer, G., 1978, Early diagenesis in anaerobic
lake sediments - 11. Thermodynamic and kinetic factors
controlling the formation of iron phosphate. Geochem.
Cosmochim. Acta 42, 1307-1316.
Emsley, J. and Hall, D., 1976, The chemistry of phosphorus.
Harper and Row Publishers. New York, p. 563.
Environmental Protection Agency, 1976, Preliminary report of
-------
103
Flathead Lake, Flathead and Lake counties, Montana, E.P.A.
region VIII. National Eutrophication Survey, 55 p.
Erdraan, J. A. and Evans, ' J. J., 19 76. Elements in wheatgrass, Dave
Johnston Mine: U.S.G.S., Open-file Report 76-729, pp. 82-
85.
Forbes, S.A., 1983, A preliminary report on aquatic invertebrate
fauna of Yellowstone National Park and of the Flathead
region of Montana. Bull. U.S. Fish Comm. 11. pp. 207-256.
Forstner, U. and van Lierae, J.H., 1979, Trace metals in water
purification processes, in, Forstner, U. and Wittman, G.,
eds. Metal Pollution in the Aquatic Environment, Springer-
Verlag, Berlin, p. 486.
Forstner, U., 19 79B, Metal pollution assessment from sediment
analysis, in, Forstner, U., and Wittman, G., eds. Metal
Pollution In the Aquatic Environment, Springer-Verlag,
Berlin, p. 486.
Forstner, U., 1979C, Metal transfer between solid and aqueous
phases, in, Forstner, U., and Wittman, G., eds. Metal
Pollution in the Aquatic Environment, Springer-\erlag,
Berlin, p. 486.
Forstner, U. and Wittmann, G.T.W., 1981, Metal Pollution in the
Aquatic Environment, Springler-Verlag, New York, 486 pp.
Forstner, U., 1981a, Metal pollution assessment from sediment
analysis. In Metal Pollution in the Aquatic Environment
(eds. U. Forstner and G. Wittman), pp. 110-196, Springer-
Verlag,
Forstner, U., 19 81b, Metal transfer between solid and aquenous
phases. In Metal Pollution in the Aquatic Environment (eds.
U. Forstner and G. Wittman), pp. 197-270, Springer-Verlag.
Froelich, P.N.G., Klinkerhammer, G.P., Bender, M.L., Luedtke,
N.A., Heath, G.R., Cullen, D., Dauphin, P., Hammond, D.,
Hartman, B., and Maynard, V., 1979, Early oxidation of
organic matter in pelagic sediments of the eastern
equitorial Atlantic: suboxic diagenesis, Geochem.,
Cosmochim Acta, 43 pp, 1075-1090.
Gaudette, H,F., Toner, L., Folger, D.W., 1974, An inexpensive
titration method for the determination of organic carbon in
recent sediments ; J.S.P., v. 44, pp. 249-253.
Golachowska, J.B., 1971, The pathways of phosphorus in lake
water. Pol. Arch. Hydrobiol, v. 18: 325-365.
Goldberg, E.D., Hodge, V.F., Griffin, J.J., Korde, M., and
-------
104
Engenton, D.N., 1981, Impact of fossil fuel combustion on
the sediments: Environ. Sci. Technol., v. 15, pp. 466-471.
Golterman, H.L., 1973, "Vertical movement of phosphate in fresh
water". Environmental Phosphorus Handbook. John WileyZ
Interscience, New York, pp. 509-529.
Golterman, H.L., 1977, Sediments as a source of phosphate for
algal growth, pp. 286-293 in H.L. Golterman (ed.).
Interaction between sediments and fresh water junk.
Griffith, E.J., Beeton, A., Spencer, J.M., and Mitchell, D.T.,
1973, Environmental Phosphorus Handbook. John Wiley & Sons,
New York, p. 718.
Gross, M.G., 1965, The carbonate content of surface sediments
from the northeast Pacific Ocean. Northwest Science, v. 39,
pp. 85-92.
Gross, M.G., 1966, Organic carbon in surface sediment from the
northeast Pacific Ocean: Oceanology and Limnology, v. 1,
pp. 46-5 4.
Gumerman, R.C., 1970, Aqueous phosphate and lake sediment
interaction: Proc. 13th conference on Great Lakes research,
pt. 11, Inter. Assoc. for Great Lakes Research.
Gupta, S.K. and Chen, K.Y., 1975, Partitioning of trace metals in
selective chemical fractions of nearshore sediments:
Environ. Letters, v. 10, pp. 129-158.
Halmann, M., 1972, Chemical ecology, Evidence for Phosphate as
the only factor limiting algal growth in Lake Kinnert.
Israel. J. Chem. 10, pp. 841-855.
Halmann, M. and Stiller, M., 1974, Turnover and uptake of
dissolved phosphate in fresh water. a study in Lake
Kinneret: Limnology and Oceanography v. 19(5), pp. 776-783.
Harrison, J.E. and Grimes, D.J., 1970, Mineralogy and
Geochemistry of some Belt rocks, Montana and Idaho:
U.S.G.S.Bull. 1312-0.
Harrison, J.E., 1972, Precambrian Belt basin of northwestern
United States, Its geometry, sedimentation, and copper
occurrences: Geol. Soc. Am. Bull., v. 83, pp. 1215-1240.
Harrison, J,E., and Dominico, J.A., 1973, Association of copper
mineralization in miogeosynclinal clesties of the Belt
Supergroup: Belt Symposium, Univ. of Idaho, Moscow, ID, v.
1, pp. 113-115.
Harrison, J.E., Lange, I.M., and Harrison, J.P., 1977,
-------
105
Stratabound copper occurrences in green beds of the Belt
Supergroup, western Montana: Geol. Soc. No. Am., Rocky Mtn.
Sec., Field Guide No. 3, p. 12.
Harter, R.D., 19 68, Absorption of phosphorus by lake sediments.
Soil Sci. Soc. Am. Proc., v. 32, pp. 514-518.
Hem, J.D., 1981, Rates of manganese oxidation in aquenous
systems. Geochim. Cosmochim. Acta 44, 1311-1317.
Hesse, P.R., 1973, "Phosphorus in lake sediments", Environmental
Phosphorus Handbook, John Wiley-Interscience, New York, pp.
573-584.
Hlebicheck, D.D., 1981, Flathead delta gravity survey, unpub.
senior thesis. Univ. of Mont., Missoula, p. 8 and
appendices.
Holdren, G.C., Jr. and Armstrong, D.E., 1977. Interstitial
inorganic phosphorus concentrations in Lakes Mendota and
Wingra. Water Research, v. 11, pp. 1041-1047.
Hunt, Allen S., Townsend, P.H., and Boardman, C.C., 1968, Lake
Champlain Drainage Basin, Champlain Research Reports, Issue
No. 2.
Hunt, Allen S., 1971, Bottom sediments of Lake Champlain,
completion report OWRP, Project No. A-003-Vt., p. 127.
Hutchinson, G.E. and Wollack, A., 1940, Studies on Connecticut
Lake sediments, 11. Chemical analyses of a core from
Linsley Pond North Branford:- Am. J. Sci., v. 238, pp. 493-
517.
Hutchinson,G.E., 1957, A treatise on limnology I. Geography,
physics, chemistry. New York, John Wiley and Sons, Inc., p.
1015.
Hwang, C.P., Huang, P.M., and Lackie, T.H., 1975, Phosphorus
distribution in Blackstrap Lake sediments, Jour. Water Poll.
Control fed., v. 47(5): 1081-1085.
Hwang, C.P., 1977, Inorganic phosporus fractions in Blackstrap
Lake sediments (technical note). Water Research, v. 11, pp.
945-946.
Hynes, H.B. and Greib, B.J., 1970, Movement of phosphate and
other ions from and through lake muds. J. Fish. Res. Bd.
Can., v. 27, pp. 653-668.
Hynes, N.J., 1978, The distribution and source of organic matter
in river sediments. Environ. Geol. 2(5): 279-287.
Jackson, M.L., 1958, Soil chemical analysis. Prentice Hall, Inc.,
-------
106
Englewood Cliffs, NJ, p. 498.
Jackson, K.S., 1975, Geochemical dispersion of elements via
organic complexing, Unpubl. thesis, Carleton, Univ., Ottawa,
Canada, 344 pp.
Jeffery, P.G., 1975, Chemical Methods of Rock Analysis, 2nd ed.,
526 pp., Pergamon Press.
Johns, W.M., 1970, Geology and mineral deposits of Lincoln and
Flathead counties, Montana: Montana Bur. of Mines and Geol.
Bull. 79, p. 182.
Jonasson, I.R., 1977, Geochemistry of Sediment/water interactions
of metals, including observations on availability, in, The
Fluvial Transport of Sediment-Associated Nutrients and
Contaminants, IJC/PLUARG. Shear, H., Watson, A.E.P. (Eds).
Windsor/Ont. pp. 255-271.
Joyce, M.J., 1980, Stratigraphy, clay mineralogy and pesticide
analvsis of Flathead Lake sediments, Flathead Lake, Montana,
unpub. M.S. thesis, Univ. of Mont., Missoula, p. 86.
Kalff, J. and Knoechel, R., 19 78, Phytoplankton and their
dynamics in oligotrophic and eutrophic lakes. Ann. Rev.
Ecol, Syst. 9: pp. 475-495.
Keis, B., 1981, The morphology and genesis of a coarse grained
spit, unpub. senior thesis. Univ. of Mont., Missoula, p. 8
and appendices.
Kennedy, C.R., 1965, Minerology and cation exchange capacity of
sediments from selected streams. U.S. Geol. Surv. Prof.
Pap, 433-D: 28.
Klinkhammer, G.P., 1980, Early diagenesis in sediments from the
eastern equatorial Pacific. II. Pore water metal results.
Earth Planet. Sci. Lett. 49, 81-101.
Klinkhammer, G.P., and Bender, M.L., 1980, The distribution of
manganese in the Pacific Ocean, Earth Planet. Sci. Lett. 46,
361-384.
Kogan, J.H., 1981, A seismic sub-bottom profiling study of recent
sedimentation in Flathead Lake, Montana, unpub. M.S. thesis,
Univ. of Mont., Missoula, p. 98.
Konizeski, R.L., Brietkrietz, A., and McMurtrey, R.G., 1968,
Geology and ground water resources of the Kalispell Valley,
northwestern Montana, Montana Bur. Mines and Geol. Bull. 68,
42 pp.
Kortmann, R.B., 198Q, Benthic and atmospheric contributions to
-------
107
the nutrient budgets of a soft-water lake. Limnology and
oceanogrphy, v. 25(2), pp. 229-239.
Krauskopf, K.B., 1979, Introduction to Geochemistry, 2nd ed., 617
pp., McGraw-Hill.
Lange, I.M. and Moore, J.N., 1981, A Cu-Ag bearing oolite bed in
the Spokane Formation, Belt Supergroup near Wolf Creek,
Montana: G.S.A. abstracts with programs, v. 13, no. 4, p.
202.
Lean, D.R.S., 1973, Phosphorus dynamics in lake water, Science,
1979, pp. 678-680.
Lee, G.P., Jones, R.A., and Rast, W. , 1980, Availability of
phosphorus to phytoplankton and its implication for
phosphorus management strategies. In Loehr, R.C., Martin,
C.S., and Rast. W. (Eds). Phosphorus Management Strategies
for Lakes, Ann Arbor Science Publ. inc. 490 pp.
Leventhal, J.S., and Shaw, V.E., 1980, Organic matter in
Appalachian Devonian black shale: I. Comparison of
techniques to measure organic carbon, II. Short range
carbon content variations: Jour. Sed. Pet., v. 50, n. 1,
pp. 77-81.
Lindgren, F.T., Stevens, G.R., and Jensen, L.C., 1972, Elemental
C, H, and N microanalysis of crushed rock and soil samples.
J. Am. Oil Chem. Soc. v. 49, pp. 208-214.
Lynn, D.C., and Bonetti, E. 19 65, Mobility of manganese in
diagenesis of deep-sea sediments: Mav. Geol., v. 3, pp.
457-474.
Martens, C.S. and Goldhaber, M.B., 1978, Early diagenesis in
transitional sedimentary environments of the White Oak River
Estuary, North Carolina, Limnol Oceanogr., 23, pp. 428-441.
Malmquist, P.A., 1975, Heavy metals in urban storm water: Abstr.
Int. Conf. Heavy Met. Environ., Toronto, C-46/48.
Marshall, C.D., 1964, The physical chemistry and mineralogy of
soils, J. Wiley and Sons.
McKeague, J.A. and Day, J.H., 1966, Dithionite- and oxalate-
extractable Fe and A1 as ids in differentiating various
classes of soils. Can. J. Soil Sc. 46, 12-22.
McKelvey, V.E., 1973, "Abundance and distribution of phosphorus
in the lithosphere." Environmental Phosphorus Handbook,
John Wiley-Interscience, New York, pp. 13-32.
Mills, G. and Quinn, J.G., 1979, Determination of organic carbon
in marine sediments by persulfate oxidation: Chem. Geology,
v. 25, pp. 155-162.
-------
108
Morgan, J.J., 1967, Chemical equilibrium and kinetic properties
of manganese in natural waters. In Principles and
Application of Water Chemistry (eds, S.D. Faust and J.V.
Hunter), pp, 561-524, Wiley.
Mortimer, C.H., 1971, Chemical exchanges between sediments and
water in the Great Lakes - Speculations on probable
regulatory mechanisms. Limnol. Oceanog. 16, 387-405.
Mudge, M.R., 19 70, Origin of the disturbed belt in northwestern
Montana: Geol. Soc. Am. Bull., v. 81. pp. 377-392.
Natusch, D.F.S., Wallace, J.R., and Evans, C.A., Jr. 1974, Toxic
trace elements: Preferential concentration in respirable
partials: Science, v. 183, pp. 202-204.
Natusch, D.F.S., Bauer, C.F., Matusiewiez, H., Evans, C.A.,
Baker, J., Loh, A., Linton,R.W., and Hopke, P.A., 1977,
Characterization of trace elements in fly ash: Institute
for Environmental Studies Report, no. 3, Univ. of 111.,
Urbana, 111.
Nie, H.H., Hull, C.H., Franklin, M.N., Jenkins, J.G., Sours,
K.J., Norusis, M.J., and Beadle, V., 1980, SCSS: A User's
Guide to the SCSS Conversational System, 595 pp., McGraw-
Hill.
Niino, Hiroshi, Emery, K.O., and Kim, C.M., 1969, Organic carbon
in sediments of the Japan Sea: Jour. Sed. Pet., v. 39, pp.
1390-1398.
NRC Committee on Accessory Elements, 1979, Redistribution of
Accessory Elemention Mining and Mineral Processing, v. 1,
National Academy of Sciences, Wash., D.C.
Nunalee, D., 1976, Water quality inventory and management plan:
Water Quality Bureau, Environmental Science Div., Montana
Dept. Health and Environmental Science, 114p.
Oglesby, R.T., 1977, Phytoplankton productivity verses dissolved
nutrient levels of Flathead Lake, Montana. Ph.D. disserta-
tion, University of Utah, 211p.
Ostrofsky, M. L. and Duthie, H.C., 1975, Primary productivity,
phytoplankton and limiting nutrient factors in Labrador
Lakes; Int. Revue Ges. Hydrobiol., 60(2), pp. 145-158.
, 1980, Trophic upsurge and the relationship between
phytoplankton biomass and productivity in Smallwood
Reservoir, Canada: Can. J. Bot. 58, pp. 1174-1180.
Otsuki, A. and Wetzel, R.G., 1972, Coprecipitation of phosphate
with carbonates in a mail lake: Limmol. Oceanog. 17. pp.763-
767.
-------
109
Perkin-Elmer Corp., 1976 , Standard methods-Atomic Absorption
Spectrophotometer Manual.
Pittman, G. , 1979, Toxil < metals, in, Forstne r, V. and Wittman,
G., Metal pollution in the aquatic environment. Springer
Veriag, Berlin, p. 486.
Potter , D.S., la?^, The zooplankton of Flathead Lake: A
historical review with suggestions for continuing lake
resource management: Unpublished Ph. D. dissertation,
University of 'Montana, Missoula.
Price, TUA,, 1965, Flathead map-area, British Columbia and
Alberta: Geol. Surv. Canada, Mem. 336, p 221.
Price, N.B., 1976 Chemical diagenesis of sediments, in, Chemical
Oceanography (eds., J.P. 'Wiley and' I Chester) v. 6, pp.l-
58.
Preuss, C. and Kollman, H., 1974, Metalgehelt in Klarsclammen:
Naurweissenschaften, v. 61, pp. 270-274.
Qamar, A.J. and Breuninger, R., 1979, Northern Tier Report No. 4,
Earthquake hazar c to the proposed Northern Tier Pipeline in
Montana: Montana Dept. of Natural Resources * nd
Conservation, Energy Div., Helena, Mt., p.54.
Rao, M.S., 1960, Organic matter in sedi! ents of the east coast of
India: AAP (Bull., v. 44, pp. 1705-1713.
Richey, J.E., 1976, Patterns of phosphorus supply and utilization
in Lake Washington and Findley Lak<2 r Limnol. Oceanog. , v.
24 (5) , pp. 906-916.
' bbbins, J.A. and Callender, E., 1975, Diagenesis of manganese in
lake Michigan sediments: Am. Jour. Sci., v. 275, pp.512-533.
Rodel, M.G. and Armstrong ,D.E.,1977, Sorption and hydrolysis of
added organic phosphorus compounds in lake sediments:
Limnol. Oceanog., v.22(3), pp. 415-422.
Sbar, M.L., Barazangi, ' L, Dorman, J., Scholz, C.H., and Smith,
R.B., 1972, Tectonics of the inte mountain seismic belt,
western U.S.' : Microea fchquake seismicity and composite
faultplane solutions: Geol. Soc. Amer. Bull., v. 83, pp. 13-23.
Schindler, D.W., 1977, Evolution of phosphorus limitation in
lakes: Science, v.195, pp. 260-262.
Schollenberg, C.J., 1927, A rapid approximate method for
deteriming soil organic matter: Soil Sci., v. 24, pp. 65-68.
Seastedt, T.R. and Tibbs, J.F., 1974, Land use and water quality
in the Flathead drainage: E.P.A. publication, 155p.
-------
110
Serruya, C. , Edelstein, M., Pollingher, U. and Serruya, S., 1974,
Lake Kinneret sediments, nutrient composition of pore water
and mud-water exchange: Limnol. Oceanog., v. 19, pp. 489-
508.
Shukla, S.S., Syers, J.K., Williams, J.D., Armstrong, D.E. and
Harris, R.F., 1971, Sorption of inorganic phsophate in
, , and Armstrong, D.E., 1972, Arsenic interference in
the determination of inorganic phosphate in lake sediments:
J. Envir. Qual., v.l, pp. 292-295.
Skei, J. and Paus, P.E., 1979, Surface metal enrichment and
partitioning of metals in a dated core from a Norwegian
fjiord: Geoch. Cosmoch. Acta, v. 43, pp. 239-246.
Sonstelie, L.C., 1924, A study of the water quality of the
Flathead River, Missoula, Mt.: M.A.T. thesis, University of
Montana, Missoula.
Stanford, J.A. and Potter, D.S., 1976, Limnology of the Flathead
Lake-River ecosystem, Montana: a perspective: Proc. Syitip.
Terrestrial and Aquatic Ecological Studies of the Northwest,
March, 26-27.
, Stuart, T.J., Coulter, J.D. and Hauer, F.R., 1981,
Limnology of the Flathead River-Lake ecosystem, Montana,
E.P.A. Annual report.
Stevenson, P.R., 1976, Microearthquakes at Flathead Lake,
Montana: A study using automatic earthquake processing:
Bull. Seis. Soc. Am., v. 66. pp. 61-80.
Stickney, M.C., 1980, Seismicity and gravity studies of the
faulting in the Kalispell Valley, Northwest Montana: Unpub-
lished M.S. thesis, University of Montana, Missoula.
Stoffel, K.L., 1980, Glacial geology of the southern Flathead
Valley, Lake county, Montana: Unpublished M.S. thesis,
University of Montana, Missoula.
Stumm, W. and Morgan, J.J., 1970, Aquatic chemistry, an
introduction emphasizing chemical equilibria in natural
waters: Wiley Interscience, New York, 583p.
1 ancj Leckie, J.O., 1971, Phosphate exchange with
sediments: Its role in the productivity of surface waters.
Proc. 5th. Int. Water Pollut. Res. Conf., Pergamon Press,
London.
Suess, E., 1978, How can we distinguish between natural and
anthropogenic materials in sediments and can we predict the
effects of men's additions; u.N.E.S.C.O. Worksop Bioch.
Estreame sediment, Melreux, Belgium, pp. 224-237.
-------
Ill
Swanson, V.E., Medlin, J.H., Hatch, J.R., Coleman, S.L.,
Woodruff, S. and Hildebrand, R.T., 1976, Collection,
chemical analysis, and evaluation of coal samples in 19 75:
U.S. Geol. Survey Open-file Report 7 6-468.
Syers, J.K., Harris, R.F. and Armstrong, D.E., 1973, Phosphate
chemistry in lake sediments: J. Envir. Qual., v.2, pp.1-14.
f Williams, J.D.H. and Walker, T.W. , 1968, The
determination of total phosphorus in soils and parent
material: New Zealand, J. Agr. Res., v. 11, pp. 757-762.
Thies, T.L. and Singer, P.C., 1973, The stabilization of ferrous
ions by organic compounds in natural waters, in, Trace
metals and metal-organic interactions in natural waters,
Singer, P.C. (ed.) Ann Arbor Science Publ., pp.303-320.
Thomas, E.A., 1965, Phosphat-elimination in der Belebtschamman-
lage von Mannedorf und Phosphat-fixation in see-und
klarchlanvm: Vierteljahrsschr Naturforsch Ges. Zurich, v. 110
pp. 419-434.
Tibbs, J.F., Gaufin, A.R. and Stanford, J.A., 1975, Distribution
and biotic effects of nutrients in Flathead Lake: Montana
Research Report to E.P.A. and State of Montana Dept. of
Health and Environmental Science, 89p.
Tipping, E., Woof, C. and Cooke, D., 1981, Iron oxide from a
seasonally anoxic lake: Geoch. Cosmoch. Acta, v. 45, pp.
1411-1419.
Tourtelot, E.B. and Vine, J.D., 1976, Copper deposits in
sedimentary and volcanic rocks: U.S. Geol. Survey Prof.
Paper 907-C, 34p.
U.S. Committee for Geochemistry, 1980, Trace element geochemistry
of coal resource development related to environmental
quality and health: National Acad. Press, Wash., D.C., 153p.
Van Olphen, H., 1963, An introduction to clay colloid chemistry:
Wiley Interscience, New York, 301p.
Vaughn, B.E., Abel, F.H., Cataldo, Da., Hales, J.M., Hane, C.E.,
Ranitelli, L.A., Roustson, R.C., Wildung, R.E. and Wolf,
E.G., 1975, Review of potential impact on health and
environmental quality from metals entering environment as a
result of coal utilization, Pacific Northwest Laboratories,
Battille Memorial Institute, Richland, Wash.
Vollenweider, R.A.,1971, Scientific fundamentals of the
eutrophication of lakes and flowing waters, wtih particular
reference to nitrogen and phosphorus as factors in
eutrophication: Tech. Report DAS/SCI/68.27, Organ. Econ.
Cooperation and Development, Paris 250p.
-------
112
, 1975, Input-output models with special reference to the
phosphorus loading concept in limnology: Schwei2 Z. Hydrol.
v. 37, pp. 53-84.
' 19 76, Advances in defining critical loading levels for
phosphorus in lake eutrophication: Mem. 1st. Ital. Idrobio,
v. 33, pp.53-83.
Walker, T.W. and Adams, A.F.R., 1957, Studies on soil organic
matter: The influence of phosphorus content cf the parent
materials on accumulations cf carbon, nitrogen, sulphur and
organic phosphorus in grassland soils: Soil Sci., v. 85, pp.
307-318.
Wetzel, R.G., 1975, Limnology. W.B. Saunders Co., Toronto,
Canada, 743 p.
Williams, J.D., Jaquet, J.M. and Thomas, R.L. , 1976, Forms of
phosphorus in the surficial sediments of Lake Erie: J. Fish.
Res. Canada, v. 33, pp. 413-429.
t Murphy, T.P. and Mayer, T. , 1976b, Rate of accumualtion
of phosphorus forms in Lkae Erie sediments : J. Fish. Res.
Canada, v. 33, pp.430-439.
Whipple, W., Jr. and Hunter, J.V., 1977, Nonpoint sources and
planning for water pollution control: J.W.P.C.F., v. 49,
pp.15-23.
Wittman, G., 1981, Toxic metals, in, Forstner, U. and Wittman, G.
(eds) Metal pollution in the aquatic environment, Springer
Verlag, Berlin, 486p.
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APPENDIX
Methods
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114
Sediment Sampling
Sediment samples were collected during the summers of 19 80
and 19 81, operating out of the University of Montana Biological
Station at Yellow Bay. Sampling sites were located on a one-mile
grid by sextant resectioning on shoreline topographic features.
Grab samples taken at 110 sites were analyzed for grain size,
extractable phosphorus and extractable heavy metals.
Originally, the Coulter counter was used to analyze for
grain size. unfortunately, because of noise generated by the
instrument in the finest size material, we feel we cannot trust
the data. Also, because the technique involves mixing two data
sets, other problems are introduced. Our statistical analysis of
the data suggests that the instrument modifies the distribution
during analysis. Because of these two problems, we abandoned all
data collected on the Coulter Counter and used established methods
of grain size analysis using a simple pipette technique developed
several decades ago and free of major analytical problems.
In many grab samples, a distinct difference was recognized
between an upper, light oxidized layer and a lower, dark reduced
layer. Whenever possible, these subsamples were collected and
analyzed separately. All grab samples were stored in
polyethylene containers, packed in ice on the boat, then
transferred to refrigerators where they were kept at 40ฐC until
analyzed.
Short cores Cup to lm long) of sediment collected at
approximately 50 sites in the southern lake were used for
establishing a sedimentary framework of the surface sediments.
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115
Long cores (up to 5m long) were collected at 11 sites to
determine sedimentation history and ellucidate near-suface units
in sub-bottom profiles. Extractable phosphorus and heavy metal
concentrations were determined for selected samples from the long
cores.
Heavy Metals
The extraction scheme used for heavy metals analysis was a
step extraction of the type developed by Chester and Hughes
(1967), Gupta and Chen (1975R, and Skei and Paus (1979). The step
extraction process used in this study was a simplified version of
the scheme devised by Skei and Paul (19 79) involving only two
steps.
The first step in the process was an extraction using a weak
acetic acid solution. A portion of the sample was oven dried at
o
50-60 C. One-third of a gram of this dried material was then
placed in a Nalgene screw-cap test tube, to which was added 25 ml
of acetic acid (20%). The test tube was then transferred to a
mechanical shaker table and shaken for 12 hours at room
temperature. The tube was then centrifuged for 15 minutes at
3000 rpm. The sample was then decanted into a polyethylene vial
o
and stored at or below 4 C. The samples were then analyzed for
metals using a Perkin-Elraer 5000 atomic absorbtion
spectrophotometers equipped with hollow cathode lamps. The
elementsiron, manganese, zinc, and copper were analyzed in
flame mode and/or graphite tube furnace mode.
The second step involved a complete fusion-dissolution of
the sediment using a procedure developed by Yule and Swanson
-------
116
(1969). One-tenth gram of dried sediment was fused with 0.6g of
o
lithium metaborata at 1000 C for 15 minutes in a platinum
crucible. The crucible was then quenched in cold, deionized
water and the resulting fused glass was then dissolved by adding
10.0 ml of cone HCl and 40.0 ml of hot dionized water in a tall
form 100 ml beaker, and stirring with a magnetic stirrer. The
solution was then diluted to 200 ml with deionized water, and
stored in polyethylene bottles. Metal analysis of the solutions
were performed using a varian model AA-6 atomic absorbtion
spectrophotometer in flame mode.
For the analysis of both the extracted solutions and the
solutions resulting from total dissolution, re-agent blanks were
analyzed and either spikes or duplicates of every third sample
were also analyzed. Standard solutions were made up with
chemical compositions and concentrations duplicating those of the
s mple solutions. Re-agent grade materials were used in all
cases.
The acetic acid extraction releases only those metal ions
that are weakly bound to carbonates, clays, iron and manganese
compounds, and organic particles (Loring, 1976). According to
Gupta and Chen (1975), those metal ions are the ones that could
become available to the biota if the sediments are disturbed,
either chemically or physically. The metal released during the
fusion-dissolution on the other hand includes all metal present,
whether weakly or tightly bound. The difference between the two
would be the metal that is tightly bound, for example in crystal
lattices, and therefore unavailable to the biota.
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117
Extractable Phosphorus
Total, inorganic and organic phosphorus were determined in
the lake sediments after extraction of the ignited and unignited
sediment sample with IN H SO . A sub-samole was taken, after
2 4
o
thoroughly mixing the grab sample, and dried at about 62 c. Two
portions of the sample weighing 0.5 gm were taken. One portion
o
was ignited for four hours at 550 C in a muffle furnace. The
ignited sample was cooled to room temperature. The ignited and
unignited samples were then extracted with IN H SO for 16 hours
2 4
on a shaking table. After extraction, these samples were
centrifuged for 15 minutes. The phosphorus was measured in both
the portions of the decantant by ascorbic acid method.
A solution of 1ml of the decantant from the extraction and
about 5 ml of deionized water was neutralized with IN NaOH using
phenophthalein as an indicator. The end point was marked by the
appearance of light pink color which persists for at least 20 to
30 seconds after neutralization, the solution was diluted to
exactly 25.0 ml. Then, 4 ml of combined re-agent was added ,
1
and the solution was allowed to stand for exactly 20 minutes in
order to give color an equal time to develop in all samples.
1. 100 ml of combined re-agent was obtained by mixing 50 ml of 5N
H SO ; 5 ml potassium antimony tartrate solution having 1.3715
2 4
gm of K(SbO)C H 0 1/2H 0 in 500 ml of deionized water; 15 ml of
4 4 6 2
ammonium molybdate solution containing 20 g (NH ) Mo O HO in
4 6 7 26 2
500 ml of deionized water; and 30 ml of 0.1 M s
-------
118
The color absorbance of each sample was then measured using a
spectrophotometer at a wavelength of 830 nra. Standard solutions
and blanks were run under similar conditions.
The phosphorus extracted from ignited sediments will be
referred herein as inorganic phosphorus and that extracted from
unignited portion as total phosphorus. The difference between
extractable total and inorganic phosphorus is termed extractable
organic phosphorus.
-------
APPENDIX II
Raw Data
Metals and phosphorus reported in ppm extractable.
Carbon, sand, silt and clay in weight percent.
Depth in feet, reference lake level is 2893 ft
-------
120
METALS
SAMPLE
ZINC
OX
NONOX
80- 1
0.0
12.5
80- 3
0.0
9.5
80- 4
0.0
11.2
80- 5
0.0
10.7
80- 6
0.0
8.3
80- 7
0.0
8.6
80- 8
0.0
9.0
80- 10
0.0
6.7
80- 12
0.0
12.0
80- 13
0.0
17.6
80- 15
0.0
5.5
80- 17
0.0
8.6
80- 19
0.0
12.8
80- 20
0.0
8.3
80- 22
0.0
6.8
80- 26
0.0
13 .2
80- 29
0.0
17 .7
80- 30
0.0
3.0
80- 31
0.0
13.0
80- 32
0.0
12.7
80- 34
0.0
19.4
80- 36
0.0
12.1
80- 38
14.2
15 .4
80- 51
14.2
18.7
80- 53
18.8
14.9
80- 54
0.0
28.7
80- 55
20.1
28.5
80- 57
0.0
26.2
80- 59
0.0
25.7
80- 60
22.4
15.6
80- 62
0.0
20.1
80- 64
0.0
27.7
80- 65
0.0
11.3
80- 67
19.0
19.6
80- 68
21.0
20.6
80- 70
20.5
19.1
80- 71
10.1
25.4
80- 73
14.7
23.9
80- 75
13.5
13.9
80- 78
15.3
21.9
80- 79
15.5
23.3
80- 81
8.1
7.4
80- 82
0.0
4.5
80- 83
0.0
3.8
80- 85
9.7
16.3
80- 86
16.5
21.3
80- 87
0.0
9.8
80- 88
0.0
16.3
80- 91
0.0
17.6
80- 92
15.0
18.3
80- 93
14.9
16.3
80- 94
15.6
26.2
80- 96
15.7
21.0
80- 98
15.7
19.6
80- 99
15.7
20.9
MANGANESE
OX
NONOX
OX
0.0
64.1
0.0
0.0
141.2
0.0
0.0
130.3
0.0
0.0
130.7
0.0
0.0
365.1
0.0
0.0
235.0
0.0
0.0
300 .7
0.0
0.0
448.1
0.0
0.0
1062.2
0.0
0.0
48.5
0.0
c.o
54.9
0.0
0.0
135.4
0.0
0.0
64.8
0.0
0.0
245.9
0.0
0.0
27.0
0.0
0.0
44.8
0.0
0.0
89 .9
0.0
0.0
251.5
0.0
0.0
86.6
0.0
0.0
87.3
0.0
0.0
41.1
0.0
0.0
29.4
0.0
1124.2
427.3
4207.1
2370.4
1065.3
5293.0
1028.8
308.0
5850.5
0.0
291.5
0.0
1641.4
699 .2
6255.0
0.0
155.6
0.0
0.0
74.1
0.0
164.8
137.5
2474.1
0.0
65.4
0.0
0.0
352.1
0.0
0.0
26.3
0.0
1439.3
1008.4
5393.3
380.3
237.5
3507.0
223.7
117.8
3031.5
1769.3
1429.8
2939.5
2490.9
1706.9
5063.4
1625.3
981.5
2577.0
2664.5
2712.9
6335.0
2327.6
1827.8
5879.1
218.2
673.5
1094.4
0.0
70.9
0.0
0.0
44.3
0.0
472.9
1844.1
2098.3
1387.9
1817.1
5515.6
0.0
477.8
0.0
0.0
3173.0
0.0
0.0
1771.7
0.0
2896.4
2175.5
5703.6
2727.4
2641.8
5972.5
2453.8
2125.7
4199.7
2612.0
2304.8
5068.4
2797.5
1946.9
5181.0
2396.2
2830.3
4326.8
COPPER
NONOX
OX
NONOX
1813.0
0.0
8.9
1928.6
0.0
13 .7
2385 .6
0.0
11.7
2403.3
0.0
15.0
3692.3
0.0
6.0
1854.0
0.0
7.2
2180.6
0.0
7.0
2763.1
0.0
11.0
3844.7
0.0
16.5
2009.5
0.0
12.8
1793.8
0.0
12.2
1462.3
0.0
3.7
2440.5
0.0
10.0
2793.1
0.0
6.3
895.9
0.0
6.8
1818.1
0.0
9.6
2618.9
0.0
11.7
501.5
0.0
2.8
2696.7
0.0
9.9
2715.4
0.0
8.5
1880.9
0.0
14.2
1335.8
0.0
11.0
5370.0
10.0
11.9
4919.1
9.2
14.5
2688.1
7.4
7.6
3636.6
0.0
12.2
5623.5
9.5
13.8
1668.8
0.0
8.6
2025.3
0.0
10.5
2765.4
11.5
13.9
1860.5
0.0
12.1
4787.3
0.0
12.9
1795.5
0.0
10.0
6752.2
12.7
14.1
3185.3
12.5
11.6
2440.0
10.2
9.3
5148.3
6.9
12.0
5410.5
9.6
11.8
4875.2
7.2
11.0
5902.3
8.1
13.4
4573.5
8.7
14.4
3158.8
3.8
9.9
1404.0
0.0
3.4
408.5
0.0
1.6
4417.8
7.3
12.9
5346.5
12.2
15.4
2172.0
0.0
7.4
6166.6
0.0
13.9
6458.5
0.0
14.3
5592.2
11.0
14.8
5680.2
10.5
16.0
5291.7
9.6
14.4
5337.0
15.9
15.6
5599.4
11.4
15.9
5072.0
11.2
13.5
-------
METALS
121
SAMPLE
80-101
80-102
80-105
80-106
80-110
80-111
81-112
81-114
81-115
81-116
81-117
81-118
81-119
81-120
81-122
81-123
81-124
81-125
81-126
81-127
81-128
81-129
81-130
81-131
81-132
81-133
81-134
81-135
81-136
81-137
81-138
81-139
81-140
81-141
81-143
81-144
81-145
81-146
81-147
81-148
81-149
81-150
81-151
81-152
81-153
81-154
81-155
81-156
81-157
81-158
81-159
81-160
81-161
81-162
81-163
ZINC
OX
NONOX
0.0
29.1
0.0
19.5
15.6
23.4
15.0
22.5
16.2
14.8
14.2
20.3
0.0
6.2
13.1
13.2
13.1
16.8
14.5
14.0
14.0
13.3
12.7
17.6
11.4
13.0
14.4
22.5
22.1
15.9
14.2
13.3
13.9
13.2
13.8
19.4
13.8
23.5
13.5
16.6
13.2
19.4
12.0
12.6
15.4
17.5
16.0
14.8
16.4
23.1
14.6
20.1
10.0
13.4
13.0
16.2
13.3
18.1
11.4
14.3
12.7
17.1
10.2
12.9
6.7
6.0
19.9
25.6
17.9
17.5
14.9
15.6
12.8
12.7
8.8
11.2
10.5
12.0
9.3
10.4
12.1
13.6
13.4
17.7
12.2
17.5
9.7
7.2
0.0
8.0
0.0
6.4
9.4
9.2
0.0
7.1
13.2
12.1
17.6
20.2
24.7
21.5
72.1
52.3
0.0
12.7
11.9
13.3
10.3
12.9
MANGANESE
OX
NONOX
0.0
1536.9
0.0
2404.7
7030.8
1462.8
2235.7
2107.5
1642.1
1699.0
2371.9
1529.0
0.0
125.2
2260.0
802.7
1627.0
589.0
1130.0
512.9
999.0
627.8
1756.0
375.8
1515.0
659.8
671.2
290.7
2132.0
1397.0
2280 .0
2125.0
2386.0
1510.0
1508.0
1060.0
1781.0
806.1
1877.0
816.2
1197.0
880.4
1678.0
1382.0
2258.0
2517.0
1876.0
1635.0
2381.0
1994.0
2124.0
1752.0
1263.0
1034.0
1651.0
690.8
1382.0
641.1
890.4
621.5
786.3
387.8
931.2
772.3
189.6
105.4
726.0
524.9
661.7
999.9
1891.0
831.9
2071.0
634.6
907.7
261.8
1044.0
245.2
1510.0
430.4
1767.0
449.5
1740.0
648.2
1884.0
456.1
257.8
124.5
0.0
179.4
0.0
174.5
365.3
304.1
0.0
131.1
1395.0
577.8
1136.0
493.5
1633.0
587.3
492.0
233.5
0.0
1646.0
262.6
112.4
717.2
455.8
IRON
OX
NONOX
0.0
5392.3
0.0
5793.2
4522.0
4271.4
3569.0
5241.0
1887.8
3001.1
4316.7
4051.0
0.0
808.5
4162.0
3862.0
3532.0
4213.0
3683.0
3707.0
3868.0
4739.0
4447.0
4428.0
2806.0
3849.0
3228.0
2901.0
3853.0
3272.0
3437.0
5792.0
4465.0
3850.0
4145.0
3827.0
4356.0
3688.0
3838.0
4883.0
3780.0
3383.0
3655.0
3541.0
4459.0
6294.0
3986.0
3699.0
4230.0
4575.0
2937.0
4358.0
3728.0
3680.0
3583.0
3347.0
3839.0
3529.0
3859.0
3568.0
3403.0
3108.0
3568.0
3390.0
675.8
711.0
4137.0
4768.0
3218.0
3721.0
3565.0
3569.0
3478.0
4183.0
2949.0
2503.0
2946.0
2339.0
4000.0
2810.0
4471.0
3869.0
3511.0
3998.0
4154.0
3080.0
1106.0
972.3
0.0
1761.0
0.0
1512.0
2203.0
2355.0
0.0
659.8
4027.0
4188.0
4155.0
4122.0
3093.0
4477.0
5085.0
3385.0
0.0
594.4
1240.0
845.8
2333.0
3254.0
COPPER
OX
NONOX
0.0
14.7
0.0
15.9
11.2
13.3
10.4
14.5
9.9
12.2
10.0
9.3
0.0
1.4
6.7
10.8
7.1
9.7
7.0
8.9
6.3
9.3
6.3
9.3
6.7
11.2
6.7
8.2
8.9
11.9
8.6
11.6
9.3
13.8
6.3
9.3
6.7
8.9
7.4
10.1
6.7
9.3
8.2
12.3
5.2
10.1
5.2
10.4
9.7
10.1
4.8
8.9
8.6
10.1
6.3
8.2
5.9
8.2
7.4
8.9
5.9
10.8
10.8
13.8
3.3
4.8
8.2
10.4
7.4
9.7
6.3
11.2
6.3
9.7
4.4
7.4
5.9
6.7
7.4
7.4
8.2
10.8
7.8
8.2
5.9
9.7
3.3
3.3
0.0
4.4
0.0
5.2
11.2
7.4
0.0
2.9
6.3
13.8
6.3
10.1
5.9
10.4
6.3
8.6
0.0
2.9
4.0
4.0
7.0
9.3
-------
1
3
4
5
6
7
8
10
12
13
15
17
19
20
22
26
29
30
31
32
34
36
38
51
53
54
55
57
59
60
62
64
65
67
68
70
71
73
75
78
79
81
82
83
85
86
87
88
91
92
93
94
96
98
99
DEPTH/SEDIMENT GRAIN SIZE
122
DEPTH
53
19
18
19
15
30
80
65
330
20
15
8
17
***
***
***
***
4
16
16
22
20
132
198
90
105
115
75
65
80
36
120
17
140
115
75
240
252
180
300
295
***
***
***
~ **
***
***
252
205
216
240
258
270
270
270
SAND
OX
NONOX
0.0
33.0
0.0
0.0
0.0
* ***
0.0
1.2
0.0
9.0
0.0
20.0
0.0
2.7
0.0
37.6
0.0
0.0
0.0
****
0.0
7.0
0.0
41.5
0.0
12.0
0.0
46.6
0.0
62.6
0.0
10.7
0.0
5.9
0.0
60.0
0.0
6.9
0.0
37.1
0.0
1.3
0.0
13.1
****
3.4
0.0
0.0
36.3
27.9
0.0
0.9
****
0.0
0.0
1.6
0.0
****
2.4
0.4
0.0
2.6
0.0
0.4
0.0
0.0
0.0
0.0
0.0
0.0
****
****
0.0
0.0
0.0
0.0
0.0
0.0
****
0.5
****
0.0
****
69.3
0.0
54.5
0.0
95.5
****
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.7
****
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
SILT
OX
NONOX
0.0
38.8
0.0
76.5
0.0
* * * *
0.0
67.3
0.0
40.9
0.0
70.2
0.0
81.8
0.0
11.2
0.0
58.6
0.0
ฆkit**
0.0
66.0
0.0
58.5
0.0
54.0
0.0
16.3
0.0
37.4
0.0
89.3
0.0
62.5
0.0
19.6
0.0
72.0
0.0
53.7
0.0
98.7
0.0
86.9
****
73.8
30.0
25.8
26.2
37.1
0.0
23.8
ฆkkkk
31.0
0.0
49.2
0.0
****
27.5
51.2
0.0
30.0
0.0
27.4
0.0
51.4
24.8
29.2
25.7
58.1
****
****
25.2
27.5
23.9
30.0
31.5
28.7
****
22.2
****
27.5
****
17.6
0.0
42.4
0.0
0.5
****
51.5
21.8
21.0
0.0
18.0
0.0
30.0
0.0
25.8
33.7
29.7
****
20.4
32.1
28.0
30.2
41.6
33.8
36.4
36.6
26.6
CLAY
OX
NONOX
0.0
28.2
0.0
23.5
0.0
* * * *
0.0
31.5
0.0
50.1
0.0
9.8
0.0
15.5
0.0
51.2
0.0
61.4
0.0
****
0.0
27.0
0.0
0.0
0.0
34.0
0.0
37.1
0.0
0.0
0.0
0.0
0.0
31.6
0.0
20.4
0.0
21.1
0.0
9.2
0.0
0.0
0.0
0.0
kit it it
22.8
70.0
74.2
37.5
35.0
0.0
75.3
****
69.0
0.0
49.2
0.0
****
70.1
48.4
0.0
67.4
0.0
72.2
0.0
48.6
75.2
70.8
74.3
41.9
****
****
74.8
72.5
76.1
70.0
68.5
71.3
****
77.3
****
72.5
****
13.1
0.0
3.1
0.0
0.0
****
48.5
78.2
79.0
0.0
82.0
0.0
70.0
0.0
74.2
66.3
69.6
****
79.6
67.9
72.0
69.8
58.4
66.2
63.6
63.4
73.4
-------
DEPTH/SEDIMENT GRAIN SIZE
SAMPLE DEPTH
SAND
SILT
CLAY
80-101
80-102
80-105
80-106
80-110
80-111
81-112
81-114
81-115
81-116
81-117
81-118
81-119
81-120
81-122
81-123
81-124
81-125
81-126
81-127
81-128
81-129
81-130
81-131
81-132
81-133
81-134
81-135
81-136
81-137
81-138
81-139
81-140
81-141
81-143
81-144
51-145
11-146
H-147
11-148
51-149
51-150
51-151
51-152
51-153
51-154
51-155
51-156
51-157
51-158
51-159
51-160
51-161
51-162
51-163
348
180
264
258
155
160
40
180
110
115
140
70
100
55
250
300
300
180
145
160
135
320
250
155
200
185
200
140
100
125
90
200
95
190
110
210
290
75
70
185
235
155
120
12
20
10
45
12
85
65
70
40
10
20
55
OX
NONOX
OX
NONOX
OX
NONOX
0.0
0.0
0.0
25.2
0.0
74.8
0.0
4.0
0.0
27.8
0.0
68.2
0.0
0.0
29.1
24.9
70.9
75.1
0.0
0.0
34.3
27.2
65.7
72.8
~ * * *
0.0
* * * *
57.7
****
42.3
0.0
0.0
34.0
47.4
66.0
52.6
0.0
87.2
0.0
9.8
0.0
3.0
0.0
0.0
32.6
30.8
67.4
69.2
0.0
0.0
36.2
41.3
63.8
58.7
0.0
0.0
37.3
37.6
62.7
62.4
0.0
0.0
36.1
37.3
63.9
62.7
0.0
0.0
38.2
36.4
61.8
63.6
0.0
0.0
42.4
38.1
57.6
61.9
0.0
0.0
39.1
33.3
60.9
64.3
1.8
1.2
26.9
24.9
71.3
73.9
0.0
0.0
30.7
23.3
69.3
76.7
0.0
0.0
32.4
35.2
67.7
64.8
****
0.0
****
28.8
hie**
71.2
0.0
0.0
35.4
31.1
64.6
68.9
0.0
0.0
36.7
41.5
63.3
58.5
0.0
0.0
37.4
40.6
62.6
59.4
0.0
0.0
40.9
41.2
59.1
58.8
0.0
0.0
27.4
22.5
72.6
77.5
1.0
0.0
41.4
24.3
57.6
75.7
0.0
0.0
33.4
27.5
66.6
72.5
0.0
0.0
40.0
29.5
60.0
70.5
0.0
0.0
39.5
43.9
60.5
56.1
****
0.0
****
49.2
****
50.8
0.0
0.0
43.3
44.8
56.7
55.2
0.0
0.0
39.9
43.0
60.1
57.0
****
****
****
ฆkith*
****
****
0.0
0.0
41.0
41.2
59.0
58.8
****
****
****
****
****
****
5.2
****
37.6
57.2
****
****
****
****
****
****
****
~ ***
0.0
****
36.9
****
63.1
0.0
0.0
51.6
47.2
48.4
52.7
1.0
2.2
57.0
70.5
42.0
27.3
0.0
1.7
61.3
65.4
38.7
32.9
0.0
0.0
70.4
70.5
29.6
29.5
0.0
1.2
56.0
44.3
44.0
54.5
0.0
0.0
49.9
47.2
50.1
52.4
3.1
3.3
59.1
51.1
37.8
45.6
****
77.7
****
16.5
****
5.8
0.0
42.1
0.0
48.7
0.0
9.2
0.0
65.5
0.0
26.5
0.0
8.0
****
8.5
****
73.4
****
18.1
0.0
86.2
0.0
9.6
0.0
4.2
0.0
****
50.6
****
49.4
****
0.0
0.0
39.3
35.7
60.7
64.3
0.0
0.0
41.0
42.7
59.0
57.3
****
0.9
****
49.7
****
49.4
0.0
86.8
0.0
8.8
0.0
4.4
67.6
72.9
18.8
17.0
13.6
10.1
0.0
0.0
68.7
69.3
31.3
30.7
-------
1
3
4
5
6
7
8
10
12
13
15
17
19
20
22
26
29
30
31
32
34
36
38
51
53
54
55
57
59
60
62
64
65
67
68
70
71
73
75
78
79
81
82
83
85
86
87
88
91
92
93
94
96
98
99
PHOSPHORUS/CARBON
124
ORGANIC
INORGANIC
TOTAL
PHOSPHORUS
PHOSPHORUS
PHOSPHORUS
CARBON
OX
NONOX
OX
NONOX
OX
NONOX
OX
NONOX
0.0
120.0
0.0
762.0
0.0
882.0
0.0
1.5
0.0
30.0
0.0
387 .0
0.0
417 .0
0.0
7 .1
0.0
218.0
0.0
502 .0
0.0
720.0
0.0
3.5
0.0
238.0
0.0
446.0
0.0
684.0
0.0:
*******
0.0
99.0
0.0
772.0
0.0
871.0
0.0:
*******
0.0
166.0
0.0
1072.0
0.0
1238.0
0.0
1.9
0.0
116.0
0.0
1190.0
0.0
1306.0
0.0
2.3
0.0
107.0
0.0
692.0
0.0
799.0
0.0
0.3
0.0
248.0
0.0
1581.0
0.0
1829.0
0.0
1.0
0.0
295.0
0.0
756.0
0.0
1051.0
0.0
4.0
0.0
194.0
0.0
444.0
0.0
638.0
0.0
4.7
0.0
469.0
0.0
673.0
0.0
1142.0
0.0
5.1
0.0
361.0
0.0
1098.0
0.0
1459.0
0.0
2.1
0.0
105.0
0.0
959 .0
0.0
1064.0
0.0
0.3
0.0
114.0
0.0
572.0
0.0
686.0
0.0
1.4
0.0
469.0
0.0
781.0
0.0
1250.0
0.0
4.1
0.0
323.0
0.0
919.0
0.0
1242.0
0.0
6.6
0.0
346.0
0.0
927.0
0.0
1273.0
0.0
0.3
0.0
318.0
0.0
1329.0
0.0
1647.0
0.0
2.3
0.0
78.0
0.0
1437.0
0.0
1515.0
0.0
2.5
0.0
40.0
0.0
670.0
0.0
710.0
0.0
1.2
0.0
35.0
0.0
633 .0
0.0
668.0
0.0
2.9
143.0
361.0
2958.0
2600.0
3101.0
2961.0
2.4*******
252.0
235.0
2425.0
1972.0
2777.0
2207.0
1.5
1.4
301.0
549.0
1752.0
1441.0
2053.0
1990.0
1.4
1.6
0.0
715.0
0.0
1325.0
0.0
2040.0
0.0
2.0
485.0
570.0
2134.0
1757.0
2619.0
2327.0
2.3
1.7
0.0
684.0
0.0
1016.0
0.0
1700.0
0.0
2.3
0.0
677.0
0.0
877.0
0.0
1554.0
0.0
3.1
709.0
493.0
1338.0
1068.0
2047.0
1561.0
2.2
2.1
0.0
390.0
0.0
798.0
0.0
1188.0
0.0
2.4
0.0
730.0
0.0
1366.0
0.0
2096.0
0.0
*******
0.0
280.0
0.0
1542.0
0.0
1822.0
0.0
*******
252.0
257.0
2090.0
1917.0
2342.0
2174.0
1.1
1.2
575.0
813.0
1541.0
1327.0
2116.0
2140.0
*******
1.2
672.0
678.0
1324.0
1274.0
1996.0
1952.0
1.8
*******
270.0
295.0
2104.0
2098.0
2374.0
2393.0
1.1
191.0
269.0
2157.0
2262.0
2348.0
2531.0
1.1
328.0
222.0
2117.0
2251.0
2445.0
2473.0
1.2
*******
392.0
344.0
3225.0
2641.0
3617.0
2985.0
*******
1.6
135.0
416.0
3205.0
2013.0
3340.0
2429.0
*******
1.2
337.0
138.0
800.0
1015.0
1137.0
1153.0
0.8
0.4
0.0
56.0
0.0
881.0
0.0
937.0
0.0
0.7
0.0
53.0
0.0
540.0
0.0
593.0
0.0
0.0
271.0
191.0
2825.0
1846.0
3096.0
2137.0
*******
1.7
394.0
510.0
2501.0
1751.0
2895.0
2261.0
1.4
1.6
0.0
497.0
0.0
1740.0
0.0
2237.0
0.0
0.4
0.0
356.0
0.0
2990.0
0.0
3346.0
0.0
1.2
0.0
278.0
0.0
2252.0
0.0
2530.0
0.0
1.2
278.0
318.0
2782.0
2276.0
3060.0
2594.0
1.8
1.7
200.0
246.0
3103.0
2167.0
3303.0
2413.0
*******
1.4
327.0
128.0
2765.0
2253.0
3092.0
2381.0
1.4
1.3
108.0
359.0
2889.0
2115.0
2997.0
2474.0
1.4
1.3
112.0
555.0
3142.0
1805.0
3254.0
2360.0
1.8
1.3
281.0
384.0
2331.0
2079.0
2612.0
2463.0
1.4
1.0
-------
SAMPLE
80-101
80-102
80-105
80-106
80-110
80-111
81-112
81-114
81-115
81-116
81-117
81-118
81-119
81-120
81-122
81-123
81-124
81-125
81-126
81-127
81-128
81-129
81-130
81-131
81-132
81-133
81-134
81-135
81-136
81-137
81-138
81-139
81-140
81-141
81-143
81-144
81-145
81-146
81-147
81-148
81-149
81-150
81-151
81-152
81-153
81-154
81-155
81-156
81-157
81-158
81-159
81-160
81-161
81-162
81-163
125
PHOSPHORUS/CARBON
ORGANIC INORGANIC
PHOSPHORUS PHOSPHORUS
OX
NONOX
OX
NONOX
0.0
374.0
0.0
1191.0
0.0
425.0
0.0
2384.0
638.0
437.0
1905.0
1878.0
934.0
225.0
1487.0
2167.0
463.0
163 .0
1513.0
1775.0
426.0
513.0
2193.0
1485.0
0.0
145.0
0.0
967.0
162.0
349.0
2003.0
1534.0
350.0
348.0
1988.0
1315.0
372.0
350.0
1740.0
1070.0
252.0
274.0
1588.0
1342.0
232.0
417.0
1876.0
1380.0
217.0
398.0
1795.0
1537.0
493.0
585.0
1404.0
1065.0
519.0
784.0
1542.0
1250.0
683.0
529.0
1397.0
1463.0
161.0
328.0
2028.0
1617.0
175.0
538.0
2553.0
1524.0
166.0
426.0
2302.0
1548.0
525.0
387.0
1619.0
1731.0
171.0
178.0
2370.0
1856.0
358.0
329.0
2099.0
1587.0
458.0
205.0
2181.0
2305.0
348.0
346.0
1911.0
1722.0
220.0
279.0
2163.0
1876.0
275.0
472.0
2248.0
1804.0
427.0
157.0
1572.0
1862.0
146.0
207.0
2008.0
1545.0
262.0
278.0
2137.0
1630.0
222.0
398.0
2035.0
1388.0
224.0
287.0
1843.0
1483.0
192.0
320.0
1794.0
1554.0
232.0
219.0
1011.0
979.0
312.0
278.0
2077.0
1774.0
208.0
208.0
1970.0
1918.0
533.0
266.0
1439.0
1515.0
227.0
259.0
1524.0
1456.0
401.0
269.0
1417.0
1541.0
290.0
248.0
2208.0
832.0
368.0
120.0
1803.0
1276.0
377.0
204.0
1573.0
1244.0
182.0
372.0
2324.0
1523.0
235.0
428.0
2147.0
1417.0
429.0
325.0
1486.0
1390.0
0.0
385.0
0.0
1629.0
0.0
27.0
0.0
1097.0
338.0
294.0
2030.0
1819.0
0.0
280.0
0.0
1285.0
252.0
316.0
1764.0
1377.0
329.0
374.0
1695.0
1339.0
232.0
125.0
1237.0
777.0
496.0
332.0
1695.0
1434.0
0.0
124.0
0.0
1618.0
53.0
76.0
1181.0
1080.0
355.0
166.0
1431.0
1521.0
TOTAL
PHOSPHORUS
CARBON
OX
NONOX
OX
NONOX
0.0
2285.0
0.0
1.6
0.0
2809.0
0.0
1.3
2543.0
2315.0
1.4
1.1
2421.0
2392.0
1.0 ** * * * * *
1976.0
1938.0
1.1
CO
o
2619.0
1898.0
1.2*
*****
0.0
1112.0
0.0*
*****
2165.0
1883.0
********
*****
2238.0
1663.0
********
*****
2112.0
1420.0
********
*****
1840.0
1616.0
********
*****
2108.0
1797.0
********
*****
2012.0
1935.0
********
*****
1897.0
1650.0
********
*****
2061.0
2034.0
********
*****
2060.0
1992.0
********
*****
2189.0
1945.0
********
*****
2728.0
2062.0
********
*****
2468.0
1974.0
********
*****
2144.0
2118.0
2541.0
2034.0
********
*****
2447.0
1916.0
********
*****
2639.0
2510.0
********
*****
2259.0
2068.0
********
*****
2383.0
2155.0
********
*****
2523.0
2276.0
1999.0
2219.0
********
*****
2154.0
1752.0
********
*****
2399.0
1908.0
********
*****
2257.0
1766.0
********
*****
2067.0
1770.0
********
*****
1986.0
1874.0
********
*****
1243.0
1198.0
********
*****
2389.0
2052.0
2178.0
2126.0
********
*****
1972.0
1781.0
1751.0
1715.0
1818.0
1810.0
2498.0
1080.0
********
*****
2171.0
1398.0
1950.0
1448.0
2506.0
1895.0
2382.0
1845.0
2015.0
1715.0
********
*****
0.0
2014.0
0.0*
0.0
1124.0
0.0*
*****
2368.0
2113.0
0.0
1565.0
0.0*
2016.0
1693.0
2024.0
1713.0
********
*****
1469.0
902.0
********
*****
2191.0
1766.0
********
*****
0.0
1842.0
0.0*
1234.0
1156.0
1787.0
1687.0
-------
126
H: Lr
-------
I"' I ฆ n
KIlWTfP'*
i i i i r~i
flifi
-------
123
' | - . M
-------
U \ S' rM\ ' N
P
129
f "7 r-
I I 1 I 1 1
! . ' i
Mllf*
-------
130
-------
131
MANGaNESl - OXIDIZED
" 1
i
i i- i i r~i
l"i I . i-i
J
-------
132
it i U I i 1 7
-------
133
v- r. r ~
r- *-
z u
n
1 i ! i ! J
M| Lr 3
-------
134
* V~Aป
V *. \
KlirซT.I f
-J
*\lf
-------
135
D L L ~ U -x. i D i. Z E D
I I I I II
3
[ r 1 i 1 .J
HI tr r.
-------
136
Clay - OXIDIZED
ฆi "i i n | 1 1 1 j
!tII P"'Iff. *
-------
137
L_ _
i . I
r P-
p 1 -UU I : I I )-
* 3 mm
-------
138
TOTAL p - REDUCED
3
-------
139
INORGANIC P - REDUCED
i 1 i 1 i ' ฆ 1
mcซrปrปc ' m lei
-------
140
ORGANIC PHOSPHORUS - REDUCED
-------
141
-------
142
!'1AN G A NEZE ~ REDUCED
KU1WCTW3 IIILf.S
-------
143
ZINC - REDUCED
KiioiCTf.Ri nuts
-------
144
rnpocD _ pens t^cn
L/ L> i ; \ i_ lj s
kuohltck
j
HUM
-------
145
SAND - REDUCED
m ' i 1 i l" i I i i I
3 miotetms J miri
-------
145
SILT - REDUCED
\rv
,4ป-a
*' * *
u-tn-i ซi t*sv-a
ปซ * * 4 ฆ* *
r\r-a
H-9
*** ***
r0*^J *ปv'
*~r *r *** * ^
* ,ar-ซ
LI MM I I I i
<3 a
HHMCU1S g rtltf.5
-------
147
CLAY - REDUCED
ฆj.j i 1 i ' i i '
OlOHCTWK 3 rtlLf:
-------
APPENDIX III
Scatterplots
-------
149
TOTAL PHOSPHORUS VS. INORGANIC PHOSPHORUS OXIDIZED
DOWN-TOPEX'T1 ACROSS-INPEX'Iป
I SYMBOLS :
3617+ RI . = 1 - 2
I .RT : = 3
I * = 4
I
I
2676+ : . .
I . i . .
I .: . .
T * *
J-
1923+ . :
I
I
I
1170+ . . .
RT
RI
I
417 +
387 1806 3225
MEAN SD
TOPEX 2.3+03 484.26
INPEX 2.0+03 531.09
R RSQ SIGF SLOPE INTCP SEE N
.952 .907 .000 .87 589.82 148.92 70
1.04-431.16 163.32 70
1923
1170
TOTAL PHOSPHORUS VS. INORGANIC PHOSPHORUS REDUCED
DOWN-TOPEX*T1 ACROSS-INPEXI'
RIRT SYMBOLS :
3617+ . = 1 - 2
. : = 3 4
* = 5 - 6
X
X
2676
^
**
*
RT...
417RI
++ + + + ++
387 1806 3225
TOPEX
INPEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
1.8+03 583.19 .950 .903 .000 1.05 250.96 182.74
1.4+03 527.23 .86 -75.35 165.21
N
110
110
-------
TOTAL PHOSPHORUS VS. ORGANIC PHOSPHORUS OXIDIZED
150
DOWN-TOPEX'T1 ACROSS-ORPEX10'
RO
3617
2676
1923
1170
417
T
RT
27
-+ RO+
481
934
SYMBOLS
. = 1
: = 2
* = 3
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 2.3+03 484.26 -.137 .019 .129 -.41 2.4+03 483.21 70
ORPEX 327.61 162.83 -4.6-02 434.06 162.47 70
TOTAL PHOSPHORUS VS. ORGANIC PHOSPHORUS REDUCED
DOWN-TOPEX'T1 ACROSS-ORPEX'O'
I RO SYMBOLS :
3617+ . = 1 - 2
I . : = 3
I * = 4 - 5
I
I
2676+ . RT
I
I .. . . ....
I . ...
1923+ .. . .
I . ..*
I . . . .
RT . .
1170+.
I
I ..
I *
417+.
++ RO+ + + ++
27 481 934
.
.
TOPEX
ORPEX
MEAN SD R RSQ SIGP SLOPE INTCP SEE
1.8+03 583.19 .435 .189 .000 1.48 1.3+03 527.49
315.29 171.10 .13 89.84 154.76
N
110
110
-------
151
TOTAL PHOSPHORUS VS. MANGANESE OXIDIZED
DOWN-TOPEX1T1 ACROSS-MNEX'M1
I RM SYMBOLS :
3617+ . RT . = 1 - 2
I . . : = 3
I . * = 4
I *
I
2676+ . .
I *
x . . . . .
la .
I
1923RT
I
I
I
1170+..
I
I
RM
417 +
++ + + + ++
26 3529 7031
MEAN SD
TOPEX 2.3+03 484.26
MNEX 1.6+03 996.86
R RSQ SIGF
.461 .212 .000
SLOPE INTCP SEE N
.22 2.0+03 432.94 70
.95-599.95 891.22 70
TOTAL PHOSPHORUS VS. MANGANESE REDUCED
DOWN-TOPEX'T1
I
3617 +
I
I
I .
I
2676 +
I
I .
I :.
1923+...
I.:*
I:..
RT..
1170+*.
RM.
I...
I*
417 + .
++
26
ACROSS-MNEX'M'
RM RT
SYMBOLS :
. = 1 - 3
: = 4 - 5
* = 6 - 8
3529
++
7031
TOPEX
MNEX
MEAN SD
1.8+03 583.19
808.72 781.83
R RSQ SIGF SLOPE INTCP SEE
741 .548 .000 .55 1.3+03 393.71
.99-944.18 527.80
N
110
110
-------
TOTAL PHOSPHORUS VS. IRON OXIDIZED
ACROSS-FEEX1F1
DOWN-TOPEX1T1
I
3617
2676
1923
1170
417
T
+RF-
409
if
*
-+ +-
3580
RF
RT
++
6752
SYMBOLS
. = 1
: = 2
* = 3
152
MEAN SD R RSQ SIGF SLOPE INTCP SEE
TOPEX 2.3+03 484.26 .652 .425 .000 .26 1.3+03 369.96
FEEX 3.8+03 1.2+03 1.62 72.90 920.27
TOTAL PHOSPHORUS VS. IRON REDUCED
DOWN-TOPEX1T' ACROSS-FEEX1F'
3617
2676
1923
1170
417
T
+-RF-
409
SYMBOLS :
. = 1 - 2
RF : = 3
* = 4
RT
ซ
*
3580
++
6752
N
70
70
TOPEX
FEEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
1.8+03 583.19 .748 .559 .000 .28 788.92 388.95
3.4+03 1.5+03 1.96 -37.88 1.0+03
N
110
110
-------
153
TOTAL PHOSPHORUS VS. ZINC OXIDIZED
DOWN-TOPEX'T1 ACROSS-ZNEX'Z'
RZ
3617
2676
1923
1170
417
RT
*
**
*
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
RT
+ RZ-+ +
3.0 37.6
72.1
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 2.3+03 484.26 .042 .002 .365 2.63 2.3+03 487.37 70
ZNEX 15.10 7.74 6.7-04 13.55 7.79 70
1923
1170RT.
417
ACROSS-ZNEX'Z"
RZ
RT
TOTAL PHOSPHORUS VS. ZINC REDUCED
DOWN-TOPEX1T1
3617
2676
SYMBOLS :
. = 1 - 3
: - 4 - 5
* = 6 - 7
+-RZ-
3.0
+-
37.6
++
72.1
TOPEX
ZNEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
1.8+03 583.19 .491 .241 .000 41.37 1.1+03 510.32
15.90 6.92 5.8-03 5.60 6.06
N
110
110
-------
154
TOTAL PHOSPHORUS VS. COPPER OXIDIZED
DOWN-TOPEX'T' ACROSS-CUEX'C'
I RC SYMBOLS :
3617+ . . = 1 - 2
I . : = 3
I . RT * = 4 - 5
I . . ป .
I
2676+ . ...
I ..... ...
X .... . ..
T * *
x . . . . . .
1923+ . *
RT ...
I
I
1170+
I
I
I
417+
++RC + + + ++
1.4 8.9 16.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE
TOPEX 2.3+03 484.26 .497 .247 .000 97.89 1.5+03 423.26
CUEX 7.97 2.46 2.5-03 2.13 2.15
TOTAL PHOSPHORUS VS. COPPER REDUCED
DOWN-TOPEXT1 ACROSS-CUEX'C1
3617-
2676
1923
117 0RT . . .
417
RC
.RT
+
1.4
-RC-
8.9
++
16.5
SYMBOLS :
. = 1 - 2
: = 3
* = 4
N
70
70
TOPEX
CUEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
1.8+03 583.19 .437 .191 .000 73.84 1.0+03 526.98
10.23 3.45 2.6-03 5.66 3.12
N
110
110
-------
TOTAL PHOSPHORUS VS. CARBON OXIDIZED
155
DOWN-TOPEX'T* ACROSS-CARTO'C1
I RC RT SYMBOLS :
3617+ . = 1
I : = 2
I * = 3
I : . .
I :
2676+ . .
I
I .:
I . .
1923+ . .
RT
I
I
1170+
I
I
I
417 +
++RC + + + ++
.00 3.57 7.13
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 2.5+03 498.94 .424 .180 .028 496.37 1.8+03 463.51 21
CARTO 1.46 .43 3.6-04 .55 .40 21
TOTAL PHOSPHORUS VS. CARBON REDUCED
DOWN-TOPEX'T' ACROSS-CARTOC *
RC
3617
2676
T
1923
1170
417
RT
+
.00
-+ RC-+-
3.57
-+ ++
7.13
SYMBOLS
. = 1
: = 2
* - 3
TOPEX
CARTO
MEAN SD R rsq SIGF SLOPE INTCP SEE
1.7+03 727.71 -.372 .138 .004-181.00 2.1+03 682.56
1.94 1.49 -7.6-04 3.24 1.40
N
50
50
-------
TOTAL PHOSPHORUS VS. SAND OXIDIZED
156
DOWN-TOPEX'T' ACROSS-SAND'S'
I SYMBOLS :
3617+ . - 1 - 4
I : = 5 - 7
I. * = 8 - 11
I.
I.
2676+.
RS.
RT.
1923+:'
I.
I.
I
1170 +
I RT
I
I
417 +
++ RS + + ++
.0 47.8 95.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 2.3+03 391.83 -.379 .144 .003 -14.10 2.3+03 366.18 52
SAND 2.28 10.54 -1.0-02 25.56 9.85 52
TOTAL PHOSPHORUS VS. SAND REDUCED
DOWN-TOPEX'T1
I
3617 +
I.
I
I..
I .
2676+.
RS
I*
I* .
1923RT.
I*
I. .
I..
1170+
I.
I. ,
I. .
417 + .
++
.0
ACROSS-SAND'S'
SYMBOLS :
. = 1 - 5
: = 6 - 9
* = 10 - 13
RT
-+ RS-+-
47.8
++
95.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 1.8+03 590.07 -.444 .197 .000 -10.73 1.9+03 531.34 101
SAND 11.95 24.43 -1.8-02 44.75 22.00 101
-------
157
TOTAL PHOSPHORUS VS. SILT OXIDIZED
DOWN-TOPEX'T1 ACROSS-SILT'S'
I RS SYMBOLS :
3617+ . = 1 - 2
I : = 3
I . * = 4
I
I . .
2676RT . ..
I .
I t ซ
I
1923+ .
I ... RT
I
I
1170+
I
I
I
417+
++ + RS + ++
.5 49.6 98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 2.3+03 391.83 -.221 .049 .058 -7.64 2.6+03 385.95 52
SILT 37.88 11.34 -6.4-03 52.48 11.16 52
RT
1923
1170
417
+
.5
ACROSS-SILT'S1
RS
TOTAL PHOSPHORUS VS. SILT REDUCED
DOWN-TOPEXT1
3617
2676
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
RT
+RS-
49.6
++
98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 1.8+03 590.07 -.307 .094 .001 -9.32 2.2+03 564.49 101
SILT 40.32 19.40 -1.0-02 58.29 18.56 101
-------
TOTAL PHOSPHORUS VS. CLAY OXIDIZED
158
DOWN-TOPEX1T1 ACROSS-CLAY1C1
I RC SYMBOLS
3617+ . = 1
I : = 2
I . * = 3
X
x
2676+ .. . RT
X ซ ซป
T *
T * . *
L ป ป .
1923+ . . .
X *
X
RT
1170 +
I
I
I
417 +
++ +-RC + + ++
.0 41.0 82.0
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
TOPEX 2.3+03 391.83 .493 .243 .000 14.64 1.4+03 344.35 52
CLAY 59.84 13.19 1.7-02 21.97 11.59 52
TOTAL PHOSPHORUS VS. CLAY REDUCED
DOWN-TOPEX'T' ACROSS-CLAY'C1
I SYMBOLS :
3617+ . = 1 - 2
I : = 3
I * = 4 - 5
I . .RC
J,
2676+
I .* .
X RT
T
X ซ
1923+ . . .,#
T
X ซ ป . ป
X
X
1170+
RT. .
X
I*
417+
++RC + + + ++
.0 41.0 82.0
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
thpfx 1.8+03 590.07 .668 .446 .000 15.56 1.0+03 441.49 101
47.86 25.31 2.9-02 -3.22 18.94 101
-------
INORGANIC PHOSPHORUS VS ORGANIC PHOSPHORUS OXIDIZED
159
DOWN-INPEX111 ACROSS-ORPEX'01
RO
3225
2390R
17 23
1055
387
I . :
*
RI
27
-+ +-RO +
481
++
934
SYMBOLS :
. = 1
: = 2
* = 3
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 2.0+03 531.09 -.430 .185 .000 -1.40 2.4+03 482.93 70
ORPEX 327.61 162.83 -.13 589.22 148.06 70
INORGANIC PHOSPHORUS VS. ORGANIC PHOSPHORUS REDUCED
DOWN-INPEX'I
I
3225 +
I
I
I
I
2390+
I
I
I
1723+
I
I .
RI
1055+..
I
I
I..
387+.
++
27
ACROSS-ORPEX'O*
RO
SYMBOLS s
. = 1 - 2
: = 3
* ฆ 4 - 5
~
RI
-RO-
481
++
934
INPEX
ORPEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
1.4+03 527.23 .161 .026 .046 .50 1.3+03 522.74
315.29 171.10 5.2-02 239.88 169.65
N
110
110
-------
INORGANIC PHOSPHORUS VS. IRON OXIDIZED
160
DOWN-INPEX111 ACROSS-FEEX1F'
I RF SYMBOLS :
3225+ . . . . = 1 - 2
I . : = 3
I . . . RI * = 4
I
I
2390+ ...
I . . . . .
I
I . .
X723+ * . . . .
I .
I ...ป.ซ
I
1055RI.
I
I
I
387+
++ RF-+ + + ++
409 3580 6752
MEAN SD
INPEX 2.0+03 531.09
FEEX 3.8+03 1.2+03
R RSQ SIGF
.628 .394 .000
SLOPE INTCP SEE N
.28 925.61 416.45 70
1.42 997.36 944.56 70
INORGANIC PHOSPHORUS VS. IRON REDUCED
DOWN-INPEX'11 ACROSS-FEEX'F1
3225
2390
1723
1055
RI
I.
387 +
. RF
SYMBOLS :
. = 1 - 2
: = 3 - 4
* = 5 - 6
RI
.
.
-RF-
409
.
._+ +-
3580
++
6752
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 1.4+03 527.23 .738 .545 .000 .25 569.42 357.20 110
FEEX 3.4+03 1.5+03 2.14 338.28 1.0+03 110
-------
INORGANIC PHOSPHORUS VS. MANGANESE OXIDIZED
161
DOWN-INPEX'11
3225
ACROSS-MNEX'M'
RM
RI
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
2390
1723
RI,
1055
387
+RM-
26
+-
3529
++
7031
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 2.0+03 531.09 .409 .167 .000 .22 1.6+03 488.29 70
MNEX 1.6+03 996.86 .77 71.84 916.52 70
INORGANIC PHOSPHORUS VS. MANGANESE REDUCED
DOWN-INPEX11ป ACROSS-MNEX'M1
I RM RI SYMBOLS :
3225+ . = 1 - 2
I . : = 3 - 4
I * = 5 - 6
I
I .
2390 +
I
I ซ ซ
I # ฆ . .
17 23+ ..
I. * .
... . ..
T . **
X .
I .
1055RI...
I*.
RM..
I:
387+:
++ + + + ++
26 3529 7031
INPEX
MNEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
1.4+03 527.23 .771 .595 .000 .52 1.0+03 337.23
808.72 781.83 1.14-839.29 500.08
N
110
110
-------
INORGANIC PHOSPHORUS VS. ZINC OXIDIZED
162
DOWN-INPEX'I'
I
3225 +
I
I
I
I
2390 +
I
RI
I
1723 +
I
I .
I
1055+ .
I
I .
I
387+
++__.
3.0
ACROSS-ZNEX1Z'
RZ
-RZ-+-
+-
37.6
RI
++
72.1
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 2.0+03 531.09 -.032 .001 .397 -2.18 2.0+03 534.71 70
ZNEX 15.10 7.74 -4.6-04 16.02 7.79 70
1723
1055RI
387
ACROSS-ZNEX'Z'
RZ
INORGANIC PHOSPHORUS VS. ZINC REDUCED
DOWN-INPEX'I'
3225-
RI
I
X
A
2390
+RZ-
3.0
+-
37.6
++
72.1
SYMBOLS :
. = 1 - 3
: = 4 - 5
* = 6 - 8
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 1.4+03 527.23 .377 .142 .000 28.73 984.41 490.51 110
ZNEX 15.90 6.92 5.0-03 8.76 6.44 110
-------
INORGANIC PHOSPHORUS VS. COPPER OXIDIZED
163
DOWN-INPEX'I' ACROSS-CUEX1C'
I RC SYMBOLS :
3225+ . . . . = 1 - 2
I . . : = 3
I . . * = 4
I . RI
I
23 90+ . . .
I
I .. *
I
1723+
I .......
RI ซ .
I
1055+
I
I
I
387+
++ RC + + ++
1.4 8.9 16.5
MEAN SD
INPEX 2.0+03 531.09
CUEX 7.97 2.46
R RSQ SIGF SLOPE INTCP SEE N
.406 .165 .000 87.78 1.3+03 488.80 70
1.9-03 4.24 2.26 70
1723
1055
387
RC
INORGANIC PHOSPHORUS VS. COPPER REDUCED
DOWN-INPEX'I' ACROSS-CUEX'C'
3225
2390
RI
*
RI ..
+
1.4
+ RC-+-
8.9
+ ++
16.5
SYMBOLS :
. = 1 - 2
: = 3
* = 4
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 1.4+03 527.23 .396 .157 .000 60.44 822.96 486.44 110
CUEX 10.23 3.45 2.6-03 6.50 3.18 110
-------
164
INORGANIC PHOSPHORUS VS. CARBON OXIDIZED
DOWN-INPEX11'
3225
2390
1723
1055
387
ACROSS-CARTO'C'
RC RI
+ RC-
.00
+-
3.57
SYMBOLS
. = 1
: = 2
* = 3
++
7.13
MEAN SD R RSQ SIGF SLOPE INTCP SEE
INPEX 2.1+03 609.09 .359 .129 .055 512.54 1.4+03 583.26
CARTO 1.46 .43 2.5-04 .92 .41
INORGAINC PHOSPHORUS VS. CARBON REDUCED
ACROSS-CARTO'C'
N
21
21
DOWN-INPEX1I'
[RC
3225
2390
1723R
1055+
387
I .
SYMBOLS
. = 1
: = 2
* = 3
.00
+ RC-+-
3.57
RI
+ ++
7.13
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 1.4+03 649.44 -.417 .174 .001-181.14 1.7+03 596.44 50
CARTO 1.94 1.49 -9.6-04 3.26 1.37 50
-------
165
INORGANIC PHOSPHORUS VS. SAND OXIDIZED
DOWN-INPEX11 1 ACROSS-SAND'S'
I SYMBOLS :
3225+. . = 1 - 3
I : = 4 - 5
I. * = 6 - 8
I.
I.
2390RS
I*.
RI.
I.
1723+*
I*
I: .
I.
1055 +
I RI
I
I
387+
++ RS+ + + ++
.0 47.8 95.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
INPEX 2.0+03 431.09 -.265 .070 .029 -10.83 2.0+03 419.84 52
SAND 2.28 10.54 -6.5-03 14.93 10.26 52
INORGANIC PHOSPHORUS VS. SAND REDUCED
DOWN-INPEX'I
I
3225+
I.
I
I.
I .
2390+..
RS
I.
I.
1723+:
RI
I:.
I..
1055+.
I
I..
I.
387+. ,
++
.0
ACROSS-SAND'S1
SYMBOLS :
. = 1 - 6
: = 7 - 11
* - 12 - 16
RI
-+-RS +-
47.8
++
95.5
INPEX
SAND
MEAN SD R RSQ SIGF SLOPE INTCP SEE
1.5+03 529.18 -.376 .141 .000 -8.14 1.6+03 492.84
11.95 24.43 -1.7-02 37.31 22.76
N
101
101
-------
INORGANIC PHOSPHORUS VS. SILT OXIDIZED
166
DOWN-INPEX111
I
3225-
2390
1723
1055
387
I
+-
.5
ACROSS-SILT'S'
RS
RI
RS+
49.6
98.7
SYMBOLS
. = 1
: = 2
* = 3
MEAN SD R RSQ SIGF SLOPE INTCP SEE
INPEX 2.0+03 431.09 -.167 .028 .119 -6.34 2.2+03 429.28
SILT 37.88 11.34 -4.4-03 46.46 11.29
INORGANIC PHOSPHORUS VS. SILT REDUCED
DOWN-INPEX'I'
3225
2390
1723R
1055
387
+
.5
ACROSS-SILT'S'
RS
+RS-
49.6
RI
++
98.7
SYMBOLS :
. = 1 - 2
: = 3
* = 4
N
52
52
MEAN SD R RSQ SIGF SLOPE INTCP SEE
INPEX 1.5+03 529.18 -.285 .081 .002 -7.77 1.8+03 509.79
SILT 40.32 19.40 -1.0-02 55.58 18.69
N
101
101
-------
INORGANIC PHOSPHORUS VS. CLAY OXIDIZED
DOWN-INPEX'I' ACROSS-CLAY'C'
t
3225-
2390
1723
1055
387
RI
RC
+ + +RC-
.0 41.0
RI
++
82.0
SYMBOLS
. = 1
: = 2
* = 3
167
MEAN SD
INPEX 2.0+03 431.09
CLAY 59.84 13.19
R RSQ SIGP SLOPE INTCP SEE N
.355 .126 .005 11.59 1.3+03 407.05 52
1.1-02 38.61 12.46 52
INORGANIC PHOSPHORUS VS. CLAY REDUCED
ACROSS-CLAY'C'
DOWN-INPEX'I'
I
3225 +
I
I
I
I
2390 +
I
I
I
1723 +
I .
I .
I .
1055+
RI.
I.
I*
387+
++
.0
ฆRC+-
.RC
RI
41.0
++
82.0
SYMBOLS :
. = 1 - 2
: = 3
* = 4
MEAN SD R RSQ SIGP SLOPE INTCP SEE N
INPEX 1.5+03 529.18 .586 .344 .000 12.26 874.59 430.79 101
CLAY 47.86 25.31 2.8-02 6.87 20.61 101
-------
ORGANIC PHOSPHORUS VS. MANGANESE OXIDIZED
168
DOWN-ORPEX'01 ACROSS-MNEX1M1
I RM SYMBOLS :
934+ . . = 1
I : = 2
I * = 3
I
I.
667+ .
I
I .
I ..
454+ . . .
I . . .
I . RO
RO . : ...
240+. ..: **...
I .. . * . ฆ
T
I
27+ .
++ RM+ + + ++
26 3529 7031
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
ORPEX 327.61 162.83 .044 .002 .358 7.2-03 316.08 163.86 70
MNEX 1.6+03 996.86 .27 1.5+03 1.0+03 70
ORGANIC PHOSPHORUS VS. MANGANESE REDUCED
DOWN-ORPEX'O'
I RM
934+
I
I .
I
I .
667 + :
I .
I . ..
I. .
454+.
I...
I.: :
RO. :
240+...
I: .
I..:
I::.
27+*
++RM-
26
ACROSS-MNEX*M'
SYMBOLS :
. = 1 - 2
: = 3 - 4
* = 5 - 6
RO
+-
3529
++
7031
MEAN SD R RSQ SIGF SLOPE INTCP SEE
ORPEX 315.29 171.10 .101 .010 .147 2.2-02 297.44 171.02
MNEX 808.72 781.83 .46 663.39 781.43
N
110
110
-------
454
240
27
ACROSS-FEEX1 F 1
RF
ORGANIC PHOSPHORUS VS. IRON OXIDIZED
DOWN-ORPEX'0'
934
667
169
0 .
RO
+
409
t i
ป
+ +-RF +-
3580
++
6752
SYMBOLS :
. = 1
: = 2
* = 3
MEAN SD R RSQ SIGF SLOPE INTCP SEE
ORPEX 327.61 162.83 -.103 .011 .199-1.4-02 380.59 163.15
FEEX 3.8+03 1.2+03 -.76 4.1+03 1.2+03
ORGANIC PHOSPHORUS VS. IRON REDUCED
ACROSS-FEEX'F'
N
70
70
DOWN-ORPEX1O1
I
934+
I
I
I
I
667 +
I
I
I
454+
I
I.
I ..
240RO
I .
I ..
I .
27 + .
++
409
RF
SYMBOLS :
. = 1 - 2
: = 3
* . 4
RO
RF+-
3580
++
6752
ORPEX
FEEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
315.29 171.10 .231 .053 .008 2.6-02 226.68 167.24
3.4+03 1.5+03 2.07 2.8+03 1.5+03
N
110
110
-------
ORGANIC PHOSPHORUS VS. ZINC OXIDIZED
170
DOWN-ORPEX'0' ACROSS-ZNEX'Z'
I RZ SYMBOLS :
934+ . . = 1 - 2
I : = 3 - 4
I * = 5 - 6
657 + . .
I RO
I . .
I .
454+ . ..
I
I . : : : .
I . : .
240RO. . .
I . ~ J .
I . :
I
27 +
++ RZ+ + + ++
3.0 37.6 72.1
MEAN SD
ORPEX 327.61 162.83
ZNEX 15.10 7.74
R RSQ SIGF
.233 .054 .026
SLOPE INTCP SEE N
4.91 253.44 159.49 70
1.1-02 11.47 7.58 70
ORGANIC PHOSPHORUS VS. ZINC REDUCED
DOWN-ORPEX*O'
I
934+
I
I
I
I
66 7+
I
I
I
454+ .
I .
I.
I :
240+
RO.
I ..
I
27 + ..
++--RZ
3.0
ACROSS-ZNEX'Z'
RZ
RO
SYMBOLS :
. = 1 - 2
: = 3 - 4
* = 5 - 6
+-
37.6
++
72.1
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
ORPEX 315.29 171.10 .448 .200 .000 11.06 139.44 153.71 110
ZNEX 15.90 6.92 1.8-02 10.19 6.22 110
-------
ORGANIC PHOSPHORUS VS. COPPER OXIDIZED
171
DOWN-ORPEX'0'
934
667
454
240
27
+
1.4
ACROSS-CUEX1C1
RC
-RC-+-
8.9
RO
++
16.5
SYMBOLS :
. = 1 - 2
: = 3
* = 4
MEAN SD R RSQ SIGF SLOPE INTCP SEE
ORPEX 327.61 162.83 .162 .026 .090 10.76 241.88 161.84
CUEX 7.97 2.46 2.5-03 7.17 2.44
ORGANIC PHOSPHORUS VS. COPPER REDUCED
DOWN-ORPEX'O' ACROSS-CUEX'C'
RC SYMBOLS :
934+ . = 1
: = 2
* = 3
667
N
70
70
454
240
27
* _
. . . RO
O
1.4
-+ RC-
8.9
16.5
MEAN SD
ORPEX 315.29 171.10
CUEX 10.23 3.45
R RSQ SIGF SLOPE INTCP SEE N
.227 .051 .009 11.23 200.41 167.42 110
4.6-03 8.79 3.38 110
-------
ORGANIC PHOSPHORUS VS. CARBON
OXIDIZED
172
DOWN-ORPEX0'
I
934+
I
I
I
X
667 +
I
I
I
454 +
RO
I
ACROSS-CARTO1C1
RC
SYMBOLS
. = 1
: = 2
* = 3
I : .
240 +
I
I
I
27+
++ RC+-
.00
RO
3.57
++
7.13
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
ORPEX 376.24 212.52 -.035 .001 .441 -17.19 401.33 217.91 21
CARTO 1.46 .43 -6.9-05 1.49 .44 21
ORGANIC PHOSPHORUS VS. CARBON REDUCED
DOWN-ORPEX'O'
I
934+
I
I
I
I
667+
I
I
I .
454+
I
I .
RO
240+
I
I
I :
27+. ,
++
.00
ACROSS-CARTO'C1
RC
SYMBOLS
. = 1
: = 2
* = 3
RO
-RC-
+-
3.57
++
7.13
MEAN SD
ORPEX 315.26 195.14
CARTO 1.94 1.49
R RSQ SIGF SLOPE INTCP SEE N
.021 .000 .443 2.73 309.95 197.12 50
1.6-04 1.89 1.51 50
-------
ORGANIC PHOSPHORUS VS. SAND OXIDIZED
173
DOWN-ORPEX'0' ACROSS-SAND1S'
I SYMBOLS :
934+. . = 1 - 4
I : = 5 - 7
I * = 8 - 10
I
I .
667 + .
I
I.
RS
454+.
I:
RO
I..
240+*.
I:
I.
I.
27+
++-RS + + + RO
.0 47.8 95.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
ORPEX 327.96 165.76 -.209 .044 .069 -3.28 335.43 163.73 52
SAND 2.28 10.54 -1.3-02 6.63 10.41 52
ORGANIC PHOSPHORUS VS. SAND REDUCED
DOWN-ORPEX'O1 ACROSS-SAND1S'
I SYMBOLS :
934+ . = 1 - 5
I : = 6 - 9
I. * = 10 - 13
I.
I.
667 + .
I.
RS
I.
454+. .
I:.
RO . . *
I: . .
240+*
I. .
Is * .
I . . . . . . RO
27 +. ฆ
++ RS + + ++
.0 47.8 95.5
ORPEX
SAND
MEAN SD R RSQ SIGF SLOPE INTCP SEE
311.94 170.14 -.363 .132 .000 -2.53 342.19 159.31
11.95 24.43 -5.2-02 28.23 22.88
N
101
101
-------
ORGANIC PHOSPHORUS VS. SILT OXIDIZED
174
DOWN-ORPEX'0' ACROSS-SILT'S'
I RS SYMBOLS
934+ . . = 1
I : = 2
I * = 3
I
I
667 +
I
I
I ...
454+
X ...
RO ..:* :
I . . . .
240+ RO
I . ซซ ซ *
I : .
I
27 +
++ + RS+ + ++
.5 49.6 98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE
ORPEX 327.96 165.76 -.084 .007 .277 -1.22 374.36 166.83
SILT 37.88 11.34 -5.7-03 39.76 11.41
ORGANIC PHOSPHORUS VS. SILT REDUCED
DOWN-ORPEX'O'
934
667
454
240
27
ACROSS-SILT'S'
RS
O
*
i
* 4rซ
~
0
+
.5
-+ RS-
49.6
RO
++
98.7
SYMBOLS :
. = 1
: = 2
* - 3
N
52
52
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
ORPEX 311.94 170.14 -.138 .019 .085 -1.21 360,68 169.36 101
SILT 40.32 19.40 -1.6-02 45.22 19.32 101
-------
ORGANIC PHOSPHORUS VS. CLAY OXIDIZED
175
DOWN-ORPEX'O' ACROSS-CLAY1C'
I RC SYMBOLS :
934 + . . = 1
I : = 2
I * = 3
I
I
667 +
I
I
I ...
454+
X HO
T
JL
I .
240+ . :
I ......
RO
I . .
27 +
++ + + RC+ ++
.0 41.0 82.0
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
ORPEX 327.96 165.76 .238 .057 .044 3.00 148.66 162.58 52
CLAY 59.84 13.19 1.9-02 53.62 12.94 52
ORGANIC PHOSPHORUS VS. CLAY REDUCED
DOWN-ORPEX'O' ACROSS-CLAY'C'
[
934-
667
454
240
27
.0
RC
...
. .
. . : * : RO
.. .
'k i
RO: . .
*
ซ
-+-RC +-
41.0
++
82.0
SYMBOLS
. = 1
: = 2
* = 3
ORPEX
CLAY
MEAN SD R RSQ SIGF SLOPE INTCP SEE
311.94 170.14 .454 .206 .000 3.05 165.80 152.33
47.86 25.31 6.8-02 26.77 22.66
N
101
101
-------
IRON VS. MANGANESE OXIDIZED
DOWN-FEEX'F1
6752
4886
3394
1901
409
ACROSS-MNEX'M'
RM
RF
RF
* *
ซ ซ #
*
176
SYMBOLS
. = 1
: = 2
* = 3
RM-
26
.+ +-
3529
++
7031
MEAN SD
FEEX 3.8+03 1.2+03
MNEX 1.6+03 996.86
R RSQ SIGF
.514 .264 .000
IRON VS. MANGANESE REDUCED
DOWN-FEEX'F1
I
6752+
I
I
I
I
4886+
I
I
I
3394+
I
Is
RF
1901+*
Is
RM
Is
409+..
++-
26
ACROSS-MNEX'M'
RM RF
t 2
SLOPE INTCP SEE
.62 2.8+03 1.0+03
.43 -32.18 861.44
SYMBOLS :
. = 1 - 3
: = 4 - 6
* = 7 - 9
N
70
70
3529
++
7031
MEAN SD R RSQ SIGF SLOPE INTCP SEE
FEEX 3.4+03 1.5+03 .743 .552 .000 1.45 2.3+03 1.0+03
MNEX 808.72 781.83 .38-492.30 525.61
N
110
110
-------
IRON VS. ZINC OXIDIZED
177
DOWN-FEEX'F'
I
6752 +
I
I
I
I
4886+
I
I
I
3394RF
I
I
I
1901+
I
I ..
I
409+ .
++-RZ
3.0
ACROSSZNEX'Z'
RZ
RF
SYMBOLS :
. = 1 - 2
: = 3 - 4
* = 5 - 6
+-
37.6
++
72.1
FEEX
ZNEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
3.8+03 1.2+03 .294 .086 .007 45.78 3.1+03 1.2+03 70
15.10 7.74 1.9-03 7.89 7.45 70
IRON VS. ZINC REDUCED
DOWN-FEEX'F'
I
6752+
I
I
I
I
4886 +
I
I
I .
3394+
I .
I ...
I
1901RF...
I ..
I.
I
409+. .
++-RZ
3.0
ACROSS-ZNEX'Z'
RZ RF
SYMBOLS :
. = 1 - 2
: = 3 - 4
* = 5 - 6
37.6
++
72.1
MEAN SD
FEEX 3.4+03 1.5+03
ZNEX 15.90 6.92
R RSQ SIGF SLOPE INTCP SEE
.531 .282 .000 117.39 1.6+03 1.3+03
2.4-03 7.66 5.89
N
110
110
-------
IRON VS. COPPER OXIDIZED
178
DOWN-FEEX'F' ACROSS-CUEX'C'
I RC SYMBOLS :
6752+ . = 1 - 2
I . . : = 3
I ... RF * = 4
J-
X
4886 +
-L ปซ
I ป
T *
3394+
L
X
RF
1901+
I
I
409+
h+ RC+ + + ++
1.4 8.9 16.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
FEEX 3.8+03 1.2+03 .476 .226 .000 232.92 2.0+03 1.1+03 70
CUEX 7.97 2.46 9.7-04 4.26 2.18 70
IRON VS. COPPER REDUCED
DOWN-FEEX'F1
I
6752+
I
I
I
I
4886+
I
I
I
3394+
I
I
I
1901+
I
I
RF
409+.
ACROSS-CUEX'C1
RC
..RF
SYMBOLS
. = 1
: = 2
* = 3
1.4
-RC-
+-
8.9
++
16.5
nppv , MEAN SD R RSQ SIGF SLOPE INTCP SEE N
rrฃv 4+03 1.5+03 .696 .485 .000 308.89 268.48 1.1+03 110
10.23 3.45 1.6-03 4.85 2.49 110
-------
IRON VS. CARBON OXIDIZED
179
DOWN-FEEX1F' ACROSS-CARTO'C'
I RC RF SYMBOLS :
6752+ . = 1
I : = 2
I * = 3
I
I . : .
4386+
I .:
I
I
3394+
I . .
RF
I
1901 +
I
I
I
409+
++ RC+ H + ++
.00 3.57 7.13
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
FEEX 4.2+03 1.4+03 .350 .122 .060 1.2+03 2.5+03 1.4+03 21
CARTO 1.46 .43 1.1-04 1.02 .41 21
IRON VS. CARBON REDUCED
DOWN-FEEX'F" ACROSS-CARTOซC'
RC
6752
4886
3394
1901
409
P
+
.00
ฆRC+-
3.57
RF
++
7.13
SYMBOLS
. = 1
: ซ 2
* = 3
FEEX
CARTO
MEAN SD R RSQ SIGF SLOPE INTCP SEE
3.4+03 1.8+03 -.280 .078 .025-328.84 4.0+03 1.7+03
1.94 1.49 -2.4-04 2.74 1.45
N
50
50
-------
IRON VS. SAND OXIDIZED 13Q
DOWN-FEEX1F1 ACROSS-SAND1S'
I SYMBOLS :
6752+ . = 1 - 3
I : = 4 - 6
I . * = 7 - 9
I.
I:
4886RS
I*
RF.
I*
3394+*
I:
I.
I..
1901+ RF
I
I
I
409+
++ RS+ + + ++
.0 47.8 95.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
FEEX 3.9+03 900.68 -.234 .055 .047 -20.02 4.0+03 884.32 52
SAND 2.28 10.54 -2.7-03 13.02 10.35 52
IRON VS. SAND REDUCED
DOWN-FEEX1F1 ACROSS-SAND'S'
I
SYMBOLS
6752+.
. = 1 -
4
I.
: = 5 -
7
I..
* = 8 -
11
I:
I: .
4886+:
RS
RF
I* .
3394+*
I..
I. . ...
I ..
1901+.... * .
I.
I
I .
409+ ป
++ + RS + RF-++
.0 47.8 95.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
FEEX 3.5+03 1.5+03 -.650 .423 .000 -41.14 4.0+03 1.2+03 101
SAND 11.95 24.43 -1.0-02 47.72 18.66 101
-------
IRON VS. SILT OXIDIZED
181
DOWN-FEEX'F1
I
6752 +
I
I
I
I
4886RF
I
I
I
3394+
I
I
I
1901 +
I
I
I
409+
++
.5
ACROSS-SILT1 S1
RS
HF
+ RS
49.6
++
98.7
SYMBOLS :
. = 1 - 2
: = 3
* = 4
MEAN SD R RSQ SIGF SLOPE INTCP SEE
FEEX 3.9+03 900.68 -.256 .066 .033 -20.35 4.7+03 879.29
SILT 37.88 11.34 -3.2-03 50.51 11.07
IRON VS. SILT REDUCED
DOWN-FEEX1F1 ACROSS-SILT'S'
SYMBOLS :
6752+ . . = 1 - 2
: = 3
* = 4
4886
RF
3394
1901
409
+
.5
I
N
52
52
RS-
49.6
RF
++
98.7
MEAN SD R rsQ SIGF SLOPE INTCP SEE N
FEEX 3.5+03 1.5+03 -.227 .051 .011 -18.07 4.2+03 1.5+03 101
SILT 40.32 19.40 -2.8-03 50.23 18.99 101
-------
IRON VS. CLAY OXIDIZED
182
DOWN-FEEX1F1
I
6752 +
I
I
I
I
4886 +
I
I
I
3394 +
I
I
RF
1901+
I
I
I
409+
++
.0
ACROSS-CLAY1C 1
RC
SYMBOLS
. = 1
: = 2
* = 3
**
RF
+ RC
41.0
+ ++
82.0
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
FEEX 3.9+03 900.68 .407 .166 .001 27.81 2.3+03 830.74 52
CLAY 59.84 13.19 6.0-03 36.47 12.17 52
IRON VS. CLAY REDUCED
DOWN-FEEX1F ACROSS-CLAYCป
I
6752+
J.
I . ..RC
X ซ
I . . *..RF
4886+ .. ..
I
*
3394+ . .
J. *
1901+. ...
I. .
RF.
X.
409+..
++-RC + + ++
.0 41.0 82'ฐ
MEAN SD R RSQ SIGF SLOPE ^TCP ฎ9 1Q1
FEEX 3.5+03 1.5+03 .807 .651 .000 49.27 15*04 101
CLAY 47.86 25.31 1.3-02 1-88
SYMBOLS :
. = 1 - 2
: = 3
* s 4
-------
MANGANESE VS. ZINC OXIDIZED
183
DOWN-MNEX'M1
I
7031 +
I
I
I
I
4971 +
I
I
I
3323 +
I
I
I
1674RM
I
I .
I
26+ ..
++
3.0
ACROSS-ZNEX'Z'
RZ
SYMBOLS :
. = 1 - 3
5 = 4-6
* = 7 - 9
RM
-RZ-+-
+-
37.6
++
72.1
MEAN SD R RSQ SIGP SLOPE INTCP SEE N
MNEX 1.6+03 996.86 -.051 .003 .338 -6.55 1.7+03 1.0+03 70
ZNEX 15.10 7.74 -3.9-04 15.73 7.78 70
MANGANESE VS. ZINC REDUCED
DOWN-MNEX'M'
7031
ACROSS-ZNEX'Z'
RZ
SYMBOLS s
. = 1 - 3
: = 4 - 5
* = 6 - 8
4971
3323
1674
26
RM
RM...*
: *: *
+ RZ
3.0
+-
37.6
++
72.1
MNEX
ZNEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE
808.72 781.83 .327 .107 .000 36.95 221.19 742.18
15.90 6.92 2.9-03 13.55 6.57
N
110
110
-------
MANGANESE VS. COPPER OXIDIZED
184
DOWN-MNEX'M1 ACROSS-CUEX'C'
I RC SYMBOLS :
7031+ . . = 1 - 2
I ซ = 3
I * = 4 - 5
I
I
4971 +
I
I
I
3323 +
I RM
I . * . .
I
1674+ ..
x *
I ~
RM
26 + . .
++ HRC + + ++
1.4 8.9 16.5
MEAN SD R RSQ SIGP SLOPE INTO? SEE N
MNEX 1.6+03 996.86 .347 .120 .002 140.54 472.48 941.88 70
CUEX 7.97 2.46 8.6-04 6.61 2.32 70
MANGANESE VS. COPPER REDUCED
DOWN-MNEX'M1 ACROSS-CUEX'C'
I SYMBOLS :
7031+ . - 1 - 2
I : = 3
I * = 4 - 5
I
I
4971+
I
I
I
3323+ . RC
I
I ...
I . . .
1674+ . RM
I .ซ
T
^ ## ซ ซ
I . . .
26 + ...
++ RM+ RC + ++
1.4 8.9 16.5
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
MNEX 808.72 781.83 .525 .276 .000 119.00-408.51 668.34 110
CUEX 10.23 3.45 2.3-03 8.35 2.95 110
-------
3323
1674
26
RM
ACROSS-CARTO'C1
RC
MANGANESE VS. CARBON OXIDIZED
DOWN-MNEX1M1
7031-
4971
+ RC+-
.00
3.57
RM
7.13
SYMBOLS :
. = 1 - 2
: = 3
* = 4
MNEX
CARTO
MEAN SD R RSQ SIGF SLOPE INTCP SEE
2.0+03 1.4+03 -.107 .011 .323-355.76 2.5+03 1.5+03
1.46 .43 -3.2-05 1.52 .44
MANGANESE VS. CARBON REDUCED
DOWN-MNEX1M' ACROSS-CARTO1C1
I
7031 +
I
I
I
I
4971+
RC
I
I
3323 +
I
I
I : .
1674+ . ...
RM
I
I ..
26+.. . *
++ +-RC + +-RM ++
.00 3.57 7.13
SYMBOLS :
. = 1 - 2
: - 3
* = 4
MEAN SD
MNEX 863.44 960.03
CARTO 1.94 1.49
R RSQ SIGF SLOPE INTCP SEE
-.350 .123 .006-225.10 1.3+03 908.47
-5.5-04 2.41 1.41
-------
MANGANESE VS. SAND OXIDIZED
DOWN-MNEX1M1 ACROSS-SAND'S'
I
SYMBOLS
J
7031+.
. = 1 -
4
I
: = 5 -
7
I
* = 8 -
11
I
I
4971+
I
I
I
3323 +
I.
RS
I:
1674RM.
I*
I:
I..
26+ .
++-RS
+-RM ++
. 0
47.8
95.5
MEAN SD R RSQ SIGP SLOPE INTCP SEE N
MNEX 1.7+03 1.0+03 -.250 .063 .037 -23.77 1.8+03 978.65 52
SAND 2.28 10.54 -2.6-03 6.87 10.31 52
MANGANESE VS. SAND REDUCED
DOWN-MNEX'M1 ACROSS-SAND'S'
I SYMBOLS :
7031+ . = 1 - 6
I : = 7 - 12
I * = 13 - 18
I
I
4971 +
I
I
I
3323+.
I.
I..
RS
1674+:
I.
RM
I*. .
26 + :
++ RS+ + + RM-++
.0 47.8 95.5
MNEX
SAND
MEAN SD R RSQ SIGF SLOPE INTCP SEE
851.42 797.15 -.345 .119 .000 -11.26 985.98 751.97
11.95 24.43 -1.1-02 20.96 23.05
N
101
101
-------
MANGANESE VS. SILT OXIDIZED
187
DOWN-MNEX1M1 ACROSS-SILT'S1
I RS SYMBOLS :
7031+ . . = 1 - 2
I : = 3
I * = 4
I
I
4971 +
I
I
I
3323 +
I
RM
I
1674+
I
I RM
I . . .
26+ . .
++ + RS-+ + ++
.5 49.6 98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
MNEX 1.7+03 1.0+03 -.182 .033 .099 -16.04 2.4+03 994.01 52
SILT 37.88 11.34 -2.1-03 41.47 11.26 52
MANGANESE VS. SILT REDUCED
DOWN-MNEX'M* ACROSS-SILT'S'
E
7031-
4971RS
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
3323
1674
26
RM
...
*
...
it ซ
...
* .
+
.5
-RS-
49.6
RM++
98.7
MNEX
SILT
MEAN SD R RSQ SIGF SLOPE INTCP SEE
851.42 797.15 -.395 .156 .000 -16.25 1.5+03 735.87
40.32 19.40 -9.6-03 48.51 17.91
N
101
101
-------
MANGANESE VS. CLAY OXIDIZED
DOWN-MNEX1M' ACROSS-CLAY1C'
7031-
4971
3323
1674
188
26RM
++
.0
RC
, . RM
-RC-+-
41.0
++
82.0
SYMBOLS
. = 1
: = 2
* = 3
MEAN SD
MNEX 1.7+03 1.0+03
CLAY 59.84 13.19
R RSQ SIGF SLOPE INTCP SEE N
.356 .127 .005 27.02 126.32 944.56 52
4.7-03 51.66 12.45 52
MANGANESE VS. CLAY REDUCED
DOWN-MNEX'M1
I
7031+
I
I
I
I
4971 +
I
I
I
3323 +
I
I
I
1674+ .
I
I
I
26+*:.:.
++-RM-
.0
ACROSS-CLAY'C'
:RC
.. .RM
41.0
++
82.0
SYMBOLS :
. ซ 1 - 2
: = 3 - 4
* = 5 - 6
CC*ฃ N
MEAN SD R RSQ SIGF SLOPE INTฃP 101
MNEX 851.42 797.15 .641 .410 .000 20.17-114.02 eio- 1Q1
CLAY 47.86 25.31 2.0-02 30.54
-------
COPPER VS. ZINC OXIDIZED
189
DOWNCUEX'C' ACROSS-ZNEX1Z'
I RZ SYMBOLS :
16.5+ . . = 1 - 3
I : = 4 - 5
I * = 6 - 7
I
I
12.0 +
I . : .
I : .. RC
I i
8.5+ ... .
RC . .
I . : .
I . *..
4.9+
I . .
I . .
I
1.4+
+H RZ 1 I I++
3.0 37.6 72.1
CUEX
ZNEX
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
7.97 2.46 .119 .014 .163 3.8-02 7.40 2.46 70
15.10 7.74 .38 12.11 7.74 70
COPPER VS. ZINC REDUCED
DOWN-CUEX'C'
I
16.5+
I
I
I
I
12.0+ .
I .
I
I
8.5+
RC
I .. ,
I .
4.9+ .
I . ,
I. : ,
I.
1.4+..
++-RZ-
3.0
ACROSS-ZNEX1Z'
RZ RC
* **
+-
37.6
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
++
72.1
CUEX
ZNEX
MEAN SD R RSQ SIGF SLOPE INTCP
10.23 3.45 .465 .216 .000 .23 6.55
15.90 6.92 .93 6.36
SEE
3.07
6.16
N
110
110
-------
COPPER VS. CARBON OXIDIZED
190
DOWN-CUEX'C1 ACROSS-CARTO * 1'
I R1 RC SYMBOLS
16.5+ . . = 1
I : = 2
I * = 3
T
I
12.0 +
I :: .
I : . .
I .:
8.5+
RC
I
I
4.9+
I
I
I
1.4+
++ Rl+ + + ++
.00 3.57 7.13
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
CUEX 10.04 2.43 .308 .095 .087 1.75 7.48 2.37 21
CARTO 1.46 .43 5.4-02 .92 .42 21
COPPER VS. CARBON REDUCED
DOWN-CUEXฆC ACROSS-CARTO111
I Rl SYMBOLS :
16.5+ ... . 1 2
I . . : = 3
I * = 4 - 5
I .. . . .
I
12.0+ .... . . . RC
RC.
X ...
I
8.5+ . . .
I .
I ...
I .
4.9+
I
I
I .
1.4+.
++ Rl + + ++
.00 3.57 7.13
MEAN SD R RSQ SIGF SLOPE INTCP
CUEX 11.35 3.72 .038 .001 .396 9.5-02 11.16
CARTO 1.94 1.49 1.5-02 1.77
SEE N
3.76 50
1.51 50
-------
COPPER VS. SAND OXIDIZED
191
DOWN-CUEX'C' ACROSS-SAND1S'
I SYMBOLS :
16.5+. . = 1 - 4
I : = 5 - 7
I * = 8 - 10
I
I.
12.0+.
I: .
RS
I:
8.5RC.
I.
I*
I*.
4.9+.
I.
I RC
I
1.4+
++RS + + + ++
.0 47.8 95.5
MEAN SD R RSQ SIGF SLOPE
CUEX 8.15 2.45 -.233 .055 .048-5.4-02
SAND 2.28 10.54 -1.00
COPPER VS. SAND REDUCED
INTCP SEE N
8.27 2.41 52
10.46 10.35 52
DOWN-CUEX1C'
I
16.5+..
I.
I*
I*
RS
12.0+!
RC
I:
I
8.5+
I
I,
I
4.9+
I
I
I
1.4+
++-*
.0
ACROSS-SAND'S'
SYMBOLS :
. = 1 - 4
: = 5 - 8
* = 9 - 12
-RS-
47.8
. RC
++
95.5
MEAN SD
CUEX 10.21 3.53
SAND 11.95 24.43
R RSQ SIGF SLOPE
-.712 .507 .000 -.10
-4.93
INTCP SEE N
11.44 2.49 101
62.29 17.24 101
-------
COPPER VS. SILT OXIDIZED
192
DOWN-CUEX'C' ACROSS-SILT1S1
I RS SYMBOLS :
16.5+ . . = 1 - 2
I : = 3
I * = 4
I
I
12.0 +
RC
I
I
8.5 +
I
I
I
4.9+
I
I RC
1.4+
++ + RS + ++
.5 49.6 98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
CUEX 8.15 2.45 -.402 .161 .002-8.7-02 11.43 2.27 52
SILT 37.88 11.34 -1.86 53.02 10.48 52
COPPER VS. SILT REDUCED
DOWN-CUEX'C* ACROSS-SILT'S'
I RS SYMBOLS :
16.5+ ... . . = 1 - 2
I : = 3
I * = 4 - 5
I ซ... .
I
12.0+ ... . ... .
I . ... . RC
I ... ... . .
RC *ซ... . .
8.5+ . . . : .
I . . .
I . ...
I
4.9+
I
I . . . .
I
1.4+. .
++ +RS+ + ++
.5 49 .6 98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE
CUEX 10.21 3.53 .089 .008 .187 1.6-02 9.56 3.53
SILT 40.32 19.40 .49 35.30 19.42
N
101
101
-------
COPPER VS. CLAY OXIDIZED
193
DOWN-CUEX'C'
T
j.
16.5 +
I
I
I
I
12.0+
I
I
I
8.5+
I
I
I
4.9+
I
I
RC
1.4+
++
.0
ACROSS-CLAY'1'
Rl
RC
ฆ+ Rl
41.0
+ ++
82.0
SYMBOLS
. - 1
: = 2
* = 3
CUEX
CLAY
MEAN SD
8.15 2.45
59.84 13.19
R RSQ SIGF SLOPE INTCP SEE N
.532 .283 .000 9.9-02 2.24 2.10 52
2.86 36.52 11.29 52
COPPER VS. CLAY REDUCED
DOWN-CUEX'C' ACROSS-CLAY'1'
]
16.5
12.0
8.5
C
4.9
1.4+..
++--R1-
.0
+-
41.0
Rl
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
.RC
++
82.0
CUEX
CLAY
MEAN SD
10.21 3.53
47.86 25.31
R RSQ SIGF SLOPE INTCP SEE N
.637 .406 .000 8.9-02 5.96 2.73 101
4.57 1.19 19.61 101
-------
ZINC VS. CARBON OXIDIZED
194
DOWN-ZNEX'Z' ACROSS-CARTO1C'
I RC SYMBOLS :
72.1+ . = 1 - 2
I : = 3 - 4
X * = 5 - 6
I
I
51.8+
I
I
I RZ
35.5 +
I
I
I
19.3 +
~
*
I
I
RZ .
. 0+
++-RC + + + ++
.00 3.57 7.13
MEAN SD R RSQ SIGF SLOPE
ZNEX 15.75 3.25 .546 .299 .005 4.16
CARTO 1.46 .43 7.2-02
19.3
ACROSS-CARTO'C'
RC
ZINC VS. CARBON REDUCED
DOWN-ZNEX'Z'
72.1
51.8+
I
I
1
35.5+
>
*
RZ . . . .
3.0+.. ,
++
.00
-RC +-
3.57
INTCP SEE N
9.67 2.79 21
.33 .37 21
SYMBOLS :
. = 1 - 2
: = 3 - 4
* = 5 - 6
. RZ
-+ ++
7.13
MEAN SD R RSQ SIGF SLOPE INTCP
ZNEX 15.80 6.89 -.029 .001 .422 -.13 16.05
CARTO 1.94 1.49 -6.2-03 2.04
SEE N
6.96 50
1.51 50
-------
ZINC VS. SAND OXIDIZED
195
DOWN-ZNEX1Z' ACROSS-SAND'S'
I RS
72.1 +
I
I
I
I
51.8+
I
I
I
35.5 +
I
I
I..
19.3+..
RZ
I*.
I.
3.0 +
+RS + +
.0 47.8
SYMBOLS :
. = 1 - 7
: = 8 - 14
* = 15 - 21
RZ
++
95.5
ZNEX
SAND
MEAN SD
14.47 3.36
2.28 10.54
R RSQ SIGF SLOPE INTCP SEE N
.018 .000 .449 5.8-03 14.46 3.39 52
5.7-02 1.45 10.64 52
ZINC VS. SAND REDUCED
DOWN-ZNEX'Z ป ACROSS-SAND1S1
72.1-
51.8+
35.5
19.3
3.0
SYMBOLS :
. = 1 - 6
: = 7 - 12
* = 13 - 18
RS
*
RZ. .
*
+
.0
-RS--+-
47.8
RZ
++
95.5
ZNEX
SAND
MEAN SD
15.81 6.99
11.95 24.43
R RSQ SIGP
-.526 .277 .000
SLOPE INTCP SEE N
-.15 17.61 5.97 101
-1.84 41.04 20.88 101
-------
ZINC VS. SILT OXIDIZED
196
DOWN-ZNEX1Z1 ACROSS-SILT1S1
I SYMBOLS :
72.1+ . = 1 - 3
I : = 4 - 5
I * = 6 - 7
I
I
51.8+
I
I
I
35.5RS
I
I
I
19.3RZ .. .
I
m "iC
I . . .. : :
I
.0+ RZ
++ + +-RS + ++
.5 49.6 98.7
MEAN
SD
R
RSQ SIGF
SLOPE
INTCP
SEE
N
ZNEX
14.47
3.36
-.499
.249 .000
-.15
20.08
2.94
52
SILT
37.88
11.34
-1.68
62.24
9.92
52
ZINC VS. SILT REDUCED
DOWN-ZNEX1Z1
I
72.1+
I
I
I
I
51.8+
I
I
I
35.5+
I
I
I
19.3 +
RZ
I
I
3.0+.
++
.5
ACROSS-SILT1S'
RS
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
*
<
-+ RS+ +-
49.6
RZ
++
98.7
MEAN SD
ZNEX 15.81 6.99
SILT 40.32 19.40
R RSQ SIGF SLOPE
-.098 .010 .166-3.5-02
-.27
INTCP SEE N
17.23 6.99 101
44.60 19.41 101
-------
ZINC VS. CLAY OXIDIZED
DOWN-ZNEX'Z1 ACROSS-CLAY1C1
72.1
51.8
35 .5
19.3
197
3.0
SYMBOLS :
. = 1 - 2
: = 3
* = 4 - 5
RC
.RZ
**
Z
.0
.+ RC
41.0
82.0
ZNEX
CLAY
MEAN SD
14.47 3.36 .414 .172 .001
59.84 13.19
R RSQ SIGF SLOPE INTCP SEE N
.11 8.15 3.09 52
1.63 36.32 12.13 52
ZINC VS. CLAY REDUCED
DOWN-ZNEX'Z' ACROSS-CLAY'C'
72.1
SYMBOLS :
. = 1 - 2
: = 3
* = 4
51.8
35.5
19.3
ซ
RZ ซ . s . .
3.0+..
++ RC +-
.0 41.0
...
. .
RC
.*. .RZ
++
82.0
ZNEX
CLAY
MEAN SD
15.81 6.99
47.86 25.31
R RSQ SIGF SLOPE INTCP
.580 .337 .000 .16 8.15
2.10 14.63
SEE N
5.72 101
20.72 101
-------
CARBON VS. SAND OXIDIZED
193
DOWN-CARTO1C1 ACROSS-SAND'S1
I SYMBOLS :
7.13 + . . = 1 - 4
I
I * = 8 - 11
RS
I
5.03 +
I .
I
I
3.36+
I
I .
RC.. .
1.68+:
I*.
I.
I. RC
. 00+
++ RS+ + + ++
.0 47.8 95.5
MEAN
SD
R
RSQ
SIGF SLOPE
INTCP
SEE
N
CARTO
1.84
1.48
-.218
.048
.070-1.4-02
2.03
1.46
47
SAND
13.96
23.22
-3.42
20.25
22.91
47
SAND
11.95
24.43
101
CARBON VS. SAND REDUCED
DOWN-CLAY1C' ACROSS-SILT'S'
I RC RS SYMBOLS :
82.0+ . = 1 - 3
I ... : = 4 - 5
I . : * = 6 - 8
I
I *:
57 .9+ .:.
I
I
I
38.6 +
I
I
I
19.3 +
I . RC
I
I
.0+
++ + + Rs ++
5 49.6 98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
CLAY 59.84 13.19 -.640 .410 .000 -.74 88.06 10.24 52
SILT 37.88 11.34 -.55 70.79 8.80 52
-------
CARBON VS. SILT OXIDIZED
199
DOWN-CARTO'C' ACROSS-SILT'S'
I RS SYMBOLS :
7.13+ . = 1 - 2
I : = 3
I * = 4
I
I
5.03 +
I
I
I
3.36 +
I
I
I
1.68+ . RC
RC
I . .
I
.00+
++ RS + + ++
.5 49.6 98.7
MEAN SD
CARTO 1.40 .31
SILT 29.67 4.38
SILT 37.88 11.34
R RSQ SIGF SLOPE
.094 .009 .365 6.6-03
1.33
INTCP SEE
1.20 .32
27.81 4.51
N
16
16
52
CARBON VS. SILT REDUCED
DOWN-CARTO1C' ACROSS-SILT'S'
I
7.13-
5.03
3.36
1.68
. 00RC
++
.5
RS
SYMBOLS :
. - 1 - 2
: = 3
* = 4 - 5
RC
-RS-
49.6
++
98.7
MEAN
SD
R
RSQ SIGF
SLOPE
INTCP
SEE
N
CARTO
1.84
1.48
.581
.337 .000
3.8-02
.26
1.22
47
SILT
41.75
22.79
8.93
25.32
18.76
47
SILT
40.32
19.40
101
-------
CARBON VS. CLAY OXIDIZED
200
DOWN-CARTO'C' ACROSS-CLAY111
I RI SYMBOLS
7.13+ . = 1
I : = 2
I * = 3
I
I
5 .03 +
I
I
I
3.36 +
I
I
I
I.68RC :
I . RC
I
I
.00 +
++ + + + R1 ++
.0 41.0 82.0
MEAN
CARTO 1.40
CLAY 67.91 9.15
CLAY 59.84 13.19
CARBON VS. CLAY REDUCED
SD R RSQ SIGP SLOPE INTCP SEE
.31 -.094 .009 .364-3.2-03 1.61 .32
-2.79 71.81 9.42
N
16
16
52
DOWN-CARTO'C'
I
7.13 +
I
I
I
I
5.03 + .
I
I.
I
3.36 +
I.
RC
I
1.68+
I.
I
I .
.00 + .
++
.0
ACROSS-CLAY'1
Rl
SYMBOLS :
. = 1 - 2
: = 3
* . 4
. . * .RC
+-
41.0
-R1+-
++
82.0
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
CARTO 1.84 1.48 -.293 .086 .023-1.5-02 2.53 1.43 47
CLAY 44.64 28.32 -5.60 54.94 27.38 47
CLAY 47.86 25.31 101
-------
CLAY VS. SAND OXIDIZED
201
DOWN-CLAY'C' ACROSS-SAND'S 1
I SYMBOLS :
0 +
. = 1 - 4
Is
: = 5 - 8
I: .
* = 9 - 12
RS
RC
9+: .
I
I.
I.
38.6+..
I
I.
I
19.3 +
I
I
I
.0+
++ +RS + + RC++
.0 47.8 95.5
CLAY
SAND
MEAN SD R RSQ SIGF
59.84 13.19 -.563 .317 .000
2.28 10.54
CLAY VS. SAND REDUCED
DOWN-CLAY'C' ACROSS-SAND1S1
82.0-
:
*
RS.
Is
57.9RC
38.6
19.3
+
.0
SLOPE INTCP SEE
-.70 61.45 11.01
-.45 29.20 8.80
SYMBOLS :
. = 1 - 5
: = 6 - 10
* = 11 - 15
N
52
52
RS-
47.8
-RC ++
95.5
CLAY
SAND
MEAN SD R RSQ SIGF
47.86 25.31 -.702 .492 .000
11.95 24.43
SLOPE INTCP SEE
-.73 56.55 18.13
-.68 44.36 17.50
N
101
101
-------
CLAY VS. SILT OXIDIZED
202
DOWN-CLAY 1C1 ACROSS-SILT1S1
I RC RS SYMBOLS :
82.0+ . = 1 - 3
I ... : = 4 - 5
I . : * = 6 - 8
I . *.
I *:
57.9+ . : .
I
I
I
38.6 +
I
I
I
19.3 +
I . RC
I
I
.0 +
++ + + RS ++
.5 49.6 98.7
CLAY
SILT
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
59.84 13.19 -.640 .410 .000 -.74 88.06 10.24 52
37.88 11.34 -.55 70.79 8.80 52
CLAY VS. SILT REDUCED
DOWN-CLAY'C'
I
82.0 +
I
RC
I
I
57.9+
I
I
I
38.6 +
I
I
I
19.3+
I
I
I
.0+.
++
.5
ACROSS-SILT'S1
RS
**
SYMBOLS :
. = 1 - 3
: = 4 - 5
* = 6 - 8
RC
ฆ+ +-RS +-
49.6
++
98.7
MEAN SD R RSQ SIGF SLOPE INTCP SEE N
CLAY 47.86 25.31 -.413 .170 .000 -.54 69.56 23.18 101
SILT 40.32 19.40 -.32 55.45 17.76 101
-------
SILT VS. SAND OXIDIZED
203
DOWN-SILT'S'
I
98.7 +
I
I
I
I
69.8+.
I.
I..
I.
46.7R1
RS
I*.
I: .
23.6+:
I
I
I
.5+
++-
.0
ACROSS-SAND11'
SYMBOLS :
. = 1 - 5
: = 6 - 9
* = 10 - 13
RS
-Rl-
47.8
++
95.5
SILT
SAND
MEAN SD R RSQ SIGF SLOPE
37.88 11.34 -.274 .075 .025 -.30
2.28 10.54 -.26
INTCP SEE N
38.55 11.01 52
11.94 10.24 52
SILT VS. SAND REDUCED
DOWN-SILT'S1
I
98.7+.
I
I
X
1
69.8R1 .
46.7+:
RS
T 1
23.6+:
1
I
I
.5+
++
.0
ACROSS-SAND'l1
SYMBOLS :
. = 1 - 6
: = 7 - 11
* = 12 - 16
RS
ฆ+R1 +-
47.8
++
95.5
SILT
SAND
MEAN SD R RSQ SIGF SLOPE
40.32 19.40 -.355 .126 .000 -.28
11.95 24.43 -.45
INTCP SEE N
43.69 18.23 101
29.99 22.95 101
-------