Phosphorus Species in the Surficial Sediments of Lakes of Eastern North America

Phosphorus Species in the Surficial Sediments of Lakes of Eastern North America

Milton L. Ostrofsky Biology Department, /$!leghew y CoBIege, Meadvisle, PA 16335, US/$

Ostrofsky, M. k. 1983. Phosphorus species in the surficial sediments of lakes of eastern North America. Can. 8 . Fish. Aquat. Sci. 44: 968-966.

Species of phosphoms, total iron, and organic matter were determined from sudicial profuaadal sediments of 66 lakes of eastern North America. The lakes represented a broad range sf lake type, from oligotrophic to eutrophic and from soft water to moderately alkaline. The sediment characteristics were less variable than the lake characteristics. Highly significant correlations were found between percent loss on ignition and sedimentary organic phosphorus and between sedimentary iron and NH4CI-extractable, NaOH-extractable, HCB-extractable, total inorganic, and total phosphorus in the sediments. There was no relationship between spring total phosphorus or alkalinity and any sediment character measured. The resuits suggest that lakes with high sedimentary iron have disproportionately higher concentrations of NH4C1 and NaOW-extractable phosphorus, two species that are most likely to contribute to internal loading of phosphorus.

On a d$terrnin$ les vari6tes de phosphore, la teneur en fer total et la quantite de matigres organiques contenues dans les &diments suprficiels recueillis au fond de 66 lacs de l'est de I@Am&rique du Nord. Ceux-ci representent un vaste kcart de types de lacs, ailant de lacs o!igotrophes a des iacs eutrsphes et de iacs d'eau douce h des lacs mod$rkrnent alcalins. Les caract4ristiques des saiments ktaient moins variables que les caractkristiques des lacs. 18 existe des correlations netterrrent significatives entre la perte en pourcentage h I'ignition et le phosphore organique sedimentaire, et entre, d'une part, le fer s6dimentaire et, d'autre part, le phosphore totas inorganique et le phosphore total extractibles par NH4Cl, NaOH et WCI contenus dans les s4dirnents. li n'y a pas de relation entre, d'une part, le phosphore total printanier ou Ifalcalinit& et, d'autre part, toadte caractkristique s6dirnentalt-e quantifiee. bes resultats portent croire que les lacs A teneur 6lev& en fer s4dimentaire contiennent de plus fortes concentrations disproportionn6es de phosphore extractible par NH4Cl et NaOH, soit deux esp$ces qui ont le plus tendance 3 contsibuer h la charge interne de phosphore.

Received june 27, 1986 Accepted lanuary 82,1987 (J8846)

A large fraction of the annual phssphoms load to lakes is retained by the lake sediments. This sedirnented phosphorus can, under appropriate circumstances, be released as biologically available phosphorus, and

recent studies have shown lake sediments to be a significant source of phosphorus in the phosphorus economy of many lakes (Niirnberg and Peters 1984). As a result, limnologists have become more interested in the quality and quantity of sediment phosphoms. The existing paradigm for '5nternal" phosphoms loading to lakes involves redox-mediated release of phosphoms bound to iron. While limnologists have available a number of models which help make predictions about anoxia, and therefore redox status, in the hypolimnia of lakes, very little is known about what determines the quantity of iron- bound or other phosphoms species in the sediments of any lake. Although temperature, bioturbation, physical mixing, etc., have all been shown to have an effect on phssphoms release rates, the chemical species of phosphoms present in the sediments almost certainly are among the more important fac- tors regulating release.

Sediment phosphoms species have been analysed pre- viously, although the amount or kinds of phosphorus were only seldom compared with other sediment or lake characteristics. A notable exception is the work of Williams et al. (19769,

Recw !e 27 jwin 3986 Accept4 %e 19 janvier 8987

where correlations were found between sediment chwac- tefistics and phosphorus species for 48 surficid sediment samples taken throughout Lake Erie. Phosphorus species, iron, manganese, organic matter, mean grain size, and percent sand, silt, and clay were all highly intercorrelated. Although the sediments of large lakes such as Lake Erie are highly hetero- geneous, these interrelationships suggest that the quality and quantity of phosphorus in these sediments may be predicted from knowledge of only a few variables.

It is unknown if these correlations exist in other lakes or are unique to each lake or group of lakes sharing similar basin geology and hydrologic characteristics. The purpose of this study w a to examine the profundal sediments of a variety of lakes from eastern North America and to look for significant correlations between species of phosphoms and other lake and sediment characteristics. It was hoped that any significant eon-elations found might serve as the basis for empirical m d - els enabling limnologists and lake managers to predict sediment phosphoms species and, ultimately, potential rates of internal phosphoms loading.

Methods

Lakes were chosen for easy accessibility and readily avail-

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TABLE 8 . Characteristics of the lakes sampled.

Temperature Spring of s u ~ a c e

Area [TP] AIkalinity Depth sediments Region and lake (ha) &/Ao (pg0$.-') (m@qsL-'? (m)

Ontario Algowquiw Park

Kemey Costello Brewer Clarke Little McCarsley Found

Haliburton Beech Green Pine Cranberry

Connecticut Linsley Quonnipaug Black Quassapaug Taunton Menosia Ball Squantz Bantam Mt. Torn Waramaug West Side Tyler West Hill Highland East Twin Wononscopmuc Mudge Wononp&osk Cream Hill

Vermont Dunmore Shelburne Iroquois Faifield C m i Eden Woleott Caspian Shadow Parker Crystal May Echo Island Groton Peacham Ewell Harvey's More y Fairlee

Pennsylvania Conneau t Crystal

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Temperature Spring of surface

Area [TB] Alkalinity Depth sediments Region and lake (ha) A,r/Ao @geL '1 (meqoL-') (m) ("Q

Sandy Sugar Canadohta Edinboro IxBoeuf Pleasant

New York Western New York

Findley Bear Lower Cassadaga Silver Java Lime

Adirondaeks South Big Moose

- - -

south and Big Moose lakes are affected by acid precipitation.

able, or easily obtainable, spring phosphoms data. Phosphorus and morphaametric data for six Algonquiw Park lakes were taken from Scheider (1978). Data for four Halibu~eon lakes were from Dillon (1974). Lake characteristics of 28 Connecti- cut lakes were from Fink and Norvell (1984). The Vermont Department of Water Resources provided unpublished data on 261% Vermont lakes. Characteristics of six western New York lakes were from the New York Department of Environmental Conservation. Data on two Adirondack lakes were provided by J. S. Owen (SLBNY-Syracuse, pers. comm.). Hnformation on eight Pennsylvania lakes is from M. L. Bstrofsky (unpubl. data).

Sediment samples were obtained from a single location in the deepest area of the lake, or, where a bathymetric map was unavailable, from the geometric center sf the lake. Samples were collected with a Wildco K.B. corer. Cores were extruded in the field, and the surface 2.5 cm of sediment was placed in polyethylene bags and held on ice until analyses could be started (always within I wk) . Surface and bottom temperature, surface and bottom dissolved oxygen concentrations, and surface alkalinity were also measured. The depth from which the sediment was obtained was also noted. Table 1 presents descriptive data on all the lakes.

In the laboratory, species of phosphoms in the sediments were determined using the sequential extraction procedure of Hielt~es and Lijklema (1980). Sediments were extracted for 2 h twice with 1 M N&C1 (interstitial plus loosely bound plus CaC03-adsorbed phosphoms), for 17 h with 0.1 N NaOH (iron-plus aluminum-bound phosphoms), and 24 h with 0.5 N HCI (calcium-bound phosphorus). Total sedimentary phosphorus was determined following K%NB3/ HC1B4 digestion. A11 phosphoms determinations were based on the heteropoly blue technique outlined in Strickland and Parsons (1968). Organic- bound phosphoms was calculated as the difference between

on WNQ/ HC104 digests, APHA 197 1 ) were also determined on all samples. All analyses and extractions were done in triplicate. Average coefficient of variation was less than 5%. Mean values are reported here and were used for subsequent regression analyses. All data are reported on a dry weight basis.

Results and Discussion

Experimental

Mean values for sedimentary phosphorus species, iron, and loss on ignition are given in Table 2, and summary statistics for the entire collection of lakes are given in Table 3. All phosphorus species demonstrated a lognormal distribution. Organic bound phosphoms (BRG-P) was the least variable phosphoms species (coefficient of variation = 28%), and loosely sorbed phosphorus (NW4GI extractable) was the most variable (coefficient of variation = 198%). Most sediment variables measured were highly intercomelated. A matrix of comeBation coefficients is given in Table 4. There was a highly significant relationship between organic content of the sediments measured as percent weight loss on ignition (LOI) and organic phosphoms (Fig. 1). Remaining phosphorus fractions were highly correlated with iron. Due to the lognormal distribution of these variables, regression analyses required the use of natural log-transformed data. These relationships are shown in Fig. 2-6.

A11 phosphorus fractions in the sediments were highly come- Bated with total sediment phosphorus (TOT-P), and all inorganic phosphoms fractions are highly conehted with total inorganic phosphoms (IN-P), and to each other:

( I ) In (NH4Cl-P) = 2.89 ln (TOT-P) - 19.36 r = 0.57

total sedimentary phosphorus and the sum of the inorganic fractions. Sediment dry weight (24 h at 100QC), loss on igni-

(2) In (NaOH-P) = 1.78 ln (TOT-P) - 7.49 r = 0.84

tion (2 h at 550°C), and total iron (orthophenanthroline method (3) In (HC1-P) = 0.77 In (TOT-P) - 0.58 r = 0.44

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TABLE 2. Sediment characteristics of the 66 lakes investigated. A11 phosphorus species in p g 4 g sediment dry weight-', iron in mgeg sediment dry weight-', and LO1 in percent of dry weight.

Region m d Bake NM4Cl-P NaOH-P HCl-P TOT-P Iron LO1

Ontario Algonquin Bark

Kearne y Costello Brewer Clarke Little McCauley Found

Haliburton Beech Green Pine Crankmy

Connecticut Limky Quonnipaug Black Quassapaug Taunton Kenosia Ball Squantz Bmtarn Mt. Tom Wararnaug West Side Tyler West Hill Highland East Twin Wononscspomuc Mudge Wononpakook Cream Hill

Vemont Dunmore Shelbrume %roquois Fairfield C m i Eden Wolcstt Caspian Shadow Parker Crystal May Echo Island Groton Peacham Ewell Harvey' s Morey Fairlee

Pennsylvania Cenneaut Crystal Sandy Sugar

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TABLE 2. ( C ~ n c l d e 4

Region a d lake NH4Gl-P NaOH-P HCI-P TOT-P Iron LO1

Cmadohta 33 773 1 62 2253 38.2 18.3 Edinboro 35 934 197 235$ 44.6 18.9 LeBoeuf 20 753 178 1 888 50.0 13.2 Pleasant 4 1 564 180 21 13 42.4 21.2

New York Western New Y s k

Findley 866 1363 243 2953 52.0 18.7 Bear 12 449 166 1693 45. 1 13.7 Lower Cassadaga 53 248 158 8 347 26.1 25.0 Silver 22 378 364 1834 32.9 18.1 f ava 52 929 152 2868 46.4 21.6 Lime 44 188 130 1397 22.7 23.9

Adirondacks South 6 413 43 1329 - 44.0 Big Moose 27 1 307 33 1 1926 - 40.0

TABLE 3. Descriptive statistics for sediment characteristics of the 66 lakes investigated. All phosphoms species in pg-g sediment dry weight-', iron in mgeg sediment dry weight-', and LO1 in percent of dry weight.

Coefficient Parameter Mean Range SD of variation

TOT-P ORG-P IN-P NHdCI-P NaOH-P HCI-P

Iron LO1

(4) Bn (IN-P) = 1.49 In (TOT-P) - 4-77 r = 8-85

(5) In (ORG-P) = 0.49 In (TOT-P) + 3.38 r = 8.48.

Spring total phosphoms, [TP], which has been used as a powerful predictor of such in-lake characteristics as mean chlorophyll (Dillon and Wigler 1974), Secchi transparency (Patalas 19721, and hygolimnetic oxygen deficit (Csrnett and Rigler 1979), and alkalinity were not significantly correlated with any sedimentary phosphorus species. This resutt suggests that neither can be used to predict the sediment chmcteristics of these lakes. The observed intercomelations of the ghss- phorus species suggest that relatively constant relationships exist among the various foms of phosphoms within the sediments regardless of a l&e9s trophic status or alkalinity.

The collection of lakes described here represents a broad range of lake types, from oligotrophic to eutrophic and from soft to alkaline. Nevertheless, the sediments of these lakes were quite similar in that there were constant relationships among the measured sediment characteristics. Organic d i - ment phosphorus was a function of sediment organic content measured as EOI (Fig. I). Sediment stganic content was

% Loss on ignition

FIG. 1. Relationship @ < 0.01) between percent dry weight bs t on ignition and sediment organic phosphoms in the 66 lakes sampled (solid circles) and in European lakes (crosses). See Table 5 for European lake data and sources.

fraction of total inorganic phosphorus, but also because other inorganic fractions are also strongly correlated with sediment iron (Fig. 2, 3, and 4). 'Total sediment phosphoms then was a function of EOI and iron although stepwise multiple regression analysis suggested that EOI does not significantly improve the predictive ability over that possible with iron alone (Fig. 6).

Sediments with more total phosphoms tended to have relatively m r e inorganic phosphorus (slope sf the regression line (4) was significantly greater than 1 , p < 8.05) and less organic phosphorus. Increased inorganic phosphoms was largely due to increased NH4Cl-P and NaOH-P (slopes significantly greater than 1). HCl-P was a relatively constant fraction of inorganic phosphorus (slope not different from 1).

correlated with the ratio of drainage basin area to lake area Literature (r = - 6). 35, n = 63) rather than to spring total phosphoms, a measure of trsphic status. Inorganic sediment phosphorus was These results are in close agreement with those of Williams highly comlated with the iron content of the sediments et al. (19'761, who also found significant relationships between (Fig. 51, mostly because iron-bound phosphorus was a large organic matter and organic phosphorus and between iron and

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TABLE 4. Matrix of correlation coefficients among I&e and sediment characteristics measured on the 66 lakes. Conelation coefficients greater than 0.24 and 8.31 ape significant at * p < 0.05 and * * p < 0.01, respectively.

NaQH-P HCI-P IN-P BRG-P TOT-P Iron LQI Alkalinity [Tp]

NM4C1-P NaOH-P HCl-P IN-P QRG-P TOT-P Iron LQI Alkalinity

FIG. 2. Relationship @ < 0.01) between total sediment iron and PlH4CB-extractable phosphorus. Symbols as in Fig. I .

FIG. 3. Relationship bg < 0.01) between total sediment iron and NaOH-extractable phosphorus. Symbols as in Fig. 1.

inorganic phosphorus species in Lake Erie sediments. Direct comparison with Williams et al. (1976) is not possible because of different analytical methods used. Hieltjes and Lijklema (1980) have suggested that the CDB extraction technique used by Williams et al. (1976) can include an appreciable fraction of the calcium-bound phosphorus in the nonapatite inorganic phosphorus (NAI-P) fraction and give incamplete extraction of

0.65 HCI-P = 20.29(Fe)

r = 0.45 x .

100 . 3 10 JQO

FIG. 4. Relationship (g < 0.01) between total sediment iron a d W61- extractable phosphorus. Symbols as in Fig. 1.

10000

IN- P 2 7 . 6 6 ( ~ 1 1 ~ . ~ ~

10 3 I0 100

IRON, mg-g'8

FIG. 5. Relationship @ < 0.01) between total sediment iron and total inorganic sediment phosphorus. Symbols as in Fig. 1.

the aluminum-bound phosphsrus. Nevertheless, total phosphorus should be comparable between the two etudies. When the two regression lines between iron (as a percentage of sediment weight) and total phosphorus were compared, the

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IRON, np.f '

FIG. 6. Relationship @ < 0.01) between total sediment iron and total sediment phosphorus. Symbols as in Fig. 1.

TABLE 5. Phosphorus species, iron, and LO1 from the sediments of European lakes. Data derived from Tiren and Pettersson (1985) for Swedish lakes and Lake Balaton, Klapwijk et al. (1982) for Netherlands lakes, and vanEck (1982) for Hollands Biep/ Haringvliet (HD/HV). AIl units as in Table 2.

Region and lake NH4Cl-P NaOH-P HCI-P TBT-P Iron LO1

Sweden Ringsjiin TAkern rysingen Osten Vallentunasjon

Hungary Balaton

Netherlands Braassem Westeinder Reeuwijk Nieuwkoop

slopes were significantly different ( p > 0.0%). Apparently, the relationship between total phosphorus and iron from all regions within Lake Erie is different from the relationship between total phosphorus and iron from the profundal zones of different lakes although different analytical methods for both phosphorus and iron may contribute somewhat to this difference.

As mentioned above, there are no other extensive data sets with which to compare these present results. A compilation of some data from European lake sediments is shown in Table 5. These data are from studies where sediment phosphorus spe-

cies were determined using the Hieltjes and Lijklerna (1980) technique. These data are, for the most part, within the ranges reported for the 66 North American lakes, and the individual lake data are plotted in the appropriate figures although these data were not included in the regression analyses. The Euro- p a n lake data ape consistent with the North American data, suggesting the possibility of widespread application of the relationships developed here.

As the regression analyses indicate, iron has more of a bearing on sediment phosphorus chemistry than does trophic status or alkalinity. Lakes with more sedimentary iron tend to have disproportionately more iron-bound and loosely sorbed phosphorus, species that are most likely to contribute to internal phosphorus lading: iron-bound phosphoms is released at low redox potentials, and loosely sorbed phosphorus includes interstitial soluble reactive phosphorus which can migrate into the overlying hypolimnetic waters. Therefore, lakes most sus- ceptible to internal loading will be those which have both iron- rich sediments and anoxic hypolimnia.

I am grateful to @. Imhoff, M. Lewis, D. Osborne, and E. Zettler for assistance in the field and to M. Green for assistance in the laboratory. The two Adirondack lakes were sampled by J. S. Owen. A. P. Zimerrnan, G. K. NGrnkrg, and an anonymous reviewer made helpful suggestions on the manuscript.

References

APHA. 1971. Standard methods for the examination sf Water and Waste- water. 14th ed. American Public Health Association, Washington, DC.

C O R N E ~ , R. b., AND F. PI. R~GLER. 1979. trypolimnetic oxygen deficits: their prediction and interpretation. Science (Wash., DC) 285: 588-581.

DILLON, P. J. 1974. TRe prediction of phosphorus and chlsrophyll csn- centrations in Bakes. Ph.D. thesis, University of Toronto, Toronto, Ont.

DILLON, P. I., AND F. H. RIGLER. 1974. m e phssphoms-chlorophyll relationship in lakes. Limnol. Oceanogr. 19: 767-773.

FWINK, C. R., AND W. A. NORVELL. 1984. Chemical and physical properties of Connecticut lakes. Conn. Agric. Exp. Stn. Bull. 817.

H~ELTJES, A. H. M., AND L. LIJKLEMA. 1988. Fractionation of inorganic phosphates in calcareous sediments. J. Environ. Qual. 9: 405-407.

KLAPWIJK, S. P., J. M. W. KROON, AND M.-&. MEIJER. 1982. Availabk phosphoms in Bake sediments in The Netherlands. Hydrobiolsgia 92: 491-500.

NORNBERG, G . , AND R. H. PETERS. 1984. The importance of internal phosphorus load to the eutrophication of lakes with anoxic hypolimnia. Verh. Int. Ver. Limnol. 22: 190-194.

PATALAS, K. 1972. Crustacean plankton amd the eutrophication sf the St. Lawrence Great Lakes. J. Fish. Res. Board Can. 29: 1451- 1462.

SCHEIDER, W. A. 1978. Applicability of phosphorus budget models to small precambrian lakes, Algonquin Park, Ontario. J. Fish. Res. Board Can. 35: 300-304.

STRICKLAND, J. D. H., AND T. R. PARSONS. 1968. A practical handbook of seawater analysis. Bull. Fish. Res. Board Can. 167.

Taae~ , T., AND K. PE~ERSSON. 8985. The influence of itb bate on the phosphorus flux to and from oxygen depleted lake sediments. Hydro- biologia 120: 207-223.

VANECK, @. T. M. 1982. Foms ~f phosphoms in particulate matter from the Mollands Diep/Haringvliet, The Netherlands. Hydrobiologia 92: 665-681.

WILLIAMS, a. D. H., J-M. JAQUET, AND R. L. THOMAS. 1976. Foms of phosphoms in the suficial sediments of Lake Erie. I. Fish. Res. Board Can. 33: 413-429.

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Documents

Phosphorus Species in the Surficial Sediments of Lakes of Eastern North America