905R79100
INTERNATIONAL JOINT COMMISSION
MENOMONEE RIVER
PILOT WATERSHED STUDY
DRAFT
FINAL REPORT
VOLUME 11
AVAILABILITY OF POLLUTANTS ASSOCIATED WITH SUSPENDED
OR SETTLED RIVER SEDIMENTS WHICH
GAIN ACCESS TO THE GREAT LAKES
Sponsored by
INTERNATIONAL JOINT COMMISSION
POLLUTION FROM LAND USE
ACTIVITIES REFERENCE GROUP
UNITED STATES ENVIRONMENTAL
PROTECTION AGENCY
JULY 1979
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AVAILABILITY OF POLLUTANTS ASSOCIATED WITH
SUSPENDED OR SETTLED RIVER SEDIMENTS
WHICH GAIN ACCESS TO THE GREAT LAKES
BY
D. E. ARMSTRONG
J. R. PERRY
D. E. FLATNESS
WATER CHEMISTRY LABORATORY
UNIVERSITY OF WISCONSIN-MADISON
GRANT NUMBER: 68-01-4479
PROJECT OFFICER: E. PINKSTAFF
WATER RESOURCES CENTER
UNIVERSITY OF WISCONSIN-MADISON
U.S. Environmental Protection Agency
GLNPO Library Collection (PL-12J)
77 West Jackson Boulevard,
Chicago, IL 60604-3590
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DISCLAIMER
This report has been reviewed by the Great Lakes National
Program Office of the U.S. Environmental Protection Agency,
Region V Chicago, and approved for publication. Mention of
trade names or commercial products does not constitute endorse-
ment or recommendation for use.
ii
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PREFACE
Efforts to control eutrophication of the Great Lakes have focused mainly
on reducing the loadings of phosphorus (P) from external sources. Decisions
on the reduction of phosphorus loadings require that target loadings, based on
the expected response of the lakes to a given loading reduction, be
established. Furthermore, decisions must be based on the expected benefit of
reduced loadings as compared to the cost of loading reduction. Assessing both
the cost and response for a given reduction in phosphorus loading requires an
understanding of the biological availability of the different P forms entering
the Great Lakes. Inorganic phosphate in solution is known to be readily
available to algae and higher plants; however, the biological availability of
particulate phosphorus is uncertain. Because approximately 75% of the P
loadings to the Great Lakes from diffuse sources may be in particulate form,
assessing the biological availability of particulate P is of considerable
importance in evaluating the benefits to be accrued from a reduction in P
loadings from point as compared to nonpoint sources.
The purpose of this investigation was to evaluate the availability of
certain elements, mainly phosphorus, transported to the Great Lakes by
suspended sediment. Nitrogen (N) was also investigated because of its
importance as a nutrient element; also included were certain trace metals
because of concern over their possible adverse effects in the Great Lakes.
Availability was estimated by chemical methods. For P, the chemical
methods (NaOH extraction and anion exchange resin desorption) have been
related to direct measurements of biologically-available P in the laboratory;
for N, measurements were made of inorganic N (available) and an organic
fraction which may be converted to inorganic N; for trace metals, measurements
were made of the fraction readily desorbed (chelating cation exchange resin)
and the fraction associated mainly with hydrous oxides (hydroxylamine hydro-
chloride extractable).
Samples were collected from five tributaries within the Great Lakes
Basin, namely, Genesee in New York, Grand in Michigan, Maumee in Ohio, and
Menomonee and Nemadji in Wisconsin. These tributaries, except the Nemadji,
were also among the pilot watersheds used by the International Reference Group
on Great Lakes Pollution from Land Use Activities to investigate pollutant
loadings to the Great Lakes for the International Joint Commission. Samples
were transported to the laboratory in Madison, Wisconsin for analysis. The
suspended sediments were fractionated according to particle size, and chemical
measurements were used to estimate the availability of P, N, and trace metals
in the suspended sediment. Samples of recessional shoreline material were
also analyzed for available P.
iii
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CONTENTS
Title Page i
Disclaimer ii
Preface iii
Contents iv
Acknowledgements v
*Part I - Suspended Sediment Sampling and Distribution . . . I-i
*Part II - Availability of Phosphorus in Suspended
Sediments and Recessional Shoreline Soils .... Il-i
*Part III - Availability of Nitrogen in Suspended and
Bottom Sediments Ill-i
*Part IV - Availability of the Trace Metals, Copper,
Lead, and Zinc in Suspended and Bottom
Sediments IV-i
*Detailed contents are presented at the beginning of each part.
iv
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ACKNOWLEDGMENTS
We wish to thank R. T. Bannerman (Wisconsin Department of
Natural Resources), A. Carlson (New York State Department of
Environmental Conservation), B. J. Eadie (Great Lakes Environ-
mental Research Laboratory, Ann Arbor, Michigan), T. J. Logan
(Ohio Agricultural Research and Development Center), and M. Sydor
(University of Minnesota-Duluth) for assistance in obtaining
tributary suspended sediment samples. The assistance of W. C.
Sonzogni (Great Lakes Basin Commission) in coordinating the sam-
pling program is gratefully acknowledged. Financial support
from the U. S. Environmental Protection Agency Region V (Contract
No. 68-01-4479) is also acknowledged.
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PART I
SUSPENDED SEDIMENT SAMPLING AND DISTRIBUTION
by
D. E. ARMSTRONG
J. R. PERRY
D. E. FLATNESS
I-i
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ABSTRACT
Suspended sediment samples were obtained from five tributaries
to the Great Lakes. Samples were collected to represent each season,
but the spring runoff period was emphasized. Measurements were made
of the total suspended sediment concentration and the distribution among
clay (0.2 - 2 urn), silt (2 to 20 urn) and sand (>20 vim) size fractions.
Comparison of mean concentrations with concentrations reported in
earlier investigations indicated the samples were representative of
the sampled tributaries. Mean suspended sediment concentrations (mg/L)
were 447 (Genesee), 34 (Grand), 171 (Maumee), 138 (Menomonee) and 211
(Nemadji). The concentrations varied widely in a given tributary;
coefficients of variation ranged from 37% (Grand) to 165% (Genesee).
Sediment distribution among the three size fractions was fairly uniform.
Comparison of the mean values for the five tributaries showed the highest
proportion (34 to 51%) was present in the silt fraction. The ranges for
the clay and sand fractions were 21 to 42% and 14 to 35%, respectively.
I-ii
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CONTENTS - PART I
Title Page ,.,,.,, „ l-i
Abstract .....,.,,,,. , I-ii
Contents ........,.*.,....... I-ili
Tables ................. ....... I-iv
1-1 Introduction 1-1
1-2 Conclusions 1-2
1-3 Watershed Characteristics 1-3
1-4 Sampling and Analysis ....... f 1-4
Collection of Suspended Sediment 1-6
Collection of Bottom Sediment 1-6
Size Fractionation of Suspended Sediment 1-6
Size Fractionation of Bottom Sediment 1-6
1-5 Results and Discussion , . 1-7
References ............... . 1-12
Appendices
I-A Description of Sediments 1-14
I-B Particle Size Distribution and Organic Matter Content of
Suspended Sediments . 1-16
I-iii
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TABLES
Number Page
1-1 Summary of tributary samples collected for suspended
sediment analysis 1-5
1-2 Comparison of suspended sediment and discharge values
between the observed (1977-78) samples and previous
(historical) samples 1-8
1—3 Mean concentrations and size distribution of suspended
sediment in tributary samples 1-9
1-4 Particle size distribution and organic matter content
of bottom sediment samples 1-11
I—A-l Identification and background information on.suspended
sediment samples obtained to evaluate particulate-
associated pollutant availability 1-14
I-A-2 Identification and background information on bottom
sediments 1-15
I-B-1 Particle size distribution of suspended sediment from
selected rivers at the Great Lakes Basin 1-16
I-B-2 Organic matter content of suspended sediment from
selected rivers of the Great Lakes Basin 1-17
I-iv
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1-1. INTRODUCTION
The approach in this investigation involved the collection of
samples to reflect the possible effects of season and discharge on
availability. Time-integrated samples were collected in an attempt
to obtain suspended sediment representative of the tributary suspended
load. However, because the number of samples collected was relatively
small, evaluation of whether the samples collected were representative
of the tributary is particularly important. The sampling program was
not designed to evaluate the suspended sediment loading, but rather to
evaluate the availability characteristics of representative samples.
1-1
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1-2. CONCLUSIONS
The mean concentrations of suspended sediment in the samples
collected were representative of the respective tributaries. Even
though total suspended sediment concentrations varied over a wide
range, the particle size distribution was fairly uniform for a given
tributary. The suspended sediment samples provided an adequate sample
set for evaluation of the availability of phosphorus, nitrogen, and
trace metals associated with suspended sediments in the five tributaries,
1-2
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1-3. WATERSHED CHARACTERISTICS
Characteristics of the watersheds drained by the tributaries have
been described (1-4) and only a brief summary is provided for background
purposes.
The Genesee River Watershed (6,420 km2) is mainly rural, except
for Rochester, New York at the mouth of the Genesee River on Lake
Ontario. Although Rochester is an important source of dissolved P,
about 80% of the particulate P is attributed to diffuse sources (2).
All samples were taken up stream from Rochester to minimize the influence
of point sources on the samples.
The Grand River (watershed of 14,660 km2) is the largest single
tributary to Lake Michigan and discharges at Grand Haven, Michigan.
Approximately 60% of the watershed is in agricultural 4ise (5,6). The
sandy loam texture of soils in the watershed leads to high infiltration
rates and relatively low erosion and particulate P loadings. The
groundwater contribution to the river discharge is relatively high and
constant, minimizing the fluctuations in discharge as related to storm
events. About 60% of the particulate P loading is attributed to nonpoint
sources.
The Maumee River Watershed (17,100 km2) is the largest watershed
draining into the Great Lakes on the U.S. side. The river discharges
into Lake Erie at Toledo, Ohio. About 90% of the watershed is in
agricultural use; the soils tend to be fine-textured and impermeable
(7). Most of the annual sediment load is attributed to soil erosion
(8). Estimates of particulate P loading range from 77 to 90% of the
total P loading mostly from nonpoint sources (2,3).
The Menomonee River Watershed (344 km2) is mostly urban, draining
into Lake Michigan at Milwaukee, Wisconsin. The soils tend to be
poorly drained (9). Particulate P represents about 80% of the annual
total P loading. Samples were taken from a site reflecting the urban
influence of the watershed—yet distant from the Milwaukee Sewage
Treatment Plant located at Jones Island.
The Nemadji River Watershed (1,290 km2) drains the red clay region
of northeastern Minnesota and northwestern Wisconsin and enters Lake
Superior at Superior, Wisconsin, The fine-textured soils are subject
to erosion even though the land is mostly forested (10); particulate
P loading is mostly from nonpoint sources.
1-3
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1-4. SAMPLING AND ANALYSIS
Collection of Suspended Sediment
Water samples were collected through the cooperation of
investigators located near the tributaries. The goal was to collect
samples during each season and representing events of different sizes
(discharge rates). Sampling stations were located near the river mouth
to obtain samples representative of the suspended sediment transported
to the Great Lakes. In most cases, sampling was conducted above large
urban areas located near the river-lake interface to avoid overemphasis
on point sources.
On the Genesee, the main sampling station was at-Avon (above
Rochester, New York), a few km from Lake Ontario. Some samples also
were obtained at Mt. Morris (above Avon) and on two tributaries to the
Genesee, namely Oatka Creek (about 35 km above Avon) and Canaseraga
Creek (about 100 km above Avon). The Maumee River was sampled at the
U.S. Geological Survey Gauging station at Waterville, Ohio, about 31
km above Lake Erie. The Menomonee River was sampled at the 70th street
bridge in Wauwatosa, Wisconsin, about 8.5 km above Milwaukee Harbor.
This station was selected to avoid possible major influences of the
Harbor on the tributary samples. The Grand River was sampled about
3 km below Grand Haven, Michigan, and these samples may reflect the
influence of point sources. The Nemadji station was located about
6 km above Lake Superior (St. Louis Bay) and should reflect largely
diffuse sources.
Samples were composited from several sub-samples obtained during
an event. The samples were shipped in polyethylene containers by
surface freight; no preservation was provided except for the Menomonee
samples which were refrigerated during transit and storage. Shipment
of samples generally took 1 to 4 days, and on arrival the samples
were refrigerated at 4°C.
Sample identification, sampling frequency, and distribution and
background information are presented in Tables 1-1 and Appendix Table
I-A-1. The importance of spring runoff was emphasized in the sampling
program.
1-4
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Table 1-1. Summary of tributary samples collected for
suspended sediment analysis
Number of Samples
Tributary Spring Summer Fall Winter
Genesee
Avon 5 Oil
Mt. Morris 0 Oil
Oatka Creek 0 010
Canaseraga Creek 2 120
Grand 4 100
Maumee 2 101
Menomonee 6 3 01
Nemadji 7 121
1-5
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Collection of Bottom Sediment
Tributary bottom sediment dredge samples (upper few cm) were
obtained from the Menomonee, Genesee, and Nemadji Rivers. These
samples are described In Appendix Table I-A-2.
Size Fractionation of Suspended Sediment
The suspended sediments were separated Into size fractions of
<0.2, 0.2 to 2, 2 to 20, and >20 ym by settling and centrifugation
techniques. The <0.2 ym fraction was defined as the "dissolved"
fraction; the other size fractions correspond to clay, silt, and sand,
respectively.
The initial separation involved continuous flow centrifugation
(Sorvall Model RC2-B) based on application of Stokes Law to angled-type
centrifuge rotors (11) to obtain the <0.2 ym (supernatant or dissolved
fraction) and >0.2 ym sized-fractlons. For this separation, the
samples were centrifuged at 13,000 rpm at a flow rate of 314 ml/min,
using the centrifuge head holding 8x50 ml centrifuge tubes. The fraction
>0.2 ym was resuspended and further fractionated by quiescent settling
(12). The respective settling velocities (cm/hr at 20°C) were 0.013 to
1.3 (0.2 to 2 ym), 1.3 to 130 (2 to 20 ym), and 130 cm/hr (>20 ym).
Sediment samples were analyzed without drying and subsamples were
analyzed for moisture content by drying at 105°C.
Size Fractionation of Bottom Sediment
The bottom sediment samples were suspended by shaking in distilled
water for about 1 hour. The samples were then sieved (2000 ym), and
the gravel fraction (>2000 ym) was discarded. The material <2000 ym
was size fractionated into clay, silt, and sand size fractions by
quiescent settling as described above for the suspended sediment samples.
1-6
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1-5. RESULTS AND DISCUSSION
To evaluate whether the samples collected were representative,
comparisons were made with the tributary loading data (2). Values for
mean discharge, mean total suspended sediment concentration (TSS) and,
the relationship between discharge and TSS were compared (Table 1-2).
These comparisons indicate the samples collected were representative of
the respective tributaries. The mean discharge values were higher and
the TSS concentration versus flow slope values were lower for the samples
collected in 1977-78 than for historical values (1,2) because the 1977-78
investigation emphasized sample collection during periods of high flow.
However, the mean TSS concentrations were in the same range for the 1977-
78 and earlier samples, Indicating the samples collected were comparable.
The correlation coefficient between TSS concentration and discharge for
the 1977-78 samples indicates a high proportion (36 to 83%) of the vari-
ance in TSS concentration was due to variation in discharge.
Concentrations of TSS varied over a wide range for the samples
collected (Table 1-3, and Appendix I-B-1). Mean concentrations were
highest for the Genesee samples and lowest for the Grand samples.
Variability in concentration was particularly high for the Genesee,
Menomonee, and Nemadji samples as shown by the coefficient of variation
for the mean TSS concentration (>0.2 \im).
The particle size distribution was fairly uniform for the samples
from a given tributary. In most cases, the highest proportion (mean -
34 to 51%) was present in the 2 to 20 urn size fraction; this fraction
also exhibited the least variability (cfv. = 17 to 33%). The >20 ym
fraction represented about 30% of the TSS for the Genesee, Grand, and
Menomonee samples, but only about 15% for the Nemadji and Maumee. The
0.2 to 2 ym fraction averaged about 20 to 40% of the TSS. The general
uniformity of the particle size distribution within a given tributary
sample set, in spite of the wide variation in TSS concentration, suggests
the sediment types transported during periods of high loading (high flow
and concentration) and low loading (low flow and concentration) may be
similar.
Comparison of individual samples (see Appendix I-B-1) indicates a
general tendency for lower TSS concentration and a higher proportion of
fine particulates during low flow events. Similarly, the organic matter
content of the suspended sediment tended to be higher for samples repre-
senting low flow and TSS concentration conditions. This was apparently
related to a higher organic matter content in the finer than in the coarser
size fractions (Appendix I-B-2).
1-7
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high percentage of sand-size particulates (2 to 2000 ym). However,
the sand fraction contained a negligible amount of organic matter,
while substantial amounts (3 to 34%) were present in the silt and clay
fractions.
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REFERENCES - I
1. Pollution from Land Use Activities Reference Group. Environmental
Management Strategy for the Great Lakes System. International Joint
Commission, Windsor, Ontario, Canada. 1978.
2. Sonzogni, W. C., T. J. Monteith, W. N. Bach and V. G. Hughes.
United States Great Lakes Tributary Loadings. PLUARG Technical
Report to Task D, Ann Arbor, Michigan, 1978. 187 pp.
3. Logan, T. J. Chemical Extraction as an Index of Unavailability of
Phosphate in Lake Erie Basin Suspended Sediments. Final Report,
Lake Erie Wastewater Management Study. U.S. Army Corps of Engineers,
Buffalo, N.Y., 1978. 42 pp.
4. Bahnick, D. A. The Contribution of Red Clay Erosion to Orthophosphate
Loadings into Southwestern Lake Superior. J. Environ. Qual. 6:217-
222, 1977.
5. Eadie, B. J. The Effect of the Grand River Spring Runoff on
Lake Michigan. PLUARG Technical Report to Task D, Ann Arbor, Michigan,
1976. 85 pp.
6. Stephenson, H. E. and J. R. Waybrant. Watershed Analysis Relating to
Eutrophication of Lake Michigan. Institute of Water Research,
Technical Report No. 11, Michigan State University, 1971. 118 pp.
7. U.S. Department of the Interior. Report on Water Pollution in the
Maumee River Basin. Fed. Water Pollution Control Admin., Great Lakes
Region, Cleveland, Ohio, 1966.
8. McCallister, D. L. and T. J. Logan. Phosphate Adsorption-Desorption
Characteristics of Soils and Bottom Sediments in the Maumee River
Basin of Ohio. J. Environ. Qual. 7:87-92, 1978.
9. Konrad, J. G., G. Chesters and K. W. Bauer. International Joint
Commission Menomonee River Pilot Watershed Study, PLUARG Work Plan,
1974. 44 pp.
10. Wisconsin Department of Natural Resources. Wisconsin Tributary Loadings
to the Upper Great Lakes. U.S. Environmental Protection Agency.
EPA-905/4-75-003, 1975. 57 pp.
11. Jackson, N. L. Soil Chemical Analysis-Advanced Course, University of
Wisconsin-Madison, 1956. 991 pp.
1-12
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12. Day, P. R. Particle Fractionation and Particle-size Analysis. In:
Methods of Soil Analysis, Part I. Am. Soc. Agron., Madison, Wis. 1965.
13. Liegel, E. A. and E. Schulte. Wisconsin Soil Testing and Plant Analysis
Procedures No. 6. Soil Fertility Series, Revised (1977). Dept. of Soil
Science, University of Wisconsin-Madison, 1977.
1-13
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APPENDIX A. DESCRIPTION OF SEDIMENTS
Appendix I-A-1. Identification and background information on suspended sediment samples obtained to evaluate particulate-associated pollutant availability
Sample So.
Location
Date
Comments
Sample Ho.
Location
Date
CENESEE RIVER
GRAND RIVER
Canaserago Creek at
Shakers Crossing, N.Y.
Itl
IV
XI
XII
XIV
XV
XVI
I
II
III
IV
III
IV
19 Kay 77 Flow rate -5.2 m /Sec.
21 June 77 Plow rate - 96.8 • /sec.
Jones flridga jt Highway 28 Sept 77
20A, Mt. Morris, N.Y.
29 Sept 77
Canasecaga Creek at 17 Febr 78
Shakers Crossing. N.Y.
Oatka Creek at 1? Febr 78
Garbutt, N.Y.
Jones Bridge at Highway 17 Febr 78
20A, Ht. Morris, N.Y.
Avon, N.Y. 17 Febr 78
Canaseraga Creek at 20 Sept 77
Shakers Crossing, N.Y.
Canaseraga Creek at 22 Sept 77
Shakers Crossing, N.Y.
21 June 7?
29 Mar 78
6 Apr 78
19 Apr 78
3 May 78
Canaseraga Creek at
Shakers Crossing, N.Y.
Avon, N.Y .
Avon, N.Y.
Avon, N.Y.
Bridge at 70th St.,
Wauwatosa, VI
Bridge at 70th St.,
Wauwatosa, HI
MEJTOMOHEg RIVER
2 Apr 77
Bridge at 70th St.,
Vauwatosa, WI
Bridge at 70th St.,
Wauuatosa, VI
Bridge at 70th St.,
Vauwatosa, WI
Bridge at 70th St.,
Wauwatosa,, VI
Bridge at 70th St.,
Wauwatosa, VI
Bridge at 70th St.,
Vauwatosa, WI
Bridge at 70th St.,
Wauwatosa, VI
Bridge at 70th St.
Vauwatosa, VI
USGS Station,
Waterville, OH
USCS Station,
Vatervllle, OH
USGS Station,
Waterville, OH
USGS Station,
Waterville, OK
18 July 77
8 Aug 77
13 Dec 77
3 Febr 78
22 Mar 78
30 Mar 78
6 Apr 78
18 Apr 78
MAUHEEJtiyER
26 Apr 77
5 July 77
7 Dec 77
22 Mar 78
Flow rate - 205.5 m /sec.
Sampled at rising portion
of hydrograph.
Flow rate - 238.9 m3/sec.
Sampled at rising portion
of hydrograph.
Flow rate « 6.2 n /sec.
Flow rate * 7.1 m /sec.
Flow rate - 22.6 m /sec.
Flow rate * 27.2 m /aec.
Flow rate - 101.3 ra3/sec.
Flow rate * 49.0 m /sec.
Flow rate » 2.4 m /sec,
Flow rate " 164,1 m /sec.
Vater temp. * 2 C.
Flow rate - 152.8 n3/sec.
Flow rate - 283 m3/aec.
Vater tenp. = 2°C
Reservoir release.
Flow rate - 73.6 m /sec.
Water temp. • 9°C.
Gage height 88 cm..
Flow rate - 13.7 m /sec.
Sampled at hydrograph
peak. Gage height 83 cm.
Rainfall -1.5 en. Flow
rate • 11.3 m^/sec.
Gage height -99 cm. Flow
rate - 15.1 mj/sec.
Gage height « 61 cm.
Sampled during hydrograph
decline. Flow rate -
3.7 m3/aec.
Gage height - 62 cm.
Flov rate -4.0 m3/sec.
Gage height - 52 cm.
Flow rate - 2-1 m3/sec,
Snowmelt.
Cage height - 79 cm. Flow
rate - 9.9 m3/sec.
Gage height - 69 cm. Flow
rate - 5.7 m3/sec.
Gage height - 75 cm. Flow
rate « 8.6 m3/sec.
Gage height * 87 cm. Flow
rate - 13.4 m3/sec.
Rainfall - 2.3 cm.
Mean daily flow rate *=
931 m-Ysec. Normal
high-flow spring runoff
event.
Mean daily flow rate »
116 mVsec. Sampled at
hydrograph peak.
Mean daily flow rate -
120 m3/sec.
Mean dally flow rate -
2572 m^/sec. Very
high flow runoff.
River mouth; 3 km.
down-stream froa Grand
Haven, MI.
River nouth, 3 km.
down-stream from Grand
Haven, HI.
River mouth; 3 km
down-stream from Grand
Haven, MI.
River mouth; 3 km.
down-stream from Grand
Haven, HI.
River mouth; 3 km
down-stream from Crand
Haven, HI.
15 June 77 Grand Rapids, MI. I'SCS
Station 04119000 at km
66. Flow rate - 41 m3/
sec. Vater temp • 16°C.
23 Aug 77 Grand Rapids, MI. I'SGS
Station 04119000 at km
66. Flow rate • 28 m3/
sec. Water temp. - 20°C
10 Apr 78 Grand Rapids. MI. I'SCS
Station 04119000 at km
66. Flow rate - 391 m3/
sec. Water temp. » 5°C.
12 Apr 78 Grand Rapids, MI. USGS
Station 04119000 at km
66. Flow rate - 359 m3/
21 Apr 78 Grand Rapids, MI. L'SGS
Station 04119000 at km
66. Flow rate - 161
m3/sec.
NEMADJI RIVER
20 May 77 Three days intermittant
thunderstorm activity.
Rainfall - 4.5 cm Flow
velocity » 4 cm/sec.
1 June 77 Sampled at hydrograph
peak. Stage « 320 cm.
Rainfall - 4.5 cm. Flow
velocity - 105 cm/sec.
4 Aug 77 Thunderstorms. Stage
at normal summer level.
5,5 kn from river mouth
(St. Louis Bay) between
Hwy A bridge and Soo Line
RR bridge. South
Superior, WI
5.5 km from river mouth
(St. Louis Bay), between
Hwy A bridge and Soo Line
RR bridge. South
Superior, VI
5.5 kn from river
mouth (St. Louis Bay),
between Hvy A bridge and
Soo Line RR bridge.
South Superior, HI
5.5 km from rlvei 29 Sept 77 Sampled after 3-day rain
mouth (St. Louis Bay), (10 cm ppt). Stage •
between Hwy A bridge 312 cm. Discharge " 40
and Soo Line RR bridge. mVsec. Flow velocity »
South Superior, VI 80 cm/sec; leaves present
In water.
5.5 km from river mouth 14 Nov 77 Cage height - 300 cm.
(St. Louis Bay), between Flow rate - 34 m3/sec,
Hwy A bridge and Soo Line
RR bridge South Superior,
WI
5.5 km from river mouth 25 Febr 78 Late winter, just prior
(St. Louis Bay), between to spring runoff.
Hwy A bridge and Soo Line
KR bridge. Soutu
Superior, WI
5,5 km from river mouth 30 Mar 78 Beginning of Spring run-
(St. Louis Bay), between off peak. Gage height «
Hwy A bridge and Soo Line 370 cm and rising slowly.
RR bridge. South Ice present. Turbidity
Superior, VI abnormally low. Not able
to calculate flow rate
due to ice cover.
5.5 km from river mouth 31 Mar 78 Peak of snow melt run-
(St. Louis Bay), between off; peak low this year.
Hvy A bridge and Soo Line Gage height - 440 cm.
RR bridge. South Flow rate - 106 m3/sec.
Superior, WI Flow velocity • 91 cm/sec
5.5 km from river 2 Apr 78 Samples obtained during
mouth (St. Louis Bay), decline of snow melt
between Hwy A bridge and runoff. Gage height *
Soo Line RR bridge. 360 cm. Flow rate - 64
South Superior, WI n3/sec. Flow velocity *
f>2 cm/sec. Large patches
of brownish scum on water
Ice and stage declining
rapidly.
5.5 km from river mouth 8 Apr 78 Samples obtained during
(St. Louis Bay), between second spring runoff
Hwy A bridge and Soo Line peak which resulted from
RR bridge. South a spring snowfall.
Superior, VI Sampled during hydrograph
decline. Gage height -
450 cm. Flow rate • 124
m3/sec.
5.5 lea from river mouth 22 Apr 78 End of spring runoff.
(St. Louis Bay), between Gage height - 340 cm.
Hwy A bridge and Soo Line Flow rate - 45 m3/sec.
RR bridge. South
Superior, WI
1-14
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1-16
-------
Appendix I-B-2. Organic matter content of suspended sediment
from selected rivers of the Great Lakes Basin
Sample
No.
VI
VII
VIII
IX
X
XI
XII
XIV
XV
XVI
XVII
VI
IX
X
III
IV
III
IV
V
V
VI
VII
VIII
IX
X
XI
Organic
>0.2 Mm
28
70
10
16
4
10
13
4
4
4
14
15
19
19
14
15
20
24
13
46
5
10
7
5
7
matter, % in particle size
0.2 to 2 Mm 2
GENESEE RIVER
52
46
40
27
9
13
24
7
9
10
70
MENOMONEE RIVER
25
13
21
MAUMEE RIVER
15
11
GRAND RIVER
23
32
26
NEMADJI RIVER
15
:"j3
8
14
12
7
8
to 20 Mm
1.5
95
7
11
4
8
10
5
4
5
4
16
20
18
13
13
18
26
9
34
5
10
7
6
6
fractions
>20 Mm
59
87
8
21
2
11
16
2
3
2
3
15
17
29
16
17
20
.19
75
0
5
10
8
4
7
1-17
-------
PART II
AVAILABILITY OF PHOSPHORUS IN SUSPENDED SEDIMENTS
AND RECESSIONAL SHORELINE SOILS
D. E, ARMSTRONG
D. E. FLATNESS
J. R. PERRY
Il-i
-------
ABSTRACT
The availability of inorganic phosphorus was measured in samples of
suspended sediment from five tributaries to the Great Lakes (Genesee, Grand,
Maumee, Menomonee, Nemadji) and in samples of recessional shoreline soils from
the northeastern shore of Lake Michigan and the southern shore of Lake Erie.
Two chemical methods were used to measure available inorganic P in the
sediment and soil samples; extraction with O.lAf NaOH (NaOH-P) and desorption
by equilibration with an anion exchange resin (resin-P). The NaOH-P was used
as an estimate of the maximum available inorganic P; resin-P was a measure of
a more readily available P fraction (released at higher concentrations of
inorganic P in solution). For the suspended sediment, mean values of NaOH-P
(as percent of sediment total P) were 14% for the Nemadji, 19% for the
Genesee, and about 35% for the Grand, Maumee, and Menomonee. Mean resin P
values ranged from 43 to 50% of the NaOH-P. The availability of inorganic P
was fairly uniform among the clay, silt and size fractions for a given
tributary. Mean concentrations of available P (NaOH-P) in the suspended
sediments(jag P/g sediment) were 825 for the Grand, 469 for the Maumee, 460 for
the Menomonee, 162 for the Genesee, and 114 for the Nemadji. Mean
concentration of NaOH-P on a volume basis (yg P/L of water) were 132 for the
Maumee, 64 for the Menomonee, 36 for the Nemadji, 28 for the Genesee, and 16
for the Grand. For the recessional shoreline soils, available P (NaOH-P)
concentrations ranged from 1 to 11 yg P/g sediment, corresponding to 1 to 3%
of the total P.
Il-ii
-------
CONTENTS - PART II
Title Page Il-i
Abstract Il-ii
Contents II-iii
Figures Il-iv
Tables H-v
II-l. Introduction II-l
II-2. Conclusions II-5
II-3. Sampling and Analysis II-7
Collection of Samples 11-7
Analysis of Phosphorus Forms . . II-7
NaOH-P II-7
HC1-P II-8
Resin-P II-8
II-4. Results and Discussion ...... 11-10
Availability of Particulate P in Suspended
Sediment 11-10
Proportion of available inorganic P in
suspended sediment 11-10
Relationships between resin-P and NaOH-P 11-10
Available P-particle size relationships 11-12
Concentrations of available P in suspended
sediments 11-15
Comparisons with other measurements ........ 11-16
Available P loadings 11-17
Availability of Particulate Inorganic P in
Recessional Shoreline Soils 11-19
References 11-23
Appendix
I-A 11-25
II-iii
-------
FIGURES
Number
II-l Diagram of the relationships between particulate- and
algal-P II-2
II-2 Hypothetical isotherm for inorganic P adsorption-
desorption by suspended sediment illustrating the
relationships between apatite and non-apatite (KAIP)
and the inorganic P extracted as resin-P, NaOH-P and
HC1-P II-9.
Il-iv
-------
TABLES
Number Page
II-l Percentage of phosphorus in suspended sediments in
available and non-available fractions ..... 11-11
II-2 Distribution of phosphorus fractions among particle
size fraction 11-13
II-3 Concentrations of phosphorus in suspended sediments . . . 11-14
II-4 Comparison of dissolved and particulate available P
loadings in tributaries 11-18
II-5 Inorganic phosphorus distribution in samples from
recessional shoreline soils along the Great .Lakes .... 11-20
II-6 Inorganic phosphorus distribution in size-fractionated
samples from recessional shoreline soils along the
Great Lakes 11-21
II-A-1 Description of recessional shoreline soil samples .... 11-25
II-A-2 Inorganic P distribution in size-fractionated suspended
sediments 11-26
II-v
-------
II-l. INTRODUCTION
The goal of the investigation was to determine the availability
of phosphorus associated with suspended sediments transported to the
Great Lakes. Dissolved inorganic phosphate is the biologically-
available form of phosphorus. Consequently, the biological availability
of phosphorus in suspended sediments (particulate P) is determined by
the rate and extent of conversion to inorganic phosphate. Because
conversion to dissolved inorganic phosphate is controlled in part by
environmental factors, biological availability in situ depends on
location-specific conditions.
The relationships between particulate phosphorus, dissolved
inorganic phosphate, and algal phosphorus are illustrated in Fig.
II-l. Particulate P in suspended sediment can be divided into non-
apatite (largely Fe- and Al-associated), apatite, and'organic forms
(1,2). The inorganic P forms tend to control the phosphate concentra-
tion in solution through adsorption-desorption or precipitation-
dissolution reactions. Particulate organic P will release dissolved
organic P to solution, but dissolved organic P must also be converted
to inorganic phosphate to become available. Phosphorus-limited algae
can reduce the phosphate concentration to low levels (<0.1 yg/L),
thereby causing the release of particulate inorganic P to solution (3).
The extent of availability of particulate P can be viewed as depending
on the competition between the algal cell and the sediment particle for
phosphate in solution. Available particulate P is the amount released
from the particle at the given phosphate concentration in solution.
Consequently, the factors controlling the availability of particulate
P in suspended sediments include 1. the forms and amounts of phosphorus
in the particulate fraction, 2. the residence time of the particle in
the lake water, 3. the phosphorus status of the algal population, 4.
the solution phosphate concentration maintained by the algal or other
phosphorus sinks, and 5. other factors controlling the solubility of
particulate phosphorus such as pH and Eh.
Assessing the actual availability of phosphorus as controlled by
the above variables would require modeling the environment around the
sediment particle throughout its residence time in the lake water.
However, the potential availability of phosphorus can be evaluated by
measuring the particulate forms of P which could be released at a low
solution phosphate concentration in a realistic time period.
II-l
-------
NON-APATITE
INORGANIC P
APATITE
INORGANIC P
ORGANIC P
INORGANIC
PHOSPHATE
ALGAL
PHOSPHATE
SOIL/SEDIMENT
PARTICLE
SOLUTION ALGAL
LAKE/STREAM WATER CELL
Fig. II-l. Diagram of the relationships between
particulate- and algal-P.
II-2
-------
Two main bioassay approaches have been used to estimate the potential
availability of particulate phosphorus: 1. Growth response bioassay
techniques (4-6), and 2. direct measurement of the conversion of sediment
inorganic P to algal organic P (5, 7-9). Both approaches can be used
to estimate the amount of available P in a given sample. However, the
direct measurement approach can also be used to determine the
availability of the different phosphorus forms.
In the direct measurement approach (7,8), uptake of sediment or
soil P was measured as the decrease in particulate inorganic P or the
increase in particulate organic P following incubation of a P-limited
algal population (Selanastrum eappieornutum)with the suspended soil or
sediment in a growth media containing the sediment or soil as the sole
source of P. This approach assumes that utilization of sediment P
involves the conversion of inorganic P (sediment) to organic P in the
algal cells; availability of sediment organic P is assumed to be
negligible. A small correction is made for inorganic P in the algal
cells. By measuring the amounts of non-apatite and apatite inorganic
P before and after incubation with the test alga, the relationships
between phosphorus forms and biological availability were evaluated.
A procedure involving sequential extraction with O.lff NaOH followed
by N HC1 was used to measure the forms of soil or sediment inorganic P
(8). Under the conditions used, the NaOH-P and HC1-P fractions correspond
closely to the non-apatite and apatite inorganic P fractions, respectively
(1). For a wide range of soils a high proportion (regression coefficient =
0.83) of the NaOH-P was available within 48 hr (8), while the HC1-P
fraction was essentially unavailable, even over a 4-week period.
Similar results were found for lake sediments (7). Consequently,
NaOH-P (or non-apatite inorganic P) appears to represent the maximum
amount of suspended sediment inorganic P likely to become available.
The uptake of the NaOH-P fraction from suspended sediment by algae
can be viewed as a desorption reaction (Fig. II-l). The NaOH-P is
desorbed because of the low solution phosphate concentration maintained
by the P-deficient algae. Consequently, an alternative approach for
measuring available inorganic P is to measure the amount of sediment
P desorbed when a low solution phosphate concentration is maintained
by an anion exchange resin (6,10,11). For several soils, it was found
that the amount of inorganic P desorbed by the resin (resin-P)
corresponded to approximately 50% of the NaOH-P (10). The solution
phosphate concentration in the soil-resin system was near the chemical
detection limit, about 1 pg/L. Apparently, P-deficient algae are able
to reduce solution phosphate to a lower concentration than the resin
(perhaps <0.1 yg/L), thereby resulting in a greater extent of inorganic
P desorption (3). Recently, it was shown that the amount of soil
inorganic P desorbed by resin-fixed aluminum corresponded closely to
the NaOH-P fraction, substantiating the belief that the NaOH-P can be
desorbed if the solution P concentration is sufficiently low (12).
11-3
-------
Thus, the availability of P in suspended sediment was estimated
by two methods. The non-apatite inorganic P fraction (estimated as
NaOH-P) was considered to represent the maximum available inorganic P.
The amount of inorganic P desorbed by equilibrating the sediment with
an anion exchange resin (resin-P) was used as a measure of the more
readily available fraction of the NaOH-P. These procedures do not
measure the availability of sediment organic P, but the organic P in
soils and sediments is apparently mineralized slowly (2,13,14) and
represents a small fraction of available P in comparison to the
inorganic P.
II-4
-------
II-2. CONCLUSIONS
Characteristic differences exist in the availability of inorganic
P in suspended sediments among the tributaries to the Great Lakes.
Available P (NaOH-P), expressed as a percent of total P, averaged 14%
for the Nemadji, 19% for the Genesee, and about 35% for the Maumee,
Menomonee, and Grand Rivers. Coefficients of variation ranged from
5 to 35%. Availability is relatively uniform among the clay, silt
and sand particle size fractions. Consequently, the available P
loading for each tributary can be estimated as the product of
availability (NaOH-P expressed as fraction of total P) and the
total P loading of the tributary.
Available P measured as NaOH-P corresponds to non-apatite inorganic
P and represents the maximum amount of inorganic P expected to be
made available through release of inorganic P to solution (desorption).
Desorption could occur within a period of a few hours. Conversion of
other forms to available P requires mineralization of organic P or
weathering of apatite P. These processes occur at slow rates and are
considered unimportant following deposition of suspended sediments
on the lake bottom. Available P measured as resin-P represents
inorganic P released to solution more readily than the total NaOH-P.
Resin-P is released at solution inorganic P concentrations of about
1 Mg/L, while complete release of NaOH-P requires lower solution
concentrations. Consequently, resin-P may be a better estimate than
NaOH-P of the amount of P typically released in the Great Lakes.
Resin-P represents 40 to 50% of the NaOH-P fraction.
While availability is relatively uniform for the different particle
size fractions, particle size can be an important factor in availability
through controlling the residence time of sediment in the water column.
Relatively rapid settling might limit the availability of the sand
(>20 ym) fraction. Conversely, the clay (0.2 to 2 ym) fraction might
remain permanently suspended and be subject to long term processes
which increase the availability of particulate P. For a suspended
sediment containing equal amounts of clay, silt and sand and 35%
available P (% of total P), complete availability of inorganic P in
the clay fraction would result in an available P level corresponding
to 57 rather than 35% of the sediment total P.
In addition to availability (available P as a fraction of total P),
suspended sediment concentration and sediment total P concentration,
are major factors controlling particulate available P concentrations
in tributary waters. Furthermore, tributary discharge rate is a major
factor in the loading of available P from the tributary.
II-5
-------
Depending on the tributary, available P (NaOH-P) in suspended
sediments represents about 25 to 75% of the total available P loading.
For the U.S. portion of the Great Lakes Basin, available P in suspended
sediments is estimated to represent about 50% of the available P loading
and about 25% of the total P loading.
The availability of inorganic P in the recessional shoreline
samples investigated was low (<3% of total P). If these samples are
representative, the contribution of shoreline erosion to available P
loadings to the Great Lakes is relatively low.
II-6
-------
II-3. SAMPLING AND ANALYSIS
Collection of Samples
The suspended sediment samples collected from the Genesee, Grand,
Maumee, Menomonee, and Nemadji are described in Appendix I-A and I-B.
Samples of recessional shoreline material were obtained from the
southern shore of Lake Erie and the northeast shore of Lake Michigan.
These samples are described in Appendix II-A-1.
Analysis of Phosphorus Forms
Dissolved reactive phosphorus (DRP) was defined as the reactive
phosphorus present in the <0.2 pm size fraction (15). Total phosphorus
was determined by the acid-persulfate digestion technique (16). Samples
digested by autoclaving (120°C at 15 psi), were neutralized and
analyzed (15). Digested sediment fractions were filtered (0.45 pm
Millipore) prior to neutralization. The total P in the sediment or
sediment size fraction was termed total particulate P (TPP).
Available inorganic P in suspended sediments was estimated by two
chemical methods, anion exchange resin desorption (resin-P) and dilute
NaOH extractable P (NaOH-P). Following the NaOH extraction, HC1 was
used to extract the remaining sediment inorganic P (HC1-P). The sum
of NaOH-P + HC1-P was used as an estimate of sediment "total" inorganic P.
NaOH-P
The sediment was extracted (18 hr) with O.ltf NaOH in N NaCl in
50 ml polypropylene centrifuge tubes using a sediment solution ratio
of 1:1000 or wider, usually 1:2000 (15 mg sediment per 30 ml reagent)
(8). The procedure is similar to procedures described elsewhere
(e.g., 17), except for the solution:sediment ratio. Following
extraction, the samples were centrifuged, filtered (0.45 Mm Millipore),
neutralized and analyzed (15).
II-7
-------
HC1-P
The sample previously extracted with O.ltfNaOH was extracted
(1 hr) with JVHCl. After centrifugation, decantation, neutralization,
and filtration (0.45 pm Millipore), the samples were analyzed (15).
Resin-P
The method (10) was similar to previously described procedures
(18,20). Dowex 1-8X anion exchange resin (Cl form), of 20 to 50 mesh
particle size, was cleaned and converted to the HC03 form by soaking
in 0.1A/KHC03. The resin was acetone rinsed, air-dried, sieved (250 Mm),
and the >250 urn fraction was retained for use. The resin, 1.6 ml
(1.0 g), was added to the sediment suspension (30 ml) in a 50 ml
polycarbonate centrifuge tube using a sediment:solution ratio > 1:1000,
usually 1:2000 (15 mg sediment per 30 ml). The resin-sediment system
was equilibrated by shaking for 18 hr. After equilibration, the
mixture was sieved (250 Mm) to separate the resin from the sediment.
The >20 Mm sediment fractions were pre-sieved to exclude >250 urn
particles prior to the resin-P measurement. The resin was rinsed with
a small amount of water and transferred to a long-neck funnel plugged
with glass wool for elution. The resin was equilibrated with 0.25 N
H2S04 (30 min), eluted (total acid volume of 75 ml) at <2 mL/min and
an aliquot (50 ml) of the eluate was analyzed (15). The acidity of the
Murphy-Riley reagent was decreased by an amount equal to the equivalents
of acid in the H2S04 eluate to eliminate the neutralization step.
The relationshipsbetween resin-P, NaOH-P, phosphorus in solution
and the phosphorus forms in the sediment are illustrated in Fig. II-2.
As the phosphorus concentration in solution is lowered, release of
phosphorus from the sediment occurs. However, until the solution
concentration reaches a low level, the fraction released from the
sediment is small. The phosphorus concentration maintained by the
resin CV1 MgP/L) results in desorption of about 50% of the NaOH-P.
However, if the concentration is lowered further (^0.1 ygP/L), desorption
of the NaOH-P fraction occurs. Desorption from the HC1-P fraction is
insignificant. The NaOH-P corresponds closely to the non-apatite inorganic
P and the HC1-P to apatite P in the sediment. The shape of the desorption
curve will vary between sediments, leading to differences in the
relative proportions of resin-P and NaOH-P. Furthermore, the phosphorus
concentrations corresponding to desorption of resin-P (point B) and
NaOH-P (point A) are difficult to measure and are only approximate
concentrations. Based on the relatively low phosphorus concentration
corresponding to the desorption of resin-P, and the phosphorus
concentrations in Great Lakes waters, it seems likely that in situ
availability might correspond more closely to resin-P than to NaOH-P.
However, available inorganic P should not exceed NaOH-P.
II-8
-------
RESIN-P
NaOH-P
>HCI-P
PHOSPHATE IN SOLUTION
Fig. II-2, Hypothetical isotherm for inorganic P
adsorption-desorption by suspended
sediment illustrating the relationships
between apatite and non-apatite (NAIP)
and the inorganic P extracted as resin-P^
NaOH-P, and HC1-P. (A ~ 0.1 yg P/L;
B ~ 1 pg P/L)
II-9
-------
II-4. RESULTS AND DISCUSSION
Availability of Particulate P in Suspended Sediment
Available P in suspended sediments was measured as NaOH-P and
resin-P; NaOH-P apparently represents the maximum amount of available
inorganic P in suspended sediments, while resin-P may correspond more
closely to the amount expected to become available from large particles
with a short residence time in the lake water or for sediment suspended
in lake water containing significant levels of dissolved inorganic P.
Proportion of available inorganic P in suspended sediment
The availability of inorganic P in suspended sediment varied
appreciably among the tributaries (Table II-l). The group mean values
for NaOH-P (% of total particulate P) were 14% for the Nemadji, 19% for
the Genesee, and about 35% for the Grand, Maumee, and Menomonee samples.
In spite of the wide variations in suspended sediment concentrations
and time of sampling, the NaOH-P fraction for the samples from a given
tributary was fairly constant (c.v. = 5 to 37%). This suggests some
uniformity in the available P characteristics of sediments transported
in a given tributary under different conditions of season, discharge
and suspended sediment load.
Relationships between resin-P and NaOH-P
The amounts of NaOH-P and resin-P in the suspended sediments were
closely related (Table II-l); the group mean values for resin-P ranged
from 43 to 50% of the NaOH-P fraction. The resin-P represents a
"readily desorbed" fraction of the NaOH-P. The remaining NaOH-P
(NaOH-P minus resin-P) also can be desorbed if the solution inorganic
phosphorus concentration is sufficiently low. Solution inorganic P
concentration maintained in resin-soil suspension systems is
approximately 1 pg/L (10). However, complete desorption of the NaOH-P
apparently requires the solution inorganic P concentration to be below
the chemical detection limit, perhaps <0.1 pg/L (8). Apparently, for
the suspended tributary sediments, a solution concentration of about
1 pg/L resulted in desorption of about 50% of the NaOH-P (see Fig. II-2)
11-10
-------
Table II-l. Percentage of phosphorus in suspended sediments in available and
non-available fractions*
P as % of sediment
Tributary
Genes ee
Grand
Maumee
Menomonee
Nemadj i
n**
14
4
4
6
11
Resin-P
9
16
17
16
7
NaOH-P
19
37
34
37
14
total P
HC1-P
34
16
20
27
49
Coefficient of variation , %
Resin-P
60
48
34
30
34
NaOH-P
37
5
14
12
37
HC1-P
33
29
16
39
20
* NaOH-P + HC1-P = total inorganic P; resin-P is a part, of the P in the NaOH-P
fraction.
** Number of samples.
11-11
-------
Similarly, Sagher (8) found that 1/2 of the P desorbed from soils
in an algal-soil suspension was desorbed when the solution inorganic P
concentration had been reduced to approximately 1 yg/L. Based on these
phosphorus concentration-desorption relationships, the amounts of inorganic
P desorbed from suspended sediments in waters of the Great Lakes may
correspond more closely to resin-P than NaOH-P.
Available P-particle size relationships
The distribution of available P according to suspended sediment
particle size was investigated because available P might be concentrated
in the fine particulates and because the residence time in the lake
water column would be longer for fine than for coarse particulates.
For the grouped samples, the proportion (% of particulate P in size
fraction) of available P (NaOH-P or resin-P) in the three size fractions
(0.2 to 2, 2 to 20, >20 ym) was fairly constant (Table II-2). The
exceptions were the higher proportion of available P (resin-P or
NaOH-P) in the fine (0.2 to 2 ym) size fraction of the Grand and
Menomonee samples. Relatedly, in the 0.2 to 2 ym fraction, the resin-P
also represented a higher proportion of the NaOH-P in the Grand (75%)
and Menomonee (63%) than in the other size fractions or composite
sample (about 50%; Table II-1). In the Grand samples, this was related
to the high proportion of resin-P in the Grand I sample (Appendix II-B).
In the Menomonee, the higher ratio of resin-P/NaOH-P was found in 5 of 8
samples collected. The high proportion of resin-P to NaOH-P indicates
the inorganic P in these fractions would be released more readily than
in the other fractions. Apparently, the slope of the adsorption-desorption
isotherm is lower for these suspended sediments. This would result in
the desorption of a higher proportion of the NaOH-P at the solution
inorganic P concentration maintained in the resin-suspended sediment
system (see Fig. II-2).
The high proportion of NaOH-P in the 0.2 to 2 ym size fraction of
the Grand and Menomonee samples was accompanied by a decrease in the
proportion of organic P (Table II-2); the proportion of HC1-P in the
0.2 to 2 ym fraction was similar to the proportion in the other size
fractions. A high proportion of HC1-P was observed for the >20 ym size
fraction of the Genesee samples (Table II-2). This increase in HC1-P
was associated with a decrease in the proportion of organic-P.
In spite of the exceptions discussed above, the relative phosphorus
composition was similar for the different size fractions (Table II-2).
This similarity in composition indicates that the larger particles may
be composed in part of aggregates of smaller size particles. The
sediments were dispersed by shaking in water 12 to 18 hours prior to
particle size fractionation. The use of chemical or vigorous physical
dispersion techniques was avoided because the goal was to obtain
particle size-settling velocity information representative of the
suspended sediment transported to the Great Lakes. The harsh dispersion
techniques would bias the results toward a higher proportion of fine
11-12
-------
Table II-2. Distribution of phosphorus fractions among particle size fraction*
P fraction as % of total particulate P in size fraction
Tributary
Genesee**
Grand
Maumee
Menomonee
Nenadji
Genesee**
Grand
Maumee
Menomonee
Nemadji
Genesee**
Grand
Maumee
Menomonee
Nemadji
Genesee**
Grand
Maumee
Menomonee
Nemadji
0.2 to 2 pm
6
40
18
29
7
24
53
36
46
16
35
18
18
28
43
41
28
46
26
41
2 to 20 ym
Resin-P
9
16
17
15
7
NaOH-P
18
36
32
36
14
HC1-P
44
19
20
25
61
Total organic
38
46
48
39
25
>20 ym
5
17
14
16
7
14
34
32
37
16
58
17
25
26
51
P
28
49
43
37
33
Composite,
>0.2 urn
8
19
17
17
7
18
37
34
38
15
44
18
20
27
51
35
48
47
38
32
*Mean values for the samples collected (see Appendix I-A-1, Table 1-3). Note:
Because data was not obtained on all size fractions for some samples, the
composite values above may differ somewhat from values calculated from the
mean size distribution (Table 1-3) and the mean P distribution in the size
fraction (above).
**Samples from Avon sampling station.
11-13
-------
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11-14
------- An error occurred while trying to OCR this image.
-------
compared to the other samples (average of 650 yg/g). The high inorganic
P concentration in the Grand samples may reflect point source contributions
from the nearby urban area. The low total inorganic P concentrations
in the Genesee and Nemadji sediments (429 and 529 yg/g, respectively)
are associated with correspondingly low NaOH-P concentrations (114 and
162 yg/g; Appendix II-A-2).
Comparisons with other measurements
The results obtained in this investigation are in agreement with
available information from previous investigations. Bahnick (19) found
P release from Nemadji River sediment suspended in Lake Superior water
was about 50 yg P/g sediment. This value is in close agreement with
the average resin-P value (59 yg/g) found in this investigation
(Table II-3). The amount released corresponded to only 44% of the
NaOH-P (114 yg/g), probably because of the relatively high inorganic P
concentration in solution in the sediment-lake water laboratory system "
(>12 yg P/L).
In sediments from the Genesee Basin, ranges of 11 to 410 yg/g for
NaOH-P and 187 to 731 yg/g for HCl-P were reported (21). For streams
in northwestern New York draining into Lake Erie reported
average values of 253 yg/g for NaOH-P + CDB-P and 265 yg/g for HCl-P
were found ( 22). The corresponding values from this investigation
(Genesee) are 162 yg/g and 284 yg/g for NaOH-P and HCl-P, respectively.
The combined amounts of P extracted by the NaOH and CDB reagents (22)
should be approximately the same as P extracted by the NaOH reagent
in this investigation because of the wider sediment .'solution ratio used
here (8).
For eastern Michigan tributaries draining into Lake Erie, Logan
(22) found average values of 823 yg/g for NaOH-P + CDB-P and 163 yg/g
for HCl-P. This compares with the average values of 825 yg/g for
NaOH-P and 359 yg/g for HCl-P found in the Genesee samples (Table II-3).
The results of this investigation are also in agreement with results
obtained by Thomas and Williams (23) for stream and lake samples on
the Canadian side of the basin. For several streams, available P
(non-apatite inorganic P) ranged from 27 to 40% of total particulate
P (mean is 33%). This compares to the range of 14 to 37% for the
U.S. streams in this investigation (Table II-l). Similarly the
Canadian values for Lake Superior (14%) and Lake Erie (37%) samples
are in agreement with the corresponding tributary values (Nemadji and
Maumee, respectively) from this investigation. The higher Canadian
value for Lake Ontario (31 to 32%) as compared to the value for the
Genesee (19%) may reflect differences in the soils on the U.S. and
Canadian sides in this region.
11-16
-------
Available P loadings
Amounts of available inorganic P in suspended sediment expressed
as a proportion of sediment total P (Table II-l) or as the concentration
of P in the sediment (Table II-3) are not necessarily reflective of the
relative amounts of available P transported on a unit volume or unit
time basis (Table II-4). Differences between streams in suspended
sediment concentration or discharge are major factors in available P
loading rates. For example, because of a low average suspended sediment
concentration, the Grand ranked lowest among the five tributaries in
particulate available P/unit volume (yg P/L) even though the Grand River
ranked highest in available P concentration (yg P/g) in the suspended
sediment (Table II-4). However, the relative ranking for available P
concentration among the other four tributaries was the same on a volume
(yg/L) or sediment weight (yg/g) basis. The relatively high average
discharge rates for the Maumee, Grand and Genesee are major factors
in accounting for the relatively high annual loadings of available
particulate P for these tributaries. However, the relatively low
suspended sediment concentration in the Grand results in a lower
available particulate P loading rate than for the Maumee in spite
of the high discharge rate, and high concentration of available P in the
suspended sediment of the Grand.
The estimated annual tributary loadings of total particulate P (24)
and the average proportion of total P present as available P (Table II-l)
in the tributary sediments can be used to calculate the estimated annual
loading of available P in suspended sediments (Table II-4). These
values can be compared with the estimated dissolved P loadings (assumed
to be available) to evaluate the relative importance of dissolved and
particulate available P loadings. According to these estimates,
available particulate P ranges from 23 to 77% of the total available P
loading for the five tributaries. The low proportion in the Grand
(43%) is related to the low suspended sediment concentration, while
the low proportion in the Nemadji (23%) reflects the low P concentration
in the sediment and the low fraction of the sediment P present as
available P. In contrast, particulate available P in the Genesee
represents about 77% of the total available Ploading even though the
available P fraction is low (19% of total particulate P), due in part
to the high suspended sediment concentrations.
Based on P loadings (24) and availability of particulate P (%)
found in this investigation, about 50% of the U.S. tributary loading
of P to the Great Lakes is in available forms; about 50% of the
available P is particulate (suspended sediment) and 50% is dissolved.
The proportions are about the same for total P loading or the loading
from diffuse sources. This calculation assumes that the availability
of sediment P in the tributaries investigated is representative; because
no tributaries to Lake Huron were measured, the proportion of suspended
sediment P present as available P in Lake Huron tributaries was assumed
11-17
-------
Table I1-4. Comparison of dissolved and participate available P loadings In tributaries.
Available participate inorganic
Tributary
Cenesee*
Grand
Maumee
Henononee
Nemadjl
Discharge*
•'/sec
78
114
141
2.7
11
Suspended
sediment*
mg/L
2S9
19
283
138++*
312
Concentration
in sediment
ug/g
110
825
469
460
114
Concentration
on volume basis
Ug/L
28
16
132
64
36
P**
Of total
participate P
Z
19
37
34
37
14
Available P from diffuse sources***
Distribution
Annual
tonnes
97
202
1034
15
52
Loading
Z++
23
58
46
52
41
Dissolved
23
57
40
40
77t -
Paniculate
77
43
60
60
23
* Mean "historical" values (24).
** NaOH-P; measured in this investigation; concentration on a volume basis vaa calculated from the measured concentration in sediment
and the mean "historical" suspended sediment concentration.
*** Calculated from the dissolved and total particulate P loadings for 1975 (24) and the mean available P level (NaOB-P as Z of total
participate P) found for each tributary in this investigation (see column 5 above). Dissolved P Is considered to be completely
available.
+ Avon station samples only.
++ Expressed as X of the total P loading.
+++ Mean value during sampling intervals In this investigation.
t Based on unit area loading (24).
11-18
-------
to be about the same as that in Lake Michigan and Lake Erie tributaries
(about 35%). However, the proportion of available P contributed by P
in suspended sediments differs appreciably among tributaries, as shown
in Table II-4.
Availability of Particulate Inorganic P in Recessional Shoreline Soils
The recessional shoreline soil samples were characterized by a low
proportion of available P (resin-P or NaOH-P) and a high proportion
of HC1-P (Tables II-5 and II-6). Total particulate P concentration
ranges were 35 to 1086 pg P/g for size-fractionated samples and 39 to
513 pg P/g for composite samples. However, resin-P and NaOH-P
concentration ranges were 3 to 36 pg P/g and 1 to 33 pg P/g, respectively,
corresponding to 2 to 12% and 1 to 11% of the total particulate P.
For all recessional shoreline samples, HC1-P was the dominant fraction,
representing >68% of total particulate P concentration for the
composite samples.
The recessional shoreline soils exhibited no clearly distinguishable
trends with respect to size fraction (Table II-6); general uniformity
existed for all P fractions, especially in the percentage of available
particulate inorganic P (NaOH-P or resin-P). The highly siliceous
sand fraction (>20 pm) of the Lake Michigan shoreline samples was
extremely low in total P content (Table II-6).
The NaOH-P and resin-P fractions were in close agreement;
consistently higher NaOH-P values, as observed for the suspended
sediments, were not found. This uniformity is shown for all size
fractions except the sand fractions of samples 0-1, 0-3 and Sleeping
Bear 3-2 (Table II-6). The resin-P values were much higher than NaOH-P
for these samples. These differences are attributed to inadequate
separation of the soil from the resin during the analysis, and partial
extraction of additional soil inorganic P into the resin-Pi fraction
as the inorganic P was eluted from the resin by acid treatment. The
resin-P method requires the sand fraction to be presieved to exclude
particles >250 pm to allow subsequent separation of the resin from the
resin-soil mixture prior to elution of the resin with acid. If soil
particles (>250 pm) are retained with resin, the acid will extract P
from the soil particles, resulting in an overestimation of the resin-Pi
fraction. For samples containing appreciable amounts of particles
>250 pm—as the case with these soils—NaOH-P results were considered
more reliable estimates of particulate inorganic P,
For the non-fractionated or composited size-fractionated samples,
(Tables II-5 and II-6), available. P (NaOH-P) ranged from 1 to 16 pg
P/g, corresponding to 1 to 4% of the total P. The one exception was the
Peterson Park 1-2 composited sample (NaOH-P is 10% of total P). However,
this corresponds to only 6 pg P/g due to the low total P content of this
sample. A small variability in the NaOH-P concentration (pg P/g) can
result in a large percentage difference in NaOH-P for those samples
exhibiting extremely low total P concentrations.
11-19
-------
Table II-5. Inorganic phosphorus distribution in samples from recessional
shoreline soils along the Great Lakes
Phosphorus Distribution
Soil
Peterson Park
1-1
1-2
1-3
Leland
2-1
2-2
2-3
Sleeping Bear
3-1
3-2
3-3
3-4
0-1
0-3
0-6
0-7
Total P
NORTHEASTERN
283
70
85
282
326
339
39
81
20
471
SOUTHERN
342
351
445
513
NaOH-P HC1-P
LAKE
2
2
2
4
8
11
1
1
5
9
LAKE
2
2
5
4
,
Vg/ S
MICHIGAN SHORE
242
61
58
249
280
292
44
66
16
425
ERIE SHORE
292
320
387
412
NaOH-P
-------
Table II-6.
Inorganic phosphorus distribution in size-fractionated samples from
recessional shoreline soils along the Great Lakes
Soil No. and
fraction
\un
0-1
0.2-2
2-20
>20
>0.2
0-3
0.2-2
2-20
>20
>0.2
0-6
0.2-2
2-20
>20
>0.2
0-7
0.2-2
2-20
>20
>0.2
Sleeping
Bear 3-2
0.2-2
2-20
>20
>0.2
Peterson
Park 1-2
0.2-2
2-20
>20
>0.2
Soil In
fraction
1
72
27
—
1
63
35
—
1
65
• 34
: —
3
50
47
—
0.4
13
99.3
—
0
9
91
™—
Phosphorus
Total P
125
354
379
358
110
367
316
343
315
462
400
439
1086
536
423
499
174
496
64
66
—
329
35
61
Resin-P NaOH-P
W.1
IJg p/g
SOUTHERN LAKE
3
10
33
16
5
18
34
23
13
7
11
8
32
11
8
10
NORTHEASTERN
15
22
8
8
—
36
3
6
ERIE
NO
5
2
(4)
HD
17
2
(11)
7
4
5
4
10
5
3
4
LAKE
8
33
1
1
38
4
6
distribution*
HC1-P
SHORE
54
326
343
328
34
342
332
332
243
377
346
365
853
410
377
408
MICHIGAN
90
296
47
48
—
297
32
58
Resin-F
X
2
3
9
5
5 '
5
11
7
4
2
3
2
3
2
2
2
SHORE
9
4
12
12
—
11
9
10
NaOH-P
of Total
—
1
1
(1)
—
5
1
(3)
2
1
1
1
1
1
1
1
5
7
2
2
—
9
11
10
HC1-P
*
43
92
91
92
31
93
105
97
77
82
87
83
79
76
89
82
52
60
73
73
—
90
91
92
*Phosphorufi present as Resin-P, NaOB-P and HC1-P. Parenthetic >0.2 pm results baaed
on Incomplete data for size fractions.
ND indicates concentration was not distinguishable from the blank..
11-21
-------
The low NaOH-F levels in the recessional shoreline soils apparently
reflects the lack of external F inputs and soil weathering processes
which increase the NaOH-P levels in surface soils. The inorganic P
in these shoreline soils is apparently contained mainly in apatite,
as shown by the HC1-P values. Apatite P is considered to be unavailable.
11-22
-------
REFERENCES - PART II
1. Williams, J. D. H., J. M. Jaquet and R. L. Thomas. Forms of
Phosphorus in Surficial Sediments of Lake Erie. J. Fish.
Res. Bd. Canada 33:413-429, 1976.
2. Syers, J. K., R. F. Harris and D. E. Armstrong. Phosphate Chemistry in
Lake Sediments. J. Environ. Qual. 2:1-14, 1973.
3. Brown, E, J. , R. F. Harris and J. F. Koonce. Kinetics of Phosphate
Uptake by Aquatic Microorganisms: Deviations from a Simple .lichaelis-
Menton Equation. Limnol. Oceanogr. 23:26-34, 1978.
4. Bartsch, A. F. Algal assay procedure—bottle test. U.S. Environmental
Protection Agency, National Eutrophication Research Program. Corvallis,
Oregon, 1971.
5. Golternan, H. L., C. C. Bakels and J. J. Jakobs-Mogelin. Availability
of Mud Phosphates for the Growth of Algae. Verh. Internat. Verein.
Limnol. 17:467-479, 1969.
6. Cowen, W. F. and G. F. Lee. Phosphorus Availability in Particulate
Materials Transported by Urban Runoff. J. Water Pollution Control Fed.
48:580-591, 1976.
7. Sagher, A. Microbial Availability of Phosphorus in Lake Sediments.
M.S. Thesis, University of Wisconsin-Madison, 1974. 122 pp.
8. Sagher, A. Availability of Soil Runoff Phosphorus to Algae. Ph.D.
Thesis, University of Wisconsin-Madison, 1976. 176 pp.
9. Sagher, A., R. F. Harris and D. E. Armstrong. Availability of Sediment
Phosphorus to Microorganisms. Technical Report, Water Resources Center,
University of Wisconsin-Madison, 1975.
10. Schroeder, D. C. Phosphate Mobility in Rural Runoff. Ph.D. Thesis,
University of Wisconsin-Madison, 1976. 123 pp.
11. Wildung, R. E. and R. L. Schmidt. Phosphorus Release from Lake
Sediments. U.S. Environmental Protection Agency Report No. EPA-R3-73-
024, Ecological Research Series, 1973.
12. Huettl, P. J. , R. C. Wendt and R. B. Corey. Prediction of Algal-
Available Phosphorus in Runoff Suspensions. J. Environ. Qual. 8:130-
132, 1979.
11-23
-------
13. Rodel, M. G., D. E. Armstrong and R. F. Harris. Sorption and Hydrolysis
of Added Organic Phosphorus Compounds in Lake Sediments. Limnol.
Oceanogr. 22:415-422, 1977.
14. Weimer, W. C. Inositol Phosphate Esters in Lake Sediments. Ph.D.
Thesis, University of Wisconsin-Madison, 1973.
15. Murphy, J. and J. P. Riley. A Modified Single Solution Method for the
Determination of Phosphate in Natural Waters. Anal. Chim. Acta 27:31-
36, 1962.
16. Gales, M. E., E. C. Julian and R. C. Kroner. Method for Quantitative
Determination of Total Phosphorus in Water. J. Am. Water Works Assoc.
58:1363-1368, 1966.
17. Williams, J. D. H., J. K. Syers, R. F. Harris and D. E. Armstrong.
Fractionation of Inorganic Phosphate in Calcareous Lake Sediments. Soil
Sci. Soc. Amer. Proc. 35:250-255, 1971.
18. Cooke, I. J. and J. Hislop. Use of Anion Exchange Resin for the
Assessment of Available Soil Phosphate. Soil Sci. 84:308-312, 1963.
19. Bahnick, D. A. The Contribution of Red Clay Erosion to Orthophosphate
Loadings into Southwestern Lake Superior. J. Environ. Qual. 6:217-222,
1977.
20. Cowen, W. F. Available Phophorus in Urban Runoff and Lake Ontario
Tributary Waters. Ph.D. Thesis, University of Wisconsin-Madison,
1974. 295 pp.
21. Reddy, M. M. A Preliminary Report: Nutrients and Metals Transported by
Sediments Within the Genesee River Watershed, New York, U.S.A. PLUARG
Technical Report to Task C, International Joint Commission, Windsor,
Ontario, 1977.
22. Logan, T. J. Chemical Extraction as an Index of Bioavailability of
Phosphate in Lake Erie Basin Suspended Sediments. Final Report, Lake
Erie Wastewater Management Study. U.S. Array Corps of Engineers,
Buffalo, N.Y., 1978. 42 pp.
23. Pollution from Lake Use Activities Reference Group. Environmental
Management Strategy for the Great Lakes System. International Joint
Commission, Windsor, Ontario, Canada. 1978.
24. Sonzogni, W. C., T. J. Monteith, W. N. Bach and V. G. Hughes. United
States Great Lakes Tributary Loadings. PLUARG Technical Report to Task
D, Ann Arbor, Michigan, 1978. 187 pp.
11-24
-------
APPENDIX A. RECESSIONAL SHORELINE SOILS AND TRIBUTARY SEDIMENTS
Appendix II-A-1. Description of recessional shoreline Boil samples*
Sample
No.
01
03
06
A7
U/
1-1
1-2
1-3
2-1
2-2
2-3
3-1
3-2
3-3
3-4
Location
Ashtabula
Bratenahl
Vermilion
Huron
Leelanau Co.
(T32N.RllW.Sec. 29)
Leelanau Co.
(T32N.RllW,Sec.29)
Leelanau Co.
(T32N,RllW,Sec.29)
Bluff 1.6km north
of harbor
Bluff 1.6kin north
of harbor
Bluff 1.6km north
of harbor
T29N.R15W.Sec.25
T29N,R15W,Sec.25
T29N.R15W.Sec.25
T29N,R15W,Sec.25
Material
Southern Lake Erie Shore, Ohio
Till
Till
Till
Peterson Park, Michigan
Light brown sandy clay
Light brown clayey sand with
few pebbles
Light brown clayey sand with
few pebbles
Leland, Michigan
Light brown clay
Light brown clay
Brown and blue-gray clay
Sleeping Bear Dune, Michigan
Sand
Sand
Sand
Hard clay layer
Comments
Recession rate 30 to 90
Recession rate 30 to 90
Recession rate 30 to 90
Recession rate 30 to 90
Sampled 10m above beach
Sampled 15m above beach
Sampled 20m above beach
Sampled in active slump
above water.
Sampled 20m above water.
below noneroded portion
Sampled 30m above beach
Sampled 45m above beach
Sampled 60m above beach
Sampled 42m above beach
cm/yr
cm/yr
cm/yr
cm/yr
6m
4m
'Sampled 6/29/77 except samples 01,03,06 and 07 for which dates are unknown.
11-25
-------
Appendix II-A-2. Inorganic P distribution in size-fractionated suspended sediments
SAnpla Sediment
No. Friction
— pa —
I 0.2-2
2-20
>20
>0.2
III 0.2-2
2-20
>20
>0. 2
IV 0.2-2
2-20
>20
>0.2
V 0.2-2
2-20
>20
>0. 2
VI 0.2-2
2-20
>20
>0.2
VII 0.2-2
2-20
>20
>0.2
VIII 0.2-2
2-20
>20
>0.2
IX 0. 2-2
2-20
>20
>0.2
X 0.2-2
2-20
>0.2
XII 0. 2-2
2-20
>20
>0.2
XIV 0.2-2
2-20
>20
XI. 2
XV 0.2-2
2-20
>20
>0.2
XVI 0.2-2
2-20
>20
>0.2
2-20
>20
>0.2
I 0.2-2
2-20
>20
>0.2
II 0.2-2
2-20
>20
>0. 2
III 0.2-2
2-20
>20
>0.2
IV 0.2-2
2-20
>20
>0.2
V 0.2-2
2-20
>20
>0.2
VI 0.2-2
IX 0.2-2
2-20
X 0.2-2
2-20
>20
>0.2
PhoaDhorul dietribution
TPP 1
Reein-P NftOK-P HC1-P Re
•in-P
ug P/g »
CENESEB RIVER
656
1104
737
942
800
762
834
795
854
621
522
658
805
453
335
494
1271
1346
1314
1319
420
1816
1580
1070
689
714
665
694
846
671
944
749
809
560
562
1390
1249
1436
1340
770
630
419
609
720
595
332
529
757
603
383
560
564
923
1103
981
1023
1748
915
978
958
1018
915
978
958
2212
1606
1800
1784
129
4217
2609
1054
608
423
1968
827
1526
1360
1290
211
248
131
211
146
94
69
92
60
30
14
34
64
30
8
29
196
232
86
200
65
172
80
97
29
29
16
25
59
42
21
41
28
10
23
78
58
67
72
74
56
68
52
21
11
25
76
34
12
37
41
10
58
353
210
228
231
507
133
174
165
214
133
174
165
452
244
222
241
40
825
119
148
201
281
63
115
135
438
314
160
290
227
176
119
161
160
84
42
92
154
74
26
74
579
409
286
440
103
405
316
236
157
97
61
93
217
117
125
134
122
40
50
301
302
315
195
117
71
125
151
34
43
64
183
122
26
101
122
50
MENOMONEE
386
399
414
406
1055
279
345
300
306
279
345
300
1172
591
598
642
90
1755 '
1051
464
172
188
828
365
537
481
475
209
335
296
307
173
278
241
249
316
300
420
351
308
290
252
278
219
403
527
368
53
227
196
134
61
296
309
283
289
520
312
320
299
257
517
307
299
394
287
177
239
225
271
270
186
237
261
212
RIVER
234
278
257
263
290
360
381
377
404
360
381
377
360
372
410
397
32
463
408
136
221
200
446
160
357
272
281
32
22
18
22
18
12
8
12
7
5
3
5
8
7
2
6
15
17
7
15
15
9
8
9
4
4
2
4
7
6
2
5
3
2
4
4
6
4
5
9
13
11
7
4
3
5
10
6
3
7
7
—
—
38
19
23
23
29
15
18
17
21
15
18
17
20
14
12
14
31
20
—
—
20
35
10
34
4
8
10
NaO«-P
of TPP-
67
28
22
31
28
23
14
20
19
14
8
14
19
16
8
15
46
30
22
33
25
22
20
22
23
14
9
13
26
17
13
18
15
7
9
3^
24
21
23
25
17
21
21
6
13
12
24
20
7
18
22
—
—
42
36
42
40
60
30
35
31
30
30
35
31
53
37
33
36
70
42
40
44
28
44
42
44
35
35
37
HC1-P
Simple
No.
Sedlucnt
Fraction
Phosphorus distribution
TPP
Resln-P
HaOH-P
HCl-P
Resln-P
— in — ug fig 1
MAUMEE RIVEB
32
30
40
33
22
36
29
31
37
48
80
53
38
64
75
56
17
30
40
28
12
13
12
12
23
41
47
41
—
44
55
—
39
57
53
19
36
40
71
48
40
29
72
42
36
45
48
42
46
—
~
25
25
26
26
17
39
39
39
40
39
39
39
16
23
23
22
25
11
16
13
37
48
23
19
24
20
21
I
II
III
IV
I
II
III
IV
I
II
III
IV
v
VI
VII
VIII
IX
X
XI
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
2-20
'
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
>20
>0.2
2-20
>20
>0.2
0.2-2
2-20
0.2-20
0.2-2
2-20
>20
'0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
2905
1100
941
1785
726
1072
755
886
572
1821
2039
1215
2329
1561
1265
1707
1039
1902
1428
1503
4968
3571
2812
3832
1173
1738
2121
1810
1344
1974
2041
1889
4445
3435
978
775
633
816
936
608
600
679
701
931
741
806
685
689
647
983
1309
963
1095
1768
1310
834
694
598
708
812
998
848
913
898
893
814
883
848
671
471
652
884
472
462
809
653
222
263
396
191
208
91
197
88
223
120
140
244
234
143
213
849
400
386
464
541
372
392
246
276
240
256
403
458
252
360
402
49
71
85
65
41
25
26
29
67
49
54
57
25
19
27
57
156
47
73
99
81
74
47
33
51
106
90
65
90
67
85
69
78
47
33
12
30
103
50
24
92
1070
370
310
636
348
367
193
354
182
476
629
347
658
502
468
538
GRAND
698
564
487
543
2652
973
850
1349
443
769
755
707
600
• 719
729
702
1924
SEMADJI
34
108
70
81
46
50
54
116
76
151
100
98
50
73
125
151
126
244
245
245
131
64
51
78
256
244
198
239
161
170
140
163
126
66
86
85
159
122
132
149
619
252
313
402
187
210
195
198
68
345
323
201
288
282
302
291
RIVER
194
317
284
279
392
378
312
376
257
402
385
370
320
458
404
410
233
559
RIVER
140
459
347
475
430
420
462
436
437
286
392
381
468
504
416
354
619
428
401
445
350
412
311
442
270
371
402
5
476
393
314
388
425
420
194
417
22
20
28
22
26
19
12
22
15
12
6
12
10
15
11
12
82
21
27
31
9
10
—
10
21
16
11
14
30
23
12
19
57
9
5
9
8
4
4
4
4
10
5
7
7
4
3
4
6
12
5
7
6
6
9
7
6
7
13
9
8
10
7
10
8
9
6
5
3
5
12
11
5
11
NaOH-P
of TPP-
37
34
33
36
48
34
26
40
32
26
31
29
28
32
37
32
67
30
34
36
53
27
30
35
38
44
36
39
45
36
36
37
64
43
3
14
9
9
8
8
8
17
8
20
12
14
7
11
13
12
13
22
14
19
16
9
9
11
32
24
23
26
18
19
17
18
15
10
18
13
17
26
29
18
HCl-P
21
23
33
23
26
20
26
22
12
19
16
17
13
18
24
17
19
17
20
19
8
11
11 _
10
22
23
18
20
23
24
20
32
21
15
14
59
42
51
71
—
—
60
50
59
54
42
57
59
47
38
43
33
35
33
48
64
58
58
38
45
32
41
45
—
46
--
56
58
67
60
49
89
42
52
11-26
-------
PART III
AVAILABILITY OF NITROGEN IN SUSPENDED
AND BOTTOM SEDIMENTS
J. R. PERRY
D. E. ARMSTRONG
IH-i
-------
Abstract
Nitrogen availability was evaluated for size-fractionated suspended
sediments obtained from selected Great Lakes tributaries. Suspended sediment
samples were obtained near river mouths and separated by centrifugation and
quiescent gravity settling into 0.2 to 2, 2 to 20 and >20 pm size-fractions.
Nitrogen analyses were performed on the individual particulate fractions
to determine the amounts and proportions of the various forms of nitrogen.
The available nitrogen included readily available inorganic nitrogen,
(i.e., exchangeable ammonium, and nitrite and nitrate) and the acid
hydrolyzable portion of the organic nitrogen that is susceptible to
preferential mineralization. Available organic nitrogen in suspended
sediments was defined as the hydrolyzable ammonium, amino acid, and hexosamine
nitrogen.
The available nitrogen in the suspended sediments ranged from 5 to 21%
and 42 to 62% of the total nitrogen for the inorganic and hydrolyzable organic
nitrogen, respectively.
Higher concentrations of available nitrogen occurred in the fine
particulate fractions except for the Maumee River suspended sediment which
contained higher concentrations of available nitrogen in the sand fraction.
This was consistent with an increased proportion of organic matter in the
sand.
The annual available nitrogen loading for the rivers—from lowest to
highest—was Menomonee < Nemadji « Genesee < Grand « Maumee. Annual
loadings were strongly influenced by river discharge.
Ill-ii
-------
CONTENTS - PART III
Title Page Ill-i
Abstract Ill-ii
Contents Ill-ill
Tables ...... Ill-iv
III-l. Introduction III-l
III-2. Conclusions III-4
III-3. Methods and Procedures II1-5
Sample Collection III-5
Nitrogen Analyses . II1-5
III-4. Results and Discussion III-6
Availability of N in Suspended Sediments II1-6
Genesee River III-6
Grand River III-9
Maumee River , III-9
Menomonee River * III-ll
Nemadji River 111-12
Factors Controlling Particulate Available-fl
Concentrations in Tributary Waters 111-13
Annual Loadings of Available-N II1-15
References 111-17
Appendix III-A Nitrogen distribution in suspended sediments .... 111-21
Ill-ill
-------
TABLES
Number
*
III-l Mean concentrations of the different nitrogen forms in
size-fractionated suspended sediments III-7
III-2 Nitrogen distribution (mean values) in tributary suspended
sediment and water III-8
III-3 Concentrations of the different nitrogen forms in
individual composite (> 0.2 Urn) suspended sediment samples . 111-10
III-4 Comparison of dissolved and particulate available N
loadings 111-16
III-A-1 Nitrogen distribution in size-fractionated suspended
sediments of samples from selected rivers in the
Great Lakes Basin II1-21
IH-iv
-------
III-l. INTRODUCTION
Information on the amounts, forms and distribution of nitrogen compounds
associated with size-fractionated suspended sediments is lacking. However,
the status of nitrogen compounds has been investigated in bottom sediments (1-
6), soils (7-9) and wastewater systems (10,11). These systems are related
closely to the suspended sediment system and offer insight into evaluation of
the nitrogen status of suspended sediments.
The quantities of nitrogen in suspended sediments range between 0.02 and
10%, representing nitrogen from eroded subsoils and sewage outfalls,
respectively. Other nitrogen sources include precipitation, fertilizers,
septic tank effluent, runoff, nitrogen fixation, organic matter decomposition
and sediment release.
The type of nitrogen present depends on the nitrogen source, sediment
geochemistry, internal transformations and environmental conditions. Up to
50% of the organic nitrogen in soil is not characterized as being among known
compounds (8,12,13).
Available nitrogen is defined as that fraction of the total nitrogen that
is readily to moderately assimilable by either phytoplankton or macrophytes.
The most important of these are the inorganic nitrogen and simple hydrolyzable
organic compounds containing free amino or amide groups. The inorganic
nitrogen forms in solution (ammonium and nitrate)are considered directly
available, while organic forms are made available through conversion to
inorganic nitrogen (mineralization). The inorganic nitrogen compounds occur
as either fixed or exchangeable ammonium and nitrite or nitrate. Exchangeable
ammonium is adsorbed to particles, especially in alkaline systems. Fixed
ammonium is held within the lattices of clay minerals and is the only form of
inorganic nitrogen considered unavailable (14). Nitrite and nitrate are
associated with the anion exchange sites and water held in the interstitial
spaces of the particulates.
Naturally occurring organic nitrogen compounds are primarily in the form
of free and condensed amino acids, amino sugars, purines and pyrimidines and
comprise the major form of nitrogen associated with particulates in aqueous
systems. These compounds, with the exception of some of the refractory
components, are mineralized fairly rapidly and are considered to be available
sources of nitrogen in aquatic systems. In soils more than 95% of the
nitrogen is organically combined and from 1 to 3% of this is mineralized
during the growing season. Much (40%) of the organic nitrogen also is in the
form of amino acids, amino sugars and nucleic acids. These compounds have
been shown to undergo rapid mineralization when added to soils (15,16).
However, mineralization of soil organic nitrogen is retarded by association
with soil organic and mineral components.
Numerous attempts have been made to develop a nitrogen availability
index. However, the biological stability inherent in various nitrogen
III-l
-------
fractions still remains a matter of conjecture. This biological stability may
be due to the formation of lignoprotein complexes involving reaction of
carbonyl groups in lignin with amino groups in proteins. These complexes may
be highly resistant to mineralization (8,17). Organic nitrogen compounds are
also known to be adsorbed on and within clay minerals, thereby retarding
enzymatic hydrolysis (18-20). Also, inorganic ammonia and nitrite have been
shown to react with organic matter, resulting in conversion to unavailable
forms (21). However, these more recalcitrant nitrogen associations and
complexes may not exist for extended periods of time (17), and generally have
not been found in soil in appreciable amounts (22).
Some of the more accepted nitrogen availability indices involve
quantifying those selected nitrogen fractions which have been shown to be
preferentially mineralized during incubation experiments (14,23-25). It
should be noted, however, that the types of organic matter found to be readily
mineralized are highly variable (26). Consequently, implication of
availability for a specific nitrogen fraction is a relative distinction, and
differences in availability between different organic nitrogen fractions may
be only moderately significant.
The amino acid-N fraction is generally accepted as the fraction
preferentially mineralized during incubation; this has .been demonstrated for
soils and sediments. For example, evaluation of the changes in the
mineralizable N distribution in soils during incubation (24) and extensive
cultivation (14) indicated that the greatest nitrogen loss was associated with
decreases in amino acid-N and hydroxy amino acid-N. Similarly, greater
nitrogen losses were observed to occur in the nondistillable acid-soluble-N
(amino acid-N) fraction than that of other nitrogen fractions during
cultivation and cropping (7). Relatedly, it was concluded that nondistillable
acid soluble-N was decomposed to a greater extent than other fractions (27-
32).
In lake sediments, amino acid-N tends to be more abundant and hexosamine-
N is less abundant in eutrophic than in oligiotrophic lakes, apparently
because the sediment organic matter has undergone less microbial turnover in
eutrophic lakes as a result of lower dissolved oxygen concentrations. This
suggests that under favorable environmental conditions the amino acid-N
fraction is mineralized preferentially (1).
The data of Kemp and Mudrochova (3) suggest preferential mineralization
of amino acid nitrogen in Lake Ontario sediments. They observed varying
organic C:organic N ratios throughout the sediment profiles. The higher C:N
ratios occurred in horizons having very low sedimentation rates. A sharp
decline in amino acid-N was observed in these horizons. It was concluded that
nonhydrolyzable nitrogen is associated with sediments that have undergone
extensive humification. The nitrogen associated with humified organic matter
is known to be more biologically stable (8). Similarly, the proportion of
amino acid nitrogen to total nitrogen was found to decrease with age in most
soils (33).
Chichester (25) evaluated the nitrogen status of size-fractionated
organo-mineral soil particulates. It was found that greater biological
mineralization of organic-N occurred within the finer than the coarser
particulates. The amount of mineralizable N in each particle size fraction
III-2
-------
varied directly with the concentration of total N and inversely with the
corresponding C:N ratios. Higher C:N ratios resulted from greater amounts of
undecomposed plant residues in the coarser particulates than in the finer
particles. Nitrogen mineralization in the fine particulates was 3 to 4 times
greater than in the coarse particle.
III-3
-------
III-2. CONCLUSIONS
The available nitrogen, consisting of the inorganic nitrogen (except
fixed ammonium) and a portion of the hydrolyzable organic nitrogen, ranged
from 52 to 73% (mean values) of the total nitrogen in the suspended
sediments. The highest and lowest percentage of available nitrogen occurred
in the Maumee and Nemadji sediments, respectively. An intermediate percentage
(mean of 65 to 67%) of available nitrogen occurred in the Genesee, Grand and
Menomonee sediments. High proportions (mean of 16 to 21%) of the available
nitrogen consisted of available inorganic nitrogen in the Grand,Maumee and
Menomonee sediments. Conversely, the percentage inorganic nitrogen was lower
(mean of 5 to 10%) in the Genesee and Nemadji sediment.
Mean concentrations of available nitrogen were 8.3, 4.1, 3.7, 2.0 and 1.6
mg/g in the Grand, Maumee, Menomonee, Nemadji and Genesee sediments,
respectively. Those rivers containing high available nitrogen concentrations
(mg/g) also had high concentrations (mg/L) of dissolved inorganic nitrogen and
a large portion of the total sediment nitrogen occurred as available inorganic
nitrogen. The concentration of all forms of nitrogen usually increased during
low flow events. This resulted from an increased proportion of fine
particulates and an increased nitrogen concentration in the fine
particulates. The Nemadji and Genesee Rivers contained low concentrations
(mg/g) of all forms of nitrogen. This was related to the forested character
of the Nemadji Watershed and the high proportion of nitrogen-poor sand in the
Genesee sediment.
The annual available nitrogen loading from different sources was
calculated using historical values for suspended sediment concentrations,
discharge and dissolved nitrogen, and the measured concentrations of
particulate available nitrogen. The annual loads were 180, 220, 3,800, 6,500
and 44,200 metric tons for the Menomonee, Nemadji, Genesee, Grand and Maumee
Rivers. These values represent 66 to 96% of the total nitrogen load. The
annual available nitrogen loadings were influenced most strongly by discharge
rate and concentration of dissolved inorganic nitrogen. The dissolved
inorganic nitrogen contributed 55 to 91% of the annual available N load. The
low loadings in the Menomonee and Nemadji reflected the low discharge and
moderate concentration (mg/L) of particulate available nitrogen. The Genesee
and Grand Rivers had intermediate available nitrogen loads. This resulted from
high discharge even though the particulate available nitrogen concentration
(mg/L) was relatively low. The Maumee River exhibited the highest annual loading
which was due to a high discharge rate and a high particulate and dissolved
available nitrogen concentration (mg/L).
III-4
-------
III-3. METHODS AND PROCEDURES
Sample Collection
The suspended and bottom sediment samples collected from tributaries to
the Great Lakes and analyzed for available nitrogen are described in Appendix
I-A.
Nitrogen Analyses
Two chemical fractions were used as estimates of available nitrogen
(N). Inorganic-N (NH4+ + N03~ + N02~)-N, except fixed NH4+ - N, was
considered readily available. A fraction of the organic N, consisting of
hydrolyzable NH^-N, amino acid-N and hexosamine-N released into solution
during acid hydrolysis, was considered more available than the remaining
organic-N.
Inorganic-N (not including fixed NH/ ) was measured by a steam
distillation procedure (12). Total N was measured by a semimicro-Kjeldahl
method (12,34). Hydrolyzable forms of organic N were determined by Kjeldahl
steam distillation procedures (12). The procedure involved refluxing the
sample with HCL (6 ), reaction of the hydrolysate with ninhydrin to cleave
amino groups, and measurement of the NH4 liberated by steam distillation.
The ninhydrin reaction is specific for a-amino groups. The sum of
hydrolyzable NH/-N (AN) + amino acid-N (AAN) + hexosamine-N (HN) was measured
directly, i.e., the procedure converted these forms to NH4 - N. Non-
hydrolyzable N (NH) + unidentified hydrolyzable N (UHN) were calculated as the
difference between total organic-N and (NH^-N + AAN + HN). The total
hydrolyzable-N (THN) is [(NH4-N + AAN + HN) + UHN]. The (NH^-N + AAN + HN)
fraction is comparable to the nondlstillable and soluble N fraction described
by (28,30) which in turn is analogous to the amino acid-N fraction of
Stevenson (33). Distillable acid soluble N is comparable to (NH^-N).
III-5
-------
III-4. RESULTS AND DISCUSSION
Availability of N in Suspended Sediments
Nitrogen in suspended sediments is evaluated according to the following
relationships: 1. the concentrations of the different forms of nitrogen,
2. relative proportions of the nitrogen forms and 3. distribution of the
different forms of nitrogen in size-fractionated suspended sediments.
Genesee River
Relatively low, but variable concentrations of nitrogen were observed in
the Genesee River (Avon) suspended sediments (Table III-l). The mean
concentrations of inorganic N, (AN + AAN + HN) and total-N in the Avon
sediment were 0.25, 1.42 and 2.42 mg/g, respectively. The range of values for
sediment total-N was similar to values observed by Reddy (35) for bottom
sediments collected in Lake Ontario at the mouth of the Genesee River. In
contrast, the bottom sediment total N was more variable and substantially
higher in samples obtained throughout the Genesee Watershed (35). Values for
these samples agree with total N values for the suspended sediments from
tributaries to the Genesee. The inorganic N concentration (0.25 mg N/g) in
the Genesee-Avon sediments was low in comparison to sediments from tributaries
to the Genesee or the other rivers evaluated in this study. However, the
concentrations at the Avon station were more consistent with values observed
for bottom sediments than for soils. Relatedly, the mean dissolved inorganic—
N concentration of 1.1 mg/L (Table III-2) was also low and similar to values
reported for the Genesee River plume in Lake Ontario (36).
The mean concentrations of AN + AAN + HN for the Genesee-Avon sediments
(Table III-l) are lower than those observed for Lake Ontario bottom sediments
(3) or suspended sediments for Genesee River tributaries. Higher nitrogen
concentrations in the bottom sediments may result from the selective sorting
of nitrogen-rich finer particulates in the far-shore depositional areas. The
higher nitrogen concentrations in the suspended sediments may be related to
the high gradients and greater sediment heterogeneity in the Genesee
tributaries. A similar trend was observed by Reddy (37) for phosphorus
concentrations.
The proportion of nitrogen as (AN + AAN + HN)—with a mean of 59%—was
slightly higher for the Genesee than for the other river sediments (Table III-
2). This slightly elevated distribution was offset by a lower proportion of
inorganic^ (5%), thereby maintaining the (NHN + UHH) distribution (35%)
similar to those of the other river sediments. In comparison to the Avon
station, the Genesee tributary sediments had a slightly increased proportion
of organic N in the (AN + AAN + HN) fraction.
II1-6
-------
Table III-l. Mean concentrations of the different nitrogen forms in size-
fractionated suspended sediments
Sediment
size fraction
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
Suspended
sediment
%*
22
46
32
332
26
44
30
546
Particulate-N distribution
Inorganic (AN+AAN+HN)
0.78
0.17
0.14
0.
,25
2.73
0.50
0.34
0.
,57
GENESEI
(11)
(12)
(7)
(10)
(13)
(10)
(5)
(7)
- mg
4.76
0.84
1.18
1.42
17.11
3.80
2.19
4.73
Is.**
1 6
(68)
(61)
(58)
(59)
(80)
(74)
(32)
(59)
(NHN+UHN)
1.
0.
0.
0.
1.
0.
4.
2.
,62
40
,75
80
71
87
,31
86
(23)
(29)
(37)
(33)
(8)
(17)
(64)
(35)
Total-N
7.00
1.
37
2.04
2.
42
21.09
5.11
6.
8.
,77
08
MENOKONEE
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
31
34
35
138
42
44
14
171
21
45
34
34
34
51
15
211
3.08
1.
03
0.39
0.
1.
0.
1.
1.
7.
1.
1.
2.
0.
0.
0.
0.
80
93
36
50
17
59
00
48
29
82
19
40
38
(27)
(18)
(8)
(16)
I1AUMEE
(33)
(8)
(20)
(21)
GRAND
(44)
(8)
(16)
(18)
NEMADJI
(15)
(6)
(17)
(10)
4.82
3.17
3.01
3.11
2.05
2.94
4.52
3.13
6.74
6.94
5.37
6.74
2.12
2.41
1.36
1.73
(42)
(56)
(16)
(55)
(35)
(63)
(61)
(55)
(39)
(55)
(57)
(54)
(40)
(42)
(57)
(43)
4.
1.
1.
2.
2.
1.
2.
1.
6.
4.
2.
4.
2.
1.
0.
1.
95
80
70
01
23
44
15
55
07
82
89
21
54
81
77
87
(43)
(32)
(35)
(35)
(38)
(31)
(29)
(27)
(35)
(38)
(31)
(34)
(48)
(54)
(32)
(48)
11.40
5.
4.
5.
5.
4.
7.
5.
17.
12.
9.
12.
5.
3.
2.
3.
71
91
65
90
69
41
64
26
58
42
49
33
36
40
87
*Values for composite (>0.2 pm) fraction expressed in mg/L.
**Values in parentheses are percentages of total-N in size fraction.
III-7
-------
Table III-2. Nitrogen distribution (mean values) In tributary suspended sediment and water
Nitrogen distribution
Dissolved
Inorganic Inorganic*
I.I (0.6-1.5) 5 (2-10)
2.2 (1.3-2.8) 16 (7-19)
5.3 (0.8-10.0) 21 (5-29)
2.1 (0.7-3.7) 18 (6-22)
1.0 (0.4-2.3) 10 (6-20)
Partlculate assoclated-N
Hydrolyzable** Available*** Nonavallablet
GENESEE
59 (37-80) 67 (36-88) 33 (12-64)
MENOMONEE
55 (49-67) 65 (61-72) 35 (28-43)
MAUMEE
55 (44-58) 73 (63-93) 27 (27-37)
GRAND
54 (45-70) 66 (63-73) 34 (27-37)
NEMADJI
49 (37-59) 52 (51-70) 48 (30-53)
Total
0.24 (0.12-0.64)
0.57 (0.39-0.98)
0.56 (0.46-0.65)
1.25 (0.72-1.82)
0.39 (0.09-0.48)
* Includes NO^ , NO) and exchangeable NH*.
** Includes ammonium, amlno acid and hexosamlne nitrogen.
*** Includes hydrolyzable-N and (NOj+NO|)-N.
t Includes total-N minus avallable-N.
tt Expressed as I of total-N, except total-N which is I of suspended partlculates.
III-8
-------
Grand River
High concentrations of all forms of particulate-associated nitrogen were
found in the Grand River suspended sediments. The mean inorganic-N, (AN + AAN
+ HN) and total-N concentrations in the combined sediments were 2.3, 6.7 and
12.5 mg N/g, respectively (Table III-l). Similar values for the Grand River
have been reported (38,39). These very high concentrations are atypical for
most mineral soils, particularly the sandy soils common in the Grand
Watershed. The high values probably reflect the influence of urban point
sources (Grand Haven). Relatedly, the dissolved inorganic-N concentration
also was quite high, averaging 2.1 mg N/L (Table III-2). Most of particulate
inorganic N (86%) was in the form of (NC>2 + NOg^N. However, the
concentration of exchangeable NH--N was high (mean of 0.30 mg/L), compared
with previously reported values (38). This high concentration of exchangeable
NH^-N may also reflect the influence of point sources.
The distribution of the various nitrogen forms was essentially uniform
among the different Grand River samples (Table III-3). Hydrolyzable-N
averaged 54% of the total partlculate-N (Table III-2).. Most of the nitrogen
(48%) was present in the form of hydrolyzable amino acid-N and hexosamine-N
(data not shown). Amino acid-N (AAN) constituted most of the nitrogen in this
fraction and are considered to be a readily mineralizable form of organic-N,
particularly under aerobic conditions. The nonhydrolyzable-N and
unidentifiable hydrolyzable-N fractions accounted for 34% of the total-N and
are considered to be less available forms of nitrogen (Table III-2). The
readily available inorganic-N comprised 18% of the total-N.
The nitrogen distribution in the size-fractionated particulates varied
with type of nitrogen (Table III-l). The nitrogen concentration was highest
in the finer particulates, resulting from increased concentrations of
inorganic-N and (UHN + NHN). The concentration in the (NH^ - N + AAN + HN)
fraction was relatively uniform among the three size fractions.
Maumee River
Interpretation of the data from the Maumee sediments is somewhat
restricted due to the limited number of samples. However, some complementary
information is available (40).
The Maumee River sediments contained high mean concentrations of all
forms of nitrogen (Table III-l). The mean inorganic-N, (AN - AAN + HN) and
total-N concentrations were 1.2, 3.1 and 5.6 mg N/g, respectively. These high
concentrations are more consistent with values observed for bottom sediments
(1,3) than for soils. The inorganic-N is particularly high and variable and
occurred primarily in the form of (N0£ + NOgJ-N. Relatedly, the high sediment
(N0£ + NOo)-N concentrations were directly proportional to the dissolved
(NC>2 + NO.j)-N concentrations. The amount of inorganic-N in sediment
particularly (NC^ + NOo)-N was inversely proportional to the river flow rate
III-9
-------
Table III-3. Concentrations of the different nitrogen forms in individual composite
(>0.2 pm) suspended samples
Sample no.
I
III
IV
V
VI1"1'
VII
VIII
IX
X
XI
XII
XIV
XV
XVI
XVII
Composite
I
II
III
IV
XIft
VII
VIII
IX
X
Composite
I
II
III
IV
Composite
Itt
IItf
III
IV
V
Composite
I
II
III
IV
V++
VI
VII
VIII
IX
X
XI
Composite
Flow
rate
m^/sec
5.2
97
206
239
6.2
7.1
23
27
101
49
2.4
164
153
283
74
96
13.7
11.3
15.1
3.7
2.1
9.9
5.7
8.6
13.4
8.6
931
116
120
2572
389
41
28
391
359
161
221
*.—
43
—
40
34
—
—
106
64
124
45
65
Exchangeable
0.92
0.74
0.03 (2)
0.15 (8)
—
—
0.46 (15)
0.61 (10)
0.08 (3)
0.36 (8)
0.91 (7)
0.05 (3)
0.04 (3)
0.17 (9)
0.03 (2)
0.49 (8)
0.21
0.84 (16)
0.68 (17)
0.62 (14)
4.71 (48)
0.36 (7)
0.89 (14)
1.66 (19)
1.10 (19)
0.80 (16)
0.31
2.19
1.88 (29)
0.29 (5)
1.17 (21)
3.73 (22)
3.89 (21)
1.22 (7)
1.94 (21)
0.65 (6)
2.29 (18)
0.49
0.29 (12)
0.20 (10)
0.21 (11)
1.18 (24)
—
0.09 (6)
0.62 (20)
0.26 (7)
0.10 (11)
0.35 (7)
0.29 (10)
Hydrolyzable
GENESEE
1.92
1.18 (87)
0.82 (46)
4.43 (73)
7.72 (55)
0.75 (24)
2.38 (37)
2.05 (78)
2.91 (63)
10.52 (81)
1.41 (76)
0.93 (80)
1.43 (73)
1.10 (80)
2.70 (62)
MENOMONEE
_.
3.50 (65)
1.80 (46)
2.26 (52)
1.74 (18)
3.25 (67)
3.48 (54)
4.26 (49)
3.20 (54)
3.11 (55)
tfAUMEE
1.70 (84)ttt
2.87 (44)
3.38 (58)
3.13 (55)
GRAND
9.69 (57)
8.19 (45)
3.51 (49)
4.60 (51)
7.70 (70)
6.74 (54)
NEMADJI
__
1.04 (44)
0.95 (49)
0.78 (40)
1.71 (34)
5.61 (42)
0.89 (59)
1.77 (58)
2.10 (53)
0.33 (37)
2.11 (44)
1.25 (49)
Non
available**
ng N/g1^
—
0.16 (12)
0.88 (49)
—
—
2.02 (64)
3.38 (53)
0.52 (20)
1.40 (30)
1.67 (13)
0.41 (22)
0.20 (17)
0.37 (19)
0.26 (19)
1.02 (29)
1.78 (33)
1.70 (43)
1.60 (37)
3.84 (39)
1.35 (28)
2.24 (35)
3.05 (35)
2.32 (39)
2.01 (35)
__
0.15 (7)+tt
1.78 (27)
2.15 (37)
1.97 (35)
6.15 (36)
6.75 (37)
2.49 (35)
2.62 (29)
3.03 (27)
4.21 (34)
__
1.20 (50)
0.86 (44)
1.01 (52)
2.31 (46)
—
0.57 (38)
0.91 (30)
1.72 (43)
0.47 (53)
2.35 (49)
1.14 (45)
Available***
2.42
1.19 (88)
0.92 (51)
—
—
1.14 (36)
2.98 (47)
2.12 (80)
3.22 (70)
11.36 (87)
1.44 (78)
0.96 (83)
1.58 (81)
1.11 (81)
2.54 (71)
3.61 (67)
2.22 (57)
2.74 (63
6.00 (61)
3.50 (72)
4.17 (65)
5.69 (65)
3.60 (61)
3.65 (65)
__
1.88 (93)1"1"1'
4.71 (73)
3.65 (63)
4.10 (73)
10.76 (64)
11.48 (63)
4.70 (65)
6.45 (71)
8.01 (73)
8.28 (66)
__
1.18 (50)
1.09 (56)
0.92 (48)
2.69 (54)
—
0.94 (62)
2.14 (70)
2.24 (53)
0.41 (47)
2.40 (51)
2.00 (52)
Total
—
1.35
1.80
6.04
14.09
3.16
6.36
2.64
4.62
13.03
1.85
1.16
1.95
1.37
4.45
5.39
3.92
4.34
9.84
4.85
6.41
8.74
5.92
5.65
__
4.62f"
6.49
5.80
5.64
16.91
18.23
7.19
9.07
11.04
12.49
2.38
1.95
1.93
5.00
13.31
1.51
3.05
4.22
0.88
4.75
3.90
*Includes (ammonium + amino acid + hexosamine)-N.
**Includes (non hydrolyzable + unidentifiable hydrolyzable)-N.
***Includes hydrolyzable-N and (N02+N03)4.
tValues in parentheses are percentage of total-N.
ttO.2-20 Mm size fraction.
ttt2-20 pm size fraction.
111-10
-------
which, in turn, was related to the granuloraetric configuration (see Appendix
Table I-A-2 and Tables III-l and III-3). Apparently, as the river flow rate
decreased, the proportion of fine particulates increased and there was an
increase in the proportion of fine (nitrogen rich) particulates as well as an
increase in the nitrogen concentration in all particulate fractions.
Therefore, the flow rate had a qualitative influence on inorganic-N loading.
Probably the dynamics of the inorganic-N loading are influenced strongly by
the high proportion (50%) of tile drained agricultural land (40).
The distribution of the nitrogen species was similar to that of the Grand
sediments (Table III-2). The proportions of the total-N occurring as (AN +
AAN + HN), and inorganic-N were 55 and 21%, respectively. The less available
nitrogen (NHN and UHN) accounted for 28% of the total N.
The similarities in the distribution of the N species between the Grand
and Maumee sediments is of interest since the nature, amount and particle size
distribution of the sediments was so dissimilar. In the Maumee, the highest N
concentrtion was found in the sand fraction in the form of (AN + AAN + HN)
(Table III-l). Conversely, the clay fraction contained the lowest
concentration of total-N and (AN + AAN + HN). However, the proportion and
concentration of inorganic-N in this fraction were higher than in either the
silt or sand fractions. The concentration of sand-assqciated N was largely a
function of the concentration of AAN and HN, whereas the clay-associated N was
influenced more strongly by the concentration of inorganic-N.
Changes were observed in the concentrations of dissolved and particulate
inorganic-N in relation to varying flow rates (see Appendix Table I-A-2 and
Table III-3). During high flow periods, the particulate and dissolved
inorganic-N concentrations decreased; increased concentrations were observed
during low discharge periods. Thus, the possibility of an equilibrium
relationship between dissolved and particulate inorganic-N exists. The high
and low N concentrations may result from the selective erosion and transport
of particulates during different runoff events or possibly from the dilution-
concentration effect of different river discharge volumes.
Menomonee River
The Menomonee River sediments contained moderately high concentrations of
inorganic-N (AN + AAN + HN) and total-N (Table III-l). The respective mean
concentrations of 0.8, 3.1 and 5.7 mg/g were similar to values for the Maumee
River sediments. Little variability was observed in the concentrations
between composite samples and values are similar to those reported for the
Menomonee River (41).
The dissolved inorganic-N concentration was relatively uniform for all
events, averaging 2.2 ing N/L (Table III-2); the form was primarily (N02 +
N03)-N.
The distribution of the various N species was similar between samples
(Table III-3). One exception was a spring snowmelt event (Sample VI) which
contained a high proportion of N in the inorganic-N fraction and a low amount
of (AN + AAN + HN). This resulted from an increased proportion of inorganic-
III-ll
-------
N-rich silt and clay during a low flow event which contained high amounts of
organic matter. The proportion of the mean total particulate N in the
composite samples occurring as inorganic-N and (AN + AAN + HN) was 16 and 55%,
respectively (Table III-2). This is similar to the distribution in the Grand
and Maumee sediments.
Approximately 50% of the total-N was contained in the clay fraction
(Table III-l). The remaining N was distributed equally between silt and sand
fractions. The increased amount of N in the clay fraction resulted in part
from the high concentrations of inorganic-N and (UHN + NHN) in this
fraction. The (AN + AAN + HN) tended to be distributed equally between the
size separates.
There was a slight seasonal trend in the concentration and distribution
of N (Tables III-3 and Appendix I-A-1). During the summer months (Samples II,
III and IV) the concentrations of all forms of N were reduced equally. This
resulted from a decrease in the N concentration in the clay fraction and/or
decrease in the proportion of N-rich clay (Appendix III-A-1 and I-A-2). The
reduced amount of N may be more a reflection of the distribution and nature of
the particulates during different runoff events than a seasonal trend. The
Menomonee particulates contained both variable and high amounts of organic
matter which affected the particle size-distribution and concentrations of N.
Nemadji River
The Nemadji River generally contained low amounts of particulate-
associated N; however, higher N concentrations were observed during the late
fall and winter months when the amount of sand was low and the organic matter
content was higher (Samples V and VI; Table III-3; Appendix I-A-2). During
the spring snowmelt the proportion of (AN + AAN + HN) increased.
The mean concentrations of inorganic-N (AN + AAN + HN) and total-N in the
composite sediments were 0.4, 1.7 and 3.9 mg N/g (Table III-l). These are
similar to concentrations reported for Genesee sediments. Much lower total
Kjeldahl N concentrations (<0.05%) were reported for suspended and bottom
sediment «0.05%) from the Nemadji River and bottom sediment from the Lake
Superior entry (42).
The average dissolved-N concentration was 1 mg N/L (Table III-2). About
60% of the dissolved inorganic-N was present as (NO^ + NC^-N. The dissolved
(NOo + N02)-N concentration in Nemadji tributaries was reported to be 10 to
60% of that present in the Nemadji River (43).
The relative proportion of the various nitrogen forms between samples was
similar, except for an increase in the (AAN + HN) during the spring snowmelt
events (Samples VII, VIII, and IX, Table III-3). The mean inorganic-N and (AN
+ AAN + HN) concentrations were 10 and 49% of the total-flf (Table III-2).
These values are somewhat low in comparison to other river sediments. During
snowmelt events, (AN + AAN + HN) increased to 57% (Table III-3) of the total-N
as a result of decreases in the amounts of (UHN + NHN) and inorganic-N. This
coincided with the observation of brown patches of scum on the water
surface. During the winter a greater portion of total-N was distributed in
111-12
-------
the inorganic-N fraction. Most of the inorganic-N was in the form of NO-j-N,
probably indicating diffuse source inputs. The high amounts of total-N during
this period resulted from the increased organic matter content of the
sediment. This organic matter may have originated from bedload in view of the
reduced possibility of erosion of organic debris from frozen soils.
The highest concentration of all N forms occurred in the clay fraction
(Table III-l). The concentration of total-N was 1.4 times greater in the clay
than in the composite sediment. This was due to a higher concentration of
inorganic-N and (UHN + NHN) in the clay. Conversely, the sand contained the
lowest amount of total-N due to lower concentrations of (UHN + NHN). The silt
fraction contained low amounts of inorganic-N and moderate amounts of organic-
N. During winter, the particle size distribution changed substantially due to
lower discharge rates (Appendix I-A-2). This resulted in an increased
proportion of N-rich fine particulates (Appendix III-A-1). However, the flow
rates and suspended sediment concentrations during the winter were so low that
the amounts of N entering Lake Superior were reduced.
Factors Controlling Particulate Available N
Concentrations in Tributary Waters
The concentrations of particulate available-N in the tributaries to the
Great Lakes are influenced by 1. tributary discharge, 2. sediment delivery
ratio, 3. sediment particle size distribution and 4. the available-N
concentration and distribution among sediment particle size fractions.
Considerable variation exists in the importance of these factors for the
different tributaries. This section is concerned with the importance of these
factors in controlling the particulate available-N concentrations (amount/unit
volume) in the different tributaries.
In the Genesee, Menomonee and Nemadji Rivers (event response
tributaries), the sediment delivery ratio increases sharply with flow. The
total suspended solids (TSS) versus discharge slope values (Table 1-2) clearly
indicate this trend. The Maumee River is also an event response tributary,
but the slope value is much lower because the Maumee Watershed is large and a
runoff event occurring in one portion of the Watershed may be moderated
elsewhere by baseflow.
Generally, the sediment load for the Genesee, Menomonee, and Nemadji
Rivers consists mostly of suspended sediment rather than bedload from channel
erosion. In addition, the particle size distribution and the concentration of
available-N in the suspended sediment depends more on intensity and location
of rainfall in the Watershed, cover conditions or other factors, than on
tributary discharge rate. These factors are particularly apparent in the
Nemadji River. For example, during high flow periods (i.e., spring snowmelt,
intense runoff events), the available nitrogen concentration in sediment was
low, but because of the very high sediment concentration the particulate
available-N concentration in the water was quite high. Conversely, during low
discharge periods (i.e., winter, summer), the concentration (mg/g) of
particulate available-N increased. However, the available-N concentration was
reduced because the suspended sediment concentration was low. The fluctuating
111-13
-------
concentrations of suspended sediment (mg/L) and available-N (mg/g) during high
and low discharges, were moderating influences on the variability in
particulate available-N concentrations. As a result, the particulate
available-N concentrations tended to be related to discharge rate.
Variations in the particulate available-N concentration in the Menomonee
River was related closely to suspended sediment load. In turn, the sediment
load was related closely to discharge rate (Table 1-2). Therefore, these two
factors largely controlled the annual available-N load from the Menomonee
River—due to the uniform concentration (mg N/g) of available-N during
moderate to high discharges. The concentration was more variable during low
discharge events as a result of increased amounts of organic matter. However,
this was insignificant because these events accounted for a very small portion
of the annual available-N loading.
The proportional relationship between sediment concentration and
available-N concentration may be due in part to the homogeneous nature of the
suspended sediment. The particulates contained a high portion of organic
matter which may act as an aggregating agent. It is possible that the
fractionation scheme did not disperse the sediments completely, and the
instrinsic nature of the particulates may not be reflected in the three size
fractions obtained (Part I). As a result, the available-N distribution among
the size fractions was relatively uniform.
The particulate available-N concentration in the Genesee River was
variable and controlled by several factors, the most important being the
sediment size-distribution and concentration. Discharge rate was not an
important factor in determining the amount of available-N in the water column
because of the rather poor relationship between TSS and discharge (Table I-
2). Also, the high mean concentration of available-N in the clay, though
several times greater than in the silt and sand (Table III-l), was too
variable to be an indicator of amount of available-N in the water (Appendix
III-A-1). However, the amount of available N (mg/L) was significantly higher
during runoff events with high suspended sediment concentrations (Samples V,
XIV, XV, Table III-3). These events occurred generally during moderate to
high discharge periods. Concentrations of clay, silt and total sediment were
the controlling factors during periods of reduced available-N
concentrations. Generally, the concentration of available-N in the sediment
had a minor effect on particulate available-N concentration, in the water.
Lower concentrations of available-N resulted from reduced TSS and more
specifically from reduction in the amount of silt and clay. Though the
available-N concentration in the sediment (mg/g) varied considerably during
these events (Samples III and XVII), the actual amount of particulate
available-N in the water was controlled by the amount of suspended sediment.
Particulate available-N concentration in the Maumee River—like that of
Nemadji River—was primarily influenced by flow rate. Sediment concentration
was not proportional to flow rate especially at high flow rates. This is
indicated by the low value for TSS against discharge relationship (Table I-
2) Also, the sediment size-distribution was quite stable (Table 1-3) and the
concentration (mg/L) of particulate available-N was controlled almost
exclusively by silt and clay particulates which comprised some 86% of the
sediment. The sand fraction had little influence on available-N loadings,
even though it contained the highest available-N concentration (mg/g).
111-14
-------
Particulate avallable-N concentrations In the Grand River were relatively
constant* This was due to the degree of uniformity of avallable-N
distribution among clay, silt, and sand fractions, and the low variability in
suspended concentrations*
Annual Loadings of Available-Nitrogen
• The available-N fromdiffuse sources represented 66 to 96% of the total-N
entering the Great Lakes from the tributaries (Table III-4). Most of this
occurred in the form of dissolved-N, although the relative distribution
between tributaries was quite variable (55 to 91%). The impact of the
dissolved N was most apparent in the Maumee Watershed* A very high proportion
(91Z) of the annual available-N load occurred as dissolved N, probably as a
result of the extensive agricultural tile drainage systems In the Maumee
Watershed. In contrast, the Nemadji River had the lowest proportion of
dissolved N (55%), probably reflecting the heavily forested character of the
Watershed. The dissolved available-N fraction also was relatively significant
in the Greand and Genesee Rivers, but for different reasons. In the Genesee
River, this reflected the low available-N concentration (1.62 mg/g) In the
suspended sediment. In the Grand River, the low suspended sediment
concentration effectively reduced the relative significance of the particulate
available-N loading.
The relative loadings of particulate available-N from the different
tributaries were strongly influenced by wide differences in suspended sediment
concentration and tributary discharge rates. For example, the Maumee and
Menomonee Rivers both contained similar moderate concentrations of particulate
available-N. However, the annual particulate available-N load varied by a
factor of 100 (Maumee, 4,000 MT/yr; Menomonee, 39 MT/yr) because the discharge
from the Maumee River is 50 times greater than that of the Menomonee River.
Likewise, relatively low loadings of particulate avallable-N occurred from the
Nemadji River because discharge was very low, even though the suspended
sediment concentration was higher than that in the other rivers. The Grand
River particulate avallable-N concentration (mg/L) was low, but because of
high discharge, the annual available-N loading was moderately high.
The major factor controlling annual particulate available-N loading was
the tributary discharge. The Menomonee and Nemadji Rivers had low discharge
rates and consequently the annual particulate available-N loading was very
low. Conversely, high annual loads occurred in the Genesee, Grand and Maumee
Rivers which had high discharge rates.
111-15
-------
Table III-4. Comparison of dissolved and particulate available N loadings
Discharge***
Available Particulate N*
Suspended Total
Sediment*** Concentration particulate N
Available N from diffuse sources**
Annual Distribution
Loading Dissolved Particulate
mVsec
mg/L
mg/L mg/g
Tonnes %t
GENESEEtt
78
259
0.42
1.62
67
3,836 82
69
31
MENOMONEE
2.7
138
0.50
3.65
65
177 90
78
22
MAUMEE
141
283
1.16
4.10
73
44,175 96
91
GRAND
114
19
0.16
8.28
66
6,468 81
66
34
NEMADJI
11
312
0.62
2.00
52
222 66
55
45
*Includes particulate NO2+ N03+NHi,+ AAN + HN measured in this investigation. Concentration (Vol)
was calculated from the observed nitrogen concentration (wt) in the sediment and the mean histori-
cal suspended sediment concentration.
**Genesee, Grand and Maumee values are calculated from the dissolved and particulate diffuse N
loadings for 1975, reported by Sonzogni et al. (44) and the mean available N distribution
(available N as % of the total particulate N) found for each tributary in this investigation (see
column 6). Menomonee and Nemadji values based on unit area loadings (44). The amount of
dissolved organic N is considered, relatively insignificant.
***Mean historical values from Sonzogni et al. (44), except Menomonee River values which are from
Bannerman et al. (41).
tExpressed as a % of the diffuse total N
ttAvon station only
111-16
-------
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Carbon Distribution in Sediment Cores of Selected Wisconsin Lakes. J.
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3. Kemp, A. L. W. and A. Mudrochova. Distribution and Forms of Nitrogen in
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4. Chen, R. L. and D. R. Keeney. Nitrogen Transformation in Sediments as
Affected by Chemical Amendments. Water Resources Bulletin 9:1136-1144,
1973.
5. Keeney, D. R. Protocol for Evaluating the Nitrogen Status of Lake
Sediments. U.S. EPA 660/3-73-024, 1974.
6. Isirimah, N. 0., D. R. Keeney and E. H. Dettmann. Nitrogen Cycling in
Lake Wingra. J. Environ. Qual. 5:182-188, 1976.
7. Porter, L. K., B. A. Stewart and H. J. Haas. Effects of Long-time
Cropping on Hydrolyzable Organic Nitrogen Fractions in Some Great Plains
Soils. Soil Sci. Soc. Amer. Proc. 28:368-360, 1964.
8. Bremner, J. M. Nitrogenous Compounds. In: Methods of Soil Analyses,
Part 2. C. A. Black (ed.). Agronomy 9:1324-1345, 1965.
9. Porter, L. K. Nitrogen Transfer in Ecosystems. In: Soil Biochemistry,
Vol. 4, (eds. E. A. Paul and A. D. McLaren). Marcel Dekker, Inc.,
New York, N.Y., 1975.
10. Ryan, J. A., D. R. Keeney and L. M. Walsh. Nitrogen Transformations and
Availability of an Anaerobically Digested Sewage Sludge in Soil. J.
Environ. Qual. 2:289-293, 1973.
11. U.S. Environmental Protection Agency. Process Design Manual for Nitrogen
Control. Technology Transfer Series, 1975.
12. Bremner, J. M. Organic Forms of Nitrogen. In: Methods of Soil
Analyses, Monograph No. 9. Am. Soc. Agron., Madison, Wis. 1965.
111-17
-------
13. Greenland, D. J. Changes In the Nitrogen Status and Physical Condition
of Soils Under Pastures, with Special Reference to the Maintenance of the
Fertility of Australian Soils Used for Growing Wheat. Soils and
Fertilizers 34:237-251, 1971.
14. Keeney, D. R. and J. M. Bremner. Effect of Cultivation on the Nitrogen
Distribution in Soils. Soil Sci. Soc. Amer. Proc. 28:653-656, 1964.
15. Bremner, J. M. and K. Shaw. Studies on the Estimation and Decomposition
of Amino Sugars in Soil. J. Agric. Sci. 44:152-159, 1954.
16. Bremner, J. M. and K. Shaw. The Mineralization of Some Nitrogenous
Materials in Soil. J. Sci. Food Agri. 8:341-347, 1957.
17. Estermann, E. F., G. H. Peterson and A. D. McLaren. Digestion of Clay-
Protein, Lignin-Protein and Silica-Protein Complexes by Enzymes and
Bacteria. Soil Sci. Soc. Amer. Proc. 23:31-36, 1959.
18. Goring, C. A. and W. V. Bartholomew. Microbial Products and Soil Organic
Matter: III. Adsorption of Carbohydrate Phosphates by Clays. Soil Sci.
Soc. Amer. Proc. 15:189-194, 1950.
19. Armstrong, D. E. and G. Chesters. Properties of Protein-Bentonite
Complexes as Influenced by Equilibration Conditions. Soil Sci. 98:39-52,
1964.
20. McLaren, A. D. and G. H. Peterson. Physcial Chemistry and Biological
Chemistry of Clay Mineral-Organic Nitrogen Complexes. In: Soil Nitrogen
(eds. W. N. Bartholomew and F. E. Clark). Am. Soc. Agron., Madison,
Wis., 1965.
21. Burge W. D. and F. E. Broadbent. Fixation of Ammonia by Organic Soil.
Soil Sci. Soc. Amer. Proc. 25:189-204, 1961.
22. Jenkinson, D. S. and G. Tinsley. A Comparison of the Ligno-Protein
Isolated from a Mineral Soil and from a Straw Compost. Royal Dublin Soc.
Sci. Proc. IA:141-148, 1960.
23. Boswell, T. C., A. C. Richer and L. E. Casida, Jr. Available Soil
Nitrogen Measurement by Microbiological Techniques and Chemical
Methods. Soil Sci. Soc. Amer. Proc. 26:254-257, 1962.
24. Keeney, D. R. and J. M. Bremner. Characterization of Mineralizable
Nitrogen in Soils. Soil Sci. Soc. Amer. Proc. 30:714-718, 1966.
25. Chichester, F. W. Nitrogen in Soil Organo-mineral Sedimentation
Fractions. Soil Sci. 107:356-363, 1969.
26. Jenkinson, D. S. In: The Use of Isotopes in Soil Organic Matter
Studies. FAO/IAEA Tech. Meeting, Brunswick-Volkenrode, Germany, 1963.
Pergamon Press, Oxford, U.K., 1966, pp. 187-197.
111-18
-------
27. Freney, J. R. and J. R. Simpson. The Mineralization of Nitrogen from
Organic Fractions in Soil. Soil Biol. and Biochem. 1:241-251, 1969.
28. Simpson, J. R. and J. R. Freney. The Fate of Labelled Mineral Nitrogen
After Addition of Three Pasture Soils of Different Organic flatter
Contents. Aust. J. Agric. Research 18:613-623, 1967.
29. Moore, A. W. and J. S. Russell. Relative Constance of Soil Nitrogen
Fractions with Varying Total Soil Nitrogen Fractions with Varying Total
Soil Nitrogen. Trans. Ninth I'national Congress of Soil Sci., Vol. 2.
American Elsevier Publ. Co. New York, N.Y. 1968.
30. Stewart, B. A., D. D. Johnson and L. K. Porter. The Availability of
Fertilizer Nitrogen Immobilized During Decomposition of Straw. Soil Sci,
Soc. Amer. Proc. 27:656-659, 1963.
31. Stevenson, F. J. Effect of Some Long-Time Rotations on Amino Acid
Composition of the Soil. Soil Sci. Soc. Amer. Proc. 20:204-208, 1956.
32. Chu, J. P-H. and R. Knowles. Mineralization of Immobilization of
Nitrogen in Bacterial Cells and in Certain Soil Organic Fractions. Soil
Sci. Soc. Amer. Proc. 30:210-213, 1966.
33. Stevenson, F. J. Distribution of the Forms of Nitrogen in Some Soil
Profiles. Soil Sci. Soc. Amer. Proc. 21:283-287, 1957.
34. Bremner, J. M. and K. Shaw. Denitrification in Soil: I. Methods of
Investigation. J. Agr. Sci. 51:22-39, 1958.
35. Reddy, M. M. A Preliminary Report: Nutrients and Metals Transported by
Sediments Within the Genesee River Watershed, New York. Pollution from
Land Use Activities Reference Group (Task C), International Joint
Commission, Windsor, Ontario, 1976.
36. Wyeth, R. K. and J. Ploscyca. Effect of Genessee River Discharge and
Wind-Induced Resuspension on the Nearshore Area of Lake Ontario. Report
to PLUARG, International Joint Commission by the Great Lakes Laboratory
SUNY College at Buffalo, New York, on EPA grant RE-802706. 1976.
37. Reddy, M. M. Personal Communication. Division of Laboratories and
Research, New York State Department of Health, Albany, N.Y. 1976.
38. Eadie, B. J. The Effect of the Grand River Spring Runoff on Lake
Michigan PLUARG Task D, Subactivity 3-1, Draft Report. 85 pp. 1976.
39. U.S. Geological Survey. Water Data Report MI-75-1. Water Resources
Center, University of Michigan. 1975.
40. Logan, T. J. CHemical Extraction as an Index of Bioavailability of
Phosphate in Lake Erie Basin Suspended Sediments. Final Project Report,
Lake Erie Watershed Management Study, U.S. Army Corps of Engineers,
Buffalo District, Buffalo, N.Y., 1978. 42 pp.
111-19
-------
41. Bannerman, R., J. Konrad and D. Becker. Effect of Menomonee River Inputs
on Lake Michigan During Peak Flow. Wisconsin Dept. of Natural Resources,
Madison, Wis. 1977.
42. Bahnick, D. A. Chemical Effects of Red Clay on Western Lake Superior.
Center for Lake Superior Environmental Studies, University of Wiscosin-
Superior. 1975.
43. Swenson, W., L. Brooke and P. DeVare. Report on the Measurement of the
Effects of Erosion Control on the Aquatic Life in the Nemadji River and
its Tributaries. In: Red Clay Project Annual Report, U.S. EPA, 1977.
44. Sonzogni, W. C., T. J. Monteith, W. N. Back and V. G. Hughes. United
States Great Lakes Tributary Loadings. PLUARG Technical Reort to Task D,
Ann Arbor, Michigan, 1978. 187 pp.
111-20
-------
APPENDIX III-A. NITROGEN DISTRIBUTION IN SUSPENDED SEDIMENTS
Saiiple
No.
I
III
IV
V
VI
VII
IX
X
XI
XII
XIV
Sediment
size
dit.«>
0 2-2
2-20
> 20
diss
0.2-2
2-20
•> 20
diss
02-2
2-20
-20
>0.2
diss
0.2-2
2-20
>20
>0 2
0 2-2
2-20
0.2-20
diss
0.2-2
2-20
-20
>0.2
?%
2-20
>20
>0.2
diss
0.2-2
2-20
> 20
>0.2
diss
0.2-2
2-20
>20
diss
0 2-2
2-20
>20
>0.2
diss
0.2-2
2-20
>20
>0.2
diss
0.2-2
>20
>0.2
Excha
rog/p.
0 51
0 14
0 16
0.20
1 01
0.11
0.11
0.02
0 05
0 02
0.02
—
0 11
0 02
0 02
0.05
0 45
—
—
—
1.80
—
—
—
0
0.02
0
0.07
—
0
0
0 06
0.01
—
0 03
0
0
0
0
0.04
0 02
—
0
0.08
0.09
0 07
—
0
0.02
0.02
rafi/L
0
LE
0 14
0 0 j2
0 OL 0 02
0 01
- 0.11
0 01
0 01
- 0 OL
0 OL
0 01
N GL
o
0 CJ
0 15
0 13
n 17
0.03
0
0 01
0 01
(CON I 'MTU)
1 26
0 02
0.0}
0
0 02
0 01
0 01
0.02
-o ni
0
0 01
0 01
1 38
1 J7
0 50
0.93
3 12
1 OS
0 4i
i. 93
0 95
0 46
1 10
0 21
0 29
0 LI
0 61
0 24
0 09
0 0;
0 67
0 13
0 19
0 99
1 65
1.32
0 66
1 16
3 25
1 62
1 22
2 22
1 40
0 66
1 37
ta!
0 25
0 36
0 15
0 76
0 25
0 13
0 13
0 77
0 18
0 27
1 22
MCVJMONFI RIVt-R
1 55
0 27
0 82
10 84
2.29
4 43
—
11 ?0
"•-38
1 12
7, 72
0 96
0 73
0 75
16.88
0 15
2.38
—
5.22
1 07
1 19
4.; 9
1 56
2.34
2.91
—
53.51
6 88
4 13
10 52
—
2. 79
0 43
1.41
0 28
0 06
n 47
0 05
0 02
0 07
—
0 06
0 02
'0 01
0 Ot}
0 07
0 03
0 10
0 27
0 01
C. 39
—
3 50
1 33
1,26
0 61
0.19
0 34
1.14
—
0.49
0 30
0 15
0 94
—
0.35
0.06
0.67
2.19
1 79
I 80
14.0
3 30
6 04
14 77
10 05
16 n
14 09
r t
1 7S
1 11.
j If,
—
28 76
1 10
6 36
C 75
1 'tS
1.40
7 30
3.55
3 18
4 62
—
62 22
7.?0
5 70
13 03
—
3 90
0 63
1.85
0 40
0 40
1 . 04
0 07
'I 03 II
0 iO
(1 OS
n o"i
0 05 HI
0 16
n.i'
0 05 IV
0.46
_
0 46
0 08
0 69
VI
—
4 53
1 82
1 48
0 94
0 42
0 46
2 16 VII!
—
0 60
0 34
0 23
1 17 IX
—
0 50
0 08
0.38
X
0.2-2
2- 2C
;n
diss
0 2-2
?-?0
20
C 2
diss
02?
?;;°
_*J
diss
0 2-2
2-20
2U
0.2
di-,-3
0 2-2
2-20
0 2-20
n 2-2
2_1Q
>0 2
(Hss
0 2-2
2-20
70
0 2
djss
0 2-2
2-20
-20
0 2
0 2-2
2-20
-20
'0 2
0 17
0 (16
0 04
fi 31
0 31
0 27
0 73
—
0 40
0.13
0 37
1 00
0 10
0 fH
0 14
—
0 24
1.29
0 45
0 64
0 05
0 05
0 11
0.67
0 13
0 08
0 20
—
0 39
0 14
0 07
0 23
] .23
0,46
0 57
0. 70
C 01
0 "1
0 01
''
0 39
0 14
0 93
0 05
0 22
0 2^
0 04
0 02
O.C3
0 Cl
• 0 01
'0 01
0 01
2.03
'0.01
' 0 01
0 0)
0 01
0 01
n CM
0 01
0,23
<0 01
•0 01
0 01
0 01
0
^0 01
'0 01
fO 01
0 0]
0.03
0 02
0 02
0 07
0 51
0 IS
1 11
'
0 53
n os
0 08
0.11
__
1 Ot
0 12
"'
—
3.09
0 63
0 03
0 48
4 26
4 25
4 !6
1 79
0 07
0 O"7
0 ^5
—
0 35
0 10
0 18
0 69
2 17
1 09
0 50
1 43
0 84
0 11
0 41
0 40
0 02
0 02
0 T>
1 05
0 01
0 01
0 02
0 03
0 £8
0 10
0 02
' I:L
1 40
0 02
0 01
0 01
0 03
0 91
0 03
-0 01
0 03
0 02
' 0 01
0 01
0 03
2 52
0 02
<0 01
'0 01
9 02
1 10
n 03
0.01
•0 01
0 04:
1 [jg
0 92
- o 01
1 01
0 05
__
—
"
15 16
2 80
2 Si
j 50
—
2 11
1 52
93
—
1.60
1 69
2 54
2 26
—
0 64
6 74
1 74
5 09
3 20
2 se
3 25
—
5 ?3
2 38
3 49
3 4 J
5 60
3 81
3 97
4 26
3 04
j !6
3 32
j 20
—
__
0 26
0 26
0 51!
1 07
—
0 20
0 24
1.
—
0 01
0 03
0 10
0 14
—
"0 01
a 01
0 01
0 04
Oil
0 10
0 25
—
0 02
0 02
0 05
0 09
—
0 07
0 04
0 02
0 13
0 07
0 12
0 09
0 28
__
—
"
33 25
4 41
4 46
5.39
—
6 84
2 33
3
—
5 09
3 23
4 65
4 34
__
fl.77
14.62
9 84
10.95
4. 24
3 99
4.85
—
9 24
3 83
5 97
6 41
—
10 97
7 50
6 82
3.74
6.93
5 64
5 30
5 C6
__
"
0.57
0 41
0.6S
1 65
0 66
0 36
9 ^i
—
0.03
0 35
0 19
0 26
—
0 06
0 16
0 22
0 10
0 14
n 14
0 38
—
0 06
n 04
0.06
0 18
—
0 14
0 OS
0 C2
0 25
0 16
0 21
0 14
(1 51
111-21
-------
Table III-A-1 (continued)
Nitrogen dlctrlbutlon
Sedlnent
al2* Exchangeable
Saaple fraction NH,
No. vw «s7g rng/L
I dlss
0.2-2
2-20
>20
>0.2
II diss
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
IV dias
0.2-2
2-20
>20
>0.2
0.09
0.05
0.04
0.07
1.13
0.08
2.83
0.69
0
0.07
0.14
0.04
_
0.03
0.02
0.03
0.02
HAUME
o
0.01
0.01
<0.01
0.02
0.35
0.07
<0.01
0.01
0.08
0
<0.01
<0.01
<0.01
0.07
<0.01
<0.01
<0.01
0.01
NO, + NO
•g/i W/1
I BIVBR
0.50
0.05
0.19
0.24
2.66
0.18
1.49
1.50
2.70
0.87
1.12
1.84
0.60
0.12
0.16
0.27
0.82
0.05
0.01
0.01
0.06
6. 06
0.17
0.01
<0.01
0.18
8.82
0.09
0.02
0.01
0.12
3.92
0.05
0.01
0.01
0.07
Hydroly table*
•g/g «g/L
-
__
1.70
—
1.38
3.81
4.58
2.87
2.70
3.30
4.40
3.38
-
0.09
—
0.05
0.09
0.04
0.18
0.20
0.37
0.28
0.85
Total Sasple
•g/g ng/I. No.
~
7.10
2.03
—
5.45
6.75
7.31
6.49
5.16
5.29
7.51
5.80
GRAND RIVER
I dlss
0.2-2
2-20
>20
>0.2
II dlss
0.2-2
2-20
>20
>0.2
<20
III disa
0.2-2
2-20
>20
>0.2
IV dlaa
2-20
>20
>0.2
V dlss
0. 2-2
2-20
>20
>0.2
—
13.45
0.32
0.32
2.66
—
1.73
0.16
1.13
0.61
0.60
—
0
0
0.03
0.03
—
0
0.07
0.03
0.09
—
0.47
0.33
0.06
0.34
0.53
0.07
<0.01
0.01
0.06
0.56
0.01
<0.01
<0.01
0.01
0.01
0.35
0
0
0.01
0.01
0.07
0
<0.01
<0.01
<0.01
0
<0.01
<0.01
<0.01
0.01
—
2.92
0.76
0.51
1.07
—
9.09
1.26
3.04
3.26
3.29
—
5.49
0.32
0.26
1.19
—
4. 77
1.55
9.85
1.85
—
0
0.22
1.16
0.31
0.21
0.02
0.01
0.01
0.04
0.42
0.04
0.02
<0.01
0.06
0.06
3.36
0.04
0.01
<0.01
0.05
3.22
0.04
0.03
0.02
0.09
1.96
0
<0.01
0.01
0.01
—
21.84
5.76
6.60
9.69
—
7.34
8.56
—
—
8.19
—
1.14
3.20
4.70
3.51
—
2. 40
5.10
4.81
4.60
—
1.00
12,10
7.70
0
0.12
0.06
0.12
0.29
—
0.03
0.11
—
0.14
—
0.01
0.05
0.08
0.13
—
0.02
0.10
0.11
0.23
—
0.01
0.17
-0.18
—
30.22
18.41
12.66
16.91
—
33.68
13.03
—
—
18.23
—
10.06
6.22
6.86
7.19
—
9. 34
9.34
8.69
9.07
—
2.94
15.97
11.04
-
0.45
0.11
—
— Ill
0.18
0.15
0.07
0.40
IV
0.39
0.59
0.49
1.47
V
—
0.16
0.18
0.23 VI
0.61
—
0,15
0.16 VII
—
—
0.31
—
0.07 VIII
0.10
0.12
0.29
—
0.07 IX
0.19
0.19
0.45
—
0.03 X
0.22
0.25
XI
Sedlsme
size
fraction
diaa
0.2-2
2-20
>20
>0.2
0.2-2
2-20
>20
>0.2
dlss
0.2-2
2-20
>20
>0.2
diss
0.2-2
2-20
>20
>0.2
diss
0.2-2
2-20
0.2-20
diss
0.2-2
2-20
0.2-20
dias
0.2-2
2-20
>20
>0.2
dias
0.2-2
2-20
'20
>0.2
dias
0.2-2
2-20
>20
>0.2
dias
0.2-2
2-20
>20
>0.2
disa
0.2-2
2-20
>20
>0.2
Exchangeable
•g/'g «g/L
0.04
0.16
0.05
0.11
0.43
0.04
0.16
0.15
0.09
0.03
0.04
0.06
0.22
0.02
0.02
0.07
0.47
0.02
0.20
—
0
—
—
—
0.03
0.05
0.03
0.04
—
0.08
0.14
0.86
0.25
0.30
0.05
0.01
0.12
0.01
0.02
0.01
0.02
__
0.01
0.01
0.01
0.06
0 18
<0.01
0.01
<0.01
0.01
0.06
0 01
0.02
0.09
<0.01
<0.01
<0.01
0.01
0.98
0.01
<0.01
<0.01
0.01
0.28
0.01
<0.01
0.01
0.07
0
—
0.07
0.01
0.01
0.01
0.02
0.14
<0.01
0.01
0.02
0.03
0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
0.01
0.49
0.05
<0.01
<0.01
0.05
Nitrogen distribution
ogt'g
NO
Hydrolyzable*
ng/g «g/L
Total
•g/g ma/I,
NEMAPJI RIVER
ft Tl
0.61
0.29
0.19
0.38
0.43
0.02
O.lb
0.14
0.15
0.14
0.12
0.14
0.11
0.17
0.07
0.14
1.52
0.65
0.98
—
2.76
—
—
—
0.15
0
0.04
0.05
—
0.43
0.03
1.30
0.37
0.33
0.03
0.21
0.14
0.25
0.01
0.05
0.06
__
0.64
0.10
0.20
0.29
0.02
0.02
<0.01
0.04
0.06
0.01
0.02
0.08
0.01
0.01
<0.01
0.01
1.33
<0.01
0.01
<0.01
0.01
0.35
0.02
0.01
0.03
0.42
0.01
—
—
0.49
0.02
<0.01
'0.01
0.03
0.70
0.02
<0.01
0.03
0.05
0.01
<0.01
<0.01
0.01
0.03
<0.01
0.01
0.04
0.70
0.02
<0.01
<0.01
0.03
~
1.43
0.68
1.73
1.34
1.17
0.71
1.18
0.95
0.87
0.74
0.75
0.78
2.27
1.33
1.71
—
6.00
4.38
5.61
—
1.14
0.87
O.S6
0.89
—
1.87
1.79
1.78
1.77
3.43
1.34
2.80
2.10
0.53
0.31
0.20
0.33
_-
2.55
1.97
1.80
2.11
::
0.1S
0.23
0.18
0.59
0.05
0.03
0.01
0.09
0.02
0.04
0.01
0.07
0.03
0.03
0.06
—
0.02
0.01
0.03
—
0.17
0.25
0.09
0.51
—
0.07
0.10
0.04
0.21
0.13
0.11
0.06
0.30
0.07
0.08
0.03
0.18
—
0.07
0.08
0.03
0.18
-
5.45
1.14
2.66
2.38
2.25
1.74
1.60
1.95
__
2.42
1.28
2.90
1.93
9.09
3.94
5.00
—
12.76
14.21
13.31
—
1.99
1.40
1.24
1.51
—
2.49
3.00
2.55
3.05
7.20
2.75
4.59
3.96
2.07
0.54
0.40
0.88
—
7.53
3.60
3.28
4.75
-
0 70
0.39
0.28
1.36
0.10
0.08
0.02
0.19
__
0.07
O.ln
0.05
0.18
„
0.12
0.07
0.19
—
0.05
0.02
0.07
—
0.29
0.40
0.16
0.85
—
0.11
0.17
0.08
0.36
O.JS
0.25
0.30
1.14
0.26
0.13
0.06
0.45
—
0.20
0.14
0.06
0.40
•Hydrolyuble » - hydrolyaable [™4-N + Aalno Acid - » + Bexoseanlne-N]
111-22
-------
PART IV
AVAILABILITY OF THE TRACE METALS, COPPER, LEAD
AND ZINC IN SUSPENDED AND BOTTOM SEDIMENTS
by
D. E. ARMSTRONG
J. R. PERRY
D. E. FLATNESS
IV-i
-------
ABSTRACT
The availability of trace metals (Cu, Fb, and Zn) was measured in sus-
pended and bottom sediments from five tributaries to the Great Lakes.
Availability was estimated as the fraction extracted by a hydroxylamine
hydrochloride reagent (HH-metal) or a chelating cation exchange resin
(resin-metal). The amount of sediment remaining following analyses for
phosphorus and nitrogen limited the number of samples available for trace
metal analysis. Mean values of the available metal fraction (HH-metal) for
the individual tributaries ranged from 25 to 45% of the sediment total metal.
Exceptions were the Menomonee samples where mean values for the three metals
ranged from 46 to 76% and Pb in the Genesee samples (mean = 60%). Differ-
ences in availability among the clay, silt, and sand size fractions were not
significant. Resin-metal was less than HH-metal (mean values), with the
exception of Pb in the Menomonee samples. However, the. relative proportions
of resin-metal and HH-metal varied among the different metals and tributaries,
IV-ii
-------
CONTENTS - PART IV
Title Page IV-i
Abstract IV-ii
Contents IV-iii
Tables IV-iv
IV-1. Introduction IV-1
IV-2. Conclusions IV-2
IV-3. Methods and Procedures IV-3
Collection of Samples. IV-3
Analysis for Trace Metals IV-3
Analysis for Available Metals IV-3
IV-4. Results and Discussion IV-4
Pveferences IV-10
Appendix
IV-A Trace metals in suspended and bottom sediments IV-11
IV-iii
-------
TABLES
Number Page
IV-1 Copper distribution in size-fractionated suspended
sediments . IV-5
IV-2 Lead distribution in size-fractionated suspended
sediments IV-6
IV-3 Zinc distribution in size-fractionated suspended
sediments • IV-7
IV-4 Mean concentrations of total and available Cu, Pb,
and Zn in tributary suspended sediments IV-8
IV-A-1 Trace metals in suspended sediments .... IV-11
IV-A-2 Trace metals in bottom sediments IV-12
IV-iv
-------
IV-1. INTRODUCTION
The availability of trace metals associated with suspended tributary
sediments is of importance in determining whether trace metals will be
transported to the bottom sediments through particle sedimentation or
whether the trace metals will be released into the lake water and possibly
accumulated by aquatic organisms. This investigation focused on Cu, Pb,
and Zn. In addition to total metal concentrations, available metal concen-
tractions were estimated using hydroxylamine hydrochloride extraction
(HH-metal) and resin desorption (resin-metal) techniques. The hydroxylamine
hydrochloride reagent solubilizes surface-bound metal associated with metal
(e.g., Fe, Mn) hydrous oxides (1). The resin desorption method is comparable
in principle to the method used for estimating available P involving
equilibration with an anion exchange resin (see Part II). In the case of
the trace metals, a metal chelating resin was used. By removing dissolved
metals from solution, the resin will promote metal desorption from the
sediment particles until an equilibrium is reached between the sediment and
the metal concentration maintained in solution by the resin.
IV-1
-------
IV-2. CONCLUSIONS
Available metal concentrations in sediments generally represents an
average of 25 to 45% of the total metal. Availability may be higher in
sediments influenced by local sources of metals. For example, mean
available metal (HH-metal) levels ranged from 46 to 76% of the total metal
for Cu, Pb, and Zn in the Menomonee River samples. Other exceptions may
also occur, such as Pb in the Genesee which averaged 60% of the sediment
total Pb.
Differences in availability among the different particle size fractions
may exist, but were not significant in the samples investigated. The resin-
metal fraction generally represents a smaller fraction than the HH-metal of
the total metal concentration. However, a consistent relationship between
HH-metal and resin-metal was not found.
IV-2
-------
IV-3. SAMPLING AND ANALYSIS
Collection of Samples
The suspended and bottom sediments collected for analysis of trace metal
availability are described in Part I of this report.
Analysis for Trace Metals
Total metal (Cu, Pb, Zn) concentrations were measured by digestion with
a HC1-HN03-H202 reagent (2 hr) at 70°C, followed by analysis by atomic
absorption spectroscopy (2).
Analysis for Available Metals
Available metals were estimated by two chemical methods, a chelating
cation exchange resin desorption technique (resin-metal) and by extraction
with a hydroxylamine hydrochloride reagent (HH-metal).
Resin-metal
Cation exchange resin (Chelex 100, 50 to 100 mesh size) in the sodium
acetate form was equilibrated at pH 7.0 for 18 hr with the sediment
suspension. The resin was separated by sieving and eluted with 2N HNOs to
remove adsorbed metals (3). The eluate was analyzed by atomic absorption
spectroscopy (AAS).
HH-metal
The sediment was extracted with hydroxylamine hydrochloride (1) and
the extracted metals were analyzed by atomic absorption spectroscopy.
IV-3
-------
IV-4. RESULTS AND DISCUSSION
The concentrations of total metal$ HH-metal, and resin-metal were
measured on size-fractionated sediments (0.2 to 2, 2 to 20, and > 20 ym)
obtained from the Genesee, Grand, Maumee, Menomonee and Nemadji Rivers
which discharge to the Great Lakes. The metals investigated were Cu
(Table IV-1), Pb (Table IV-2) and Zn (Table IV-3). Analysis of metal
concentrations and distribution was limited to some extent by the number of
samples available. Becatise priority was given to analysis of phosphorus and
nitrogen in the suspended sediment samples collected, the amount remaining
for trace metal analysis was frequently insufficient, especially where the
suspended sediment concentrations were low. For the Grand and Maumee, only
two samples were analyzed and, with a few exceptions, only total metal
concentrations in the three particle size fractions were measured. However,
the sample number/size fraction ranged from 6 to 8 for'the Genesee, 4 to 6
for the Menomonee, and 3 to 5 for the Nemadji. A few bottom sediments and
intact suspended sediment samples also were analyzed. Details of individual
sample analyses are given in Appendix IV-A-1 and IV-A-2.
The expected tendency for higher total metal concentrations (mean
values) in the fine (0.2 to 2 ym) particulate fraction was observed for Cu
and Pb in the Genesee, Maumee, and Nemadji and for Zn in the Genesee and
Maumee samples (Tables IV-1, IV-2, IV-3). However, as shown by the high
coefficient of variation for the mean values (^ 20 to 80%), there were
exceptions to this trend for individual samples. For the other sample
groups (Cu, Pb and Zn in the Grand and Menomonee, and Zn in the Nemadji),
mean total metal concentrations were either fairly uniform among the size
fractions or highest in one of the larger size fractions.
The proportion of the total metal present as available metal (HH-metal
or resin-metal) did not differ appreciably among the three particle size
fractions (Tables IV-1, IV-2, IV-3). While some differences were noted in
mean values, the differences were not considered significant in view of
the relatively higher coefficients of variation and the small sample size.
The concentrations and distribution of total and available metals in
intact suspended sediment samples were calculated by summing the individual
size-fraction sediment-weighted metal concentrations (Table IV-4). The
highest concentrations of Cu, Pb, and Zn occurred in the Menomonee sedi-
ments. This likely reflects the numerous sources of trace metals in the
urbanized Menomonee Watershed. Intermediate concentrations were observed
in the Grand and Maumee suspended sediments, while concentrations of all
three metals were appreciably lower in the Genesee and the Nemadji than in
the suspended sediments of the other three tributaries.
IV-4
-------
Table IV-1. Copper distribution in size-fractionated suspended sediments
Sediment
size fraction
0.2 to 2 Mm
2 to 20 Mm
>20 Urn
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
Total
Mg/g
82
61
46
64
124
168
144
187
88
51
49
84
92
87
64
64
57
39
35
50
Cu
HH-Cu
35
36
53
49
64
35
42
40
34
20
—
29
23
18
22
Coefficient of
Resin-Cu
GENESEE RIVER
32
28
14
14
MENOMONEE RIVER
61
25
28
25
MAUMEE RIVER
32
19
GRAND RIVER
8
NEMADJI RIVER
22
10
16
13
Total
35(7)
41(8)
77(6)
29(2)
41(6)
54(5)
57(4)
23(3)
72(2)
11(2)
-(1)
-U)
35(2)
41(2)
-(1)
-U)
35(5)
37(4)
49(3)
3(2)
HH-Cu
46(6)*
38(5)
61(4)
0(2)
14(4)
42(4)
21(4)
3(2)
42(2)
-(1)
—
27(3)
24(3)
0(2)
-(1)
variation
Resin-Cu
60(4)
106(4)
49(3)
16(2)
19(4)
39(3)
64(3)
45(2)
-(1)
12(2)
-(1)
35(4)
50(2)
-(1)
-(1)
*Number of samples analyzed.
IV-5
-------
Table IV-2. Lead distribution in size-fractionated suspended sediments
Sediment
size fraction
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mia
2 to 20 Mm
>20 Mm
>0.2 Mm
Total
86
48
28
38
569
666
643
847
117
81
87
124
97
177
117
126
39
28
33
34
Pb
HH-Pb
52
68
54
52
76
71
81
68
33
40
—
13
30
29
25
Coefficient of variation
Resin-Pb Total Pb
%_ ,.
GENESEE RIVER
49
89
64
MENOMONEE RIVER
22
9
18
13
MAUMEE RIVER
7
GRAND RIVER
...
NEMADJI RIVER
5
3
29(7)*
64(8)
53(6)
19(2)
47(5) .
60(5)
64(4)
31(3)
64(2)
26(2)
-(1)
-(1)
10(2)
17(2)
(1)
(1)
27(5)
40(4)
71(3)
17(2)
HH-Pb
20(5)
32(3)
38(3)
2(3)
11(4)
26(4)
17(4)
12(2)
66(2)
-(1)
—
11(2)
26(2)
(1)
(1)
Resin-Pb
(1)
(1)
(1)
50(4)
72(3)
44(3)
11(2)
(1)
—
(1)
(1)
*Number of samples analyzed.
IV-6
-------
Table IV-3. Zinc distribution in size-fractionated suspended sediments
Sediment
size fraction
0.2 to 2 Vm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
0.2 to 2 Mm
2 to 20 Mm
>20 Mm
>0.2 Mm
Zn
Total
Mg/g
203
159
96
124
376
598
431
593
386
214
161
354
221
336
198
221
150
116
262
138
HHX
35
26
26
32
62
48
58
46
20
23
—
"-"""
«,«
™_
.
-»-»
22
21
43
26
Resin
%
GENESEE RIVER
13
8
4
10
MENOMONEE RIVER
23
13
21
18
MAUMEE RIVER
13
10
™"~
GRAND RIVER
..«
__
_,_
-""""
NEMADJI RIVER
13
7
__
7
Coefficient of variation
Total
33(7)*
35(8)
73(6)
6(2)
53(5) '
47(5)
45(4)
18(3)
74(2)
1(2)
-(1)
-(1)
28(2)
20(2)
-(1)
-(1)
26(5)
46(4)
57(3)
8(2)
HHX
23(6)
39(5)
64(3)
33(2)
16(4)
29(4)
23(4)
11(2)
25(2)
-d)
—
— •"»
— _
— — .
46(3)
53(3)
87(2)
-d)
Resin
35(3)
63(3)
26(4)
10(2)
14(4)
12(3)
17(3)
12(2)
44(2)
28(2)
—
-•— .
— —
— ^
54(4)
81(2)
—
-(D
*Number of samples analyzed.
IV-7
-------
Table IV-4. Mean concentrations of total and available
Cu, Pb, and Zn in tributary suspended
sediments.*
Tributary
Total Metal
HH-Metal
Resin-metal
yg/L yg/g
Copper
Genesee
Menomonee
Maumee
Grand
Nemadji
27
25
11
3
10
61
146
66
80
45
41
46
26
24
25
37
25
15
Lead
Genesee
Menomonee
Maumee
Grand
Nemadji
23
87
17
5
7
51
628
97
140
32
60
76
37
24
71
16
• 7**
Zinc
Genesee
Menomonee
Maumee
Grand
Nemadji
67
65
48
9
32
150
471
279
265
150
25
56
22
25
8
19
12
10
* Calculated from the mean concentrations in the three
particle size fractions (Tables IV-1, IV-2, IV-3) and
the average size distribution and concentrations of the
suspended sediments (Table 1-3).
** Based on one sample.
IV-8
-------
Available metal concentrations, measured as HH-metal, ranged from 24
to 41% of the total Cu, 24 to 76% of the total Pb, and 22 to 56% of the
total Zn. For resin-metal, concentrations ranged from 15 to 37% for Cu, 5
to 71% for Pb, and 8 to 19% for Zn. The expected Ipwer proportion of
resin-metal (as compared to HH-metal) was observed in most of the sample
groups, but Pb in the Genesee samples was an exception. These samples also
exhibited a high degree of availability (60 and 71% for HH-Pb and resin-Pb,
respectively). Only Pb in the Henomonee samples exhibited a higher degree
of availability (76%).
The fraction of the total metal present as HH-metal was higher in the
Menomonee samples than in samples from the other tributaries. Relatedly,
total metal concentrations were also highest in the Menomonee samples. This
likely reflects the local sources of trace metals in the urban/industrial
Menomonee Watershed.
The trace metal concentrations expressed on a volume basis did not
follow the same order as concentrations expressed on a sediment basis
(Table IV-4). These differences result from the large differences in mean
suspended sediment concentration among the five tributaries. For example,
the Genesee samples exhibited the highest concentrations of Cu and Zn
expressed on a yg/L basis even though concentrations on-a yg/g basis were
relatively low compared to the other tributaries.
The HH-metal is considered the best estimate of the available fraction
of the total trace metal in the sediment. With the exception of the
Menomonee samples and Pb in the Genesee samples, mean HH-metal concentrations
were in the range 22 to 46% of the total metal concentration. The reason for
the high proportion of HH-Pb in the Genesee samples (60%) as compared to Cu
and Zn (41 and 25%, respectively) is uncertain.
IV-9
-------
REFERENCES - IV
1. Chester, R. and M. J. Hughes. A Chemical Technique for the Separation
of Ferro-Manganese Minerals, Carbonate Minerals, and Absorbed Trace
Metals from Pelagic Sediments. Chem. Geol. 2:249-269, 1967.
2. Krishnamurty, K. V., E. Shprit and M. M. Reddy. Trace Metal Extraction
of Soils and Sediment by Nitric Acid-Hydrogen Peroxide. Atomic Absorp-
tion Newsletter 15:68-70, 1976.
3. Riley, J. P. and D. Taylor. Chelating Resins for Concentration of
Trace Metals from Sea Water and Their Analytical Use in Conjunction
with Atomic Absorption Spectrophotometry. Anal. Chera. Acta 40:479-
485, 1968.
IV-10
-------
Sanple Sedlnent
I
III
IV
V
Vtll
IX
X
XI
I
lit
IV
Mm
0.2 to 2
2 to 20
>20
>0.2
0.2 to 2
2 to 20
>20
>0.2
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
2 to 20
>20
>0.2
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
0.2 to 2
>20
>0.2
2 to 20
>20
>0.2
0.2 to 2
2 to 20
>20
0.2 to 2
2 to 20
>20
>0.2
90
56
46
—
91
67
74
77
95
61
17
51
121
72
102
—
SI
10
21
—
84
—
—
—
27
107
162
147
327
191
234
116
126
—
165
150
200
185
Cu
"
—
17(19)
4(6)
12(16)
11(15)
15(16)
5(8)
1(6)
6(12)
ND
ND
ND
ND
27(33)
7(70)
4(19)
~
__
—
—
—
-
63(59)
46(28)
48(33)
58(18)
20(10)
39(17)
54(47)
26(21)
—
—
—
—
~
—
50(55)
33(49)
32(43)
38(49)
49(52)
30(49)
7(39)
25(49)
24(20)
—
—
—
18(22)
4(40)
22
~
17(20)
29
—
~
46O100)
65(61)
62(38)
60(41)
99(30)
86(45)
94(40)
61(53)
60(48)
—
121(73)
—
106(53)
—
91
67
52
60
23
19
33
73
39
27
43
60
31
39
—
1C4
36
14
—
66
—
—
—
132
720
1223
1122
1112
666
814
198
233
"
467
475
668
604
s
Pb
"£/
mix
*•
CEHESEE
—
ND
ND
ND
ND
ND
ND
ND
tCD
—
—
—
51(49)
32(89)
9(64)
—
_~
—
—
"
~
ltt;oMO!.Tt;
260(36)
145(12)
162(14)
79(9)
101(9)
9fl(15)
93(12)
35(18)
8(3)
—
—
—
—
~
31(52)
16(70)
6(3D)
17(52)
37(51)
18(46)
18(67)
23(53)
„
--
—
'-
51(49)
32(89)
9(64)
—
„
—
—
—
"
RIVER
513(71)
873(71)
816(73)
521(47)
480(72)
504(62)
141(71)
166(71)
—
409(88)
—
535(80)
—
Total
232
259
212
—
188
131
67
125
230
137
46
1!2
151
121
151
—
IB:
112
42
—
166
—
—
—
53(40)
530
626
680
1001
439
625
418
341
—
428
438
493
474
2n
Resin
--
—
15(8)
17(13)
3(4)
11(9)
39(17)
4(3)
1(2)
12(10)
—
—
--
__
—
—
--
„
—
—
—
344
.
120(23)
111(18)
108(16)
124(12)
109(25)
116(19)
111(27)
50(15)
—
—
—
—
1IHX
--
--
50(27)
27(21)
14(21)
29(24)
105(46)
35(26)
15(33)
47(3'))
50(33)
—
—
--
4K25)
17(15)
8(19)
"
65(42)
29
—
—
139(40)
289(55)
265(42)
284(42)
336(34)
27^(62)
305(49)
208(50)
172(50)
--
330(77)
_.
359(73)
—
tlAUriLE RIVER
I
II
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
2 to 20
>20
>0. 2
132
55
49
84
43
47
—
—
42(32)
11(20)
—
—
„
8(17)
—
—
32(24)
11(20)
—
—
19(44)
—
—
—
170
96
87
124
64
66
—
—
12(7)
ND
—
—
r.'D
ND
—
—
82(48)
38(40)
--
—
11(17)
—
—
--
588
214
161
354
184
213
—
—
50(9)
18(8)
—
32(17)
25(12)
—
—
96(16)
50(23)
—
—
42(23)
—
—
—
GRAND RIVER
I
II
I
II
III
IV
*HHX
ND is
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
>20
>0.2
0.2 to 2
2 to 20
>20
>0. 2
0.2 to 2
2 to 20
>20
>0. 2
sample below
69
61
64
64
114
112
--
—
26
45
—
—
51
51
49
75
51
—
—
71
44
38
50
detect!
„
—
—
—
9(8)
—
—
—
8(31)
6(13)
—
—
13(25)
3(6)
8(16)
7(13)
12(16)
3(6)
—
—
11(15)
—
—
~
on limit.
__
—
__
10(38)
13(29)
—
__
12(24)
11(23)
9(18)
11(22)
__
—
—
"
__
—
—
—
103
156
117
126
90
198
—
—
21
41
—
"
42
59
38
38
23
—
—
48
23
24
30
__
—
—
—
SD
—
—
—
KEMADJI R
ND
t;o
—
—
2(5)
2(3)
KD
ND
ND
—
—
KD
—
—
—
tal.
..
—
—
—
__
—
—
—
IVER
3(14)
10(24)
—
~
5(12)
17(29)
10(25)
_-
—
—
~
__
—
—
—
177
289
198
221
265
382
—
—
93
161
—
—
157
139
146
180
133
—
—
187
118
83
130
..
—
132(50)
—
—
—
20(22)
18(11)
—
—
20(13)
17(12)
11(7)
17(9)
12(9)
—
—
12(6)
—
—
—
„
—
29(31)
47(29)
—
—
36(23)
48(35)
3R(26)
—
—
—
—
—
—
IV-11
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-------
|