Suspended Particulate Elements in Anoxic Hypolimnionof a Eutrophic Lake
Masahito SuGIYA M A * a n d Toshitaka HoR1***Department of Environmental Sciences, Faculty of Integrated H u m a n Studies,
Kyoto University, Kyoto 606‑01**Graduate School of H u m a n and Environmental Studies,
Kyoto University, Kyoto 606‑01

A B S T R A C T ‑ T h e distribution of suspended particulate elements was measured at thedredged area in the southern basin of Lake B i w a with a seasonal anoxic hypolimnion. In
order to reveal the net effect from authigenic suspended particles, the total particulate
concentration measured was corrected by the use of particulate Al content as a tracer for
terrigeneous matter. Particulate Fe concentration increased with depth near the bottom in
the anoxic hypolirnnion. Distributions of M n , M g , Ca, Sr, and V also showed profiles
similar to Fe. There were positive correlations between these elements and Fe concentra‑
tions and, in particular, the plots of M n , C a and Sr against Fe showed good linearities.
The concentrations of C u and Z n started to increase from just below the thermocline, at a
depth shallower than the above elements did, and were almost constant near the bottom.
These geochemical behaviors are discussed in terms of the formation of slightly soluble
sulfide precipitate and adsorption of metal ions onto it.
INTRODUCTION
In oxic lacustrine and marine environments, Fe and M n oxides perform as an effec‑
tive adsorbate of trace elements (Singh and Subramanian, 1984). These oxides often
accumulate at the oxic‑anoxic water boundary by repeating reductive dissolution and oxi‑
dative re‑deposition. It is a typical example to demonstrate these characteristics of Fe andM n oxides that ferro‑manganese nodules which are discovered on the sediment surface ofsome lakes and the ocean greatly concentrate m a n y kinds of metal in themselves (Cronan,
1976; Takamatsu et al., 1993).
However, where dissolved oxygen is completely depleted and waters become highly
reductive, as in the bottom water of eutrophic lakes, fjords or seas, Fe and M n oxides are
not formed and, inversely, reductively dissolve into water phase. In such a water, F esulfides are thought to succeed these oxides to play the role of scavenger of trace ele‑(8)

海 洋 化 学 研 究 第 9 巻第 1 号 平 成 8 年 4 月

ments. This is because Fe2+ and s2‑ ions accumulate by the reduction of Fe oxides andS O / ions, respectively, and Fe sulfides are abundantly precipitated (Davison and Heaney,
1978; Kawashima et al., 1985; Dyrssen and Kremling, 1990). O f course, Mn2+ ions also
accumulate in the water, but M n S is seldom precipitated because the sulfide is more soluble
than FeS (Kawashima et al., 1985; Balistrieri et al., 1992a).
It has been confirmed in m a n y laboratory experiments that various heavy metals
and other elements are effectively removed from aqueous phase by the addition of Fe
sulfides. Morse and Arakaki (1993) showed that metal ions such as Mn2+, Co2+ and Ni2+
exhibit good affinities to one of the Fe sulfide minerals, mackinawite (FeS). Pyrrhorite(Fei‑xS) and pyrite (FeS2) were also reported to adsorb m a n y metal ions well (Brown etal., 1979; Jean and Bancroft, 1986; Kornicker and Morse, 1991; Schoonen et al., 1992).
However, there are few papers which have discussed the formation of Fe sulfides andtheir interaction with trace elements in a natural environment. Although Mn, C a and P
were reported to be associated with FeS‑rich particles (Davison and Dickson, 1984; Davison
et al., 1992), the geochemical behaviors of other elements are poorly understood (Dyrssen
and Kremling, 1990; Balistrieri et al., 1992b).
Sulfide formation is observed in most sediments of lakes and oceans, even if thebottom water is strongly oxic. This reaction is known to be one of most important diage‑
netic processes (Morse et al., 1987). Accordingly, studies of the chemical dynamics ofmetals in highly reductive waters are closely related to the investigation of the diagenesis
which settling particles encounter in the sediment.
In the present paper, based on the distribution profiles of particulate suspended
elements measured in the anoxic hypolimnion of a eutrophic freshwater lake, the southernbasin of Lake Biwa, w e discuss the geochemical behavior of the elements and their asso‑
ciation with formation of sulfide precipitates, especially FeS.
SAMPLING A N DANALYTICAL M E T H O D S
Sampling
Water samples were collected at the dredged area of the southern basin of Lake
Biwa on 19 July 1989 and 3 August 1990 using a p u m p system equipped with Tygon
tubing (Sugiyama and Hori, 1994). Immediately thereafter, the sample (300‑500 ml) was
filtered through a 0.4 μm Nuclepore filter (diameter: 47 mm). The substance collected on
the filter was defined in the present work as suspended particulate matter (SPM). The
filtrate was acidified to p H 1 by adding superpure grade hydrochloric acid (Merck).

Transactions of The Research Institute of
Oceanochemistry Vol. 9, No.I, April. 1 9 9 6(9)Analysis of dissolved iron and manganese
Both Fe and M n in the filtrate were directly determined with a Japan Jarrel Ashmodel I C A P 96‑953 inductively coupled plasma atomic emission spectrometer (ICPAES).
Analysis of suspended particulate elements
The S P M and Nuclepore filter used were transferred into a 30 ml Teflon screw vial
and mixed with 0.5 m l of 25 % aqueous ammonia in order to hydrolyze the filter. After
standing for 12 hr, the mixture was dried at 110°
C, then digested with 0.5 ml of 70 %perchloric acid at 150 °C for 2 hr with the vial cap fit loosely. Thereafter 0.5 ml of 65 %nitric acid was added. The mixture was digested at 170°C for 4 hr, and then heated todryness by taking off the cap. T o the residue, hydrofluoric acid (40%, 0.5 ml) was added,
and the mixture was homogenized ultrasonically for 10 min, then brought to dryness byheating at 150 ℃ The residue was dissolved in 3 ml of 0.1 M hydrochloric acid. Con‑
centrations of Fe, M n , Mg, Ca, Sr, Ba, V, Cu, Zn, Al, and Ti were then determined simul‑
taneously with ICPAES.
All the samples were manipulated in a clean box with a 0.1 μm air‑filter. All
reagents used were of superpure grade (Merck).
Analysis of terrigeneous manganese fraction in suspended particulate matter
Surface water samples were collected at 7 stations [le‑1, Kc‑3, Lc‑4, Lc‑2, Mb‑3,
Nb‑5, and Na‑3 (Hori et al., 1992)] in the southern and northern basins of Lake Biwa on 6
June 1995. The sample (500‑1000 ml) was filtered through a 0.4 μm Nuclepore filter. In
order to dissolve the M n oxide fraction, 1.5 ml of reductive extractant, which contained 1
M hydroxylammonium chloride and 0.175 M sodium citrate and was controlled to p H
5.0, was added to the S P M on the filter kept in a filter folder. After standing for 30 min,the extract was filtered. This treatment was repeated a second time. After washing withpure water, the treated S P M was transferred into a 30 m l Teflon screw vial together withthe filter used. The sample was digested and analyzed by the method previously reported(Sugiyama, 1996). This method is essentially the same as the one described in the above
section.
R E S U L T S A N D DISCUSSION
Deoxygenation in the hypolimnion
Hypolimnion at the dredged area in the southern basin of Lake Biwa was reported
to become anoxic in the summer stratification period because the dissolved oxygen was(10)

海 洋 化 学 研 究 第 9 巻第 1 号 平 成 8 年 4 月

completely consumed to decompose organic settling particles from the eutrophic epilim‑
nion (Terashima and Ueda, 1982; Kawashima et al., 1985). In the present work, althoughdissolved oxygen was not measured, its depletion in the hypolirnnion was confirmed by
the distribution profiles of dissolved Fe and Mn. These results are shown in Fig. 1, to‑gether with that for water temperature (WT). The thermocline was around 8 m depth in
1989, and was around 6 m depth in 1990. Although both dissolved Fe and M n were atvery low level in the epilirnnion (Fe: 0.01 ‑0.4 μ M ; M n : 0.02 ‑0.08 μ M), their con‑centrations in the hypolirnnion sharply increased from just below the them訳 line andreached 20‑30 m M near the bottom.
Correction for the terrigeneous fraction in suspended particulate matter
Limnetic S P M is divided into terrigeneous, authigenic mineral and biogeneous frac‑
tions, according to their origins. In order to reveal the distribution of authigenic particles
in the present anoxic hypolimnion more clearly, the terrigeneous fraction was eliminatedfrom the total particulate concentration measured (Sugiyama and Hori, 1994). Figure 2
shows the correlation between particulate Al and another element using all data sets ob‑
tained during July 1989 and August 1990. A s reported previously, when limited to theresults in the hypolimnion, plots of elements against Al were sufficiently linear indepen‑dently of sampling times for most of the elements analyzed.
Manganese was poorly correlated with Al, because M n concentration is affectedeven in the epilimnion by authigenic oxide particles produced from dissolved M n ionsabundantly supplied through rivers (Kawashima et al., 1988). Therefore, w e removed the
M n oxide fraction from the S P M by using a reductive extractant. Robbins et al. (1984)
reported that p H 5.0 solution containing 1 M hydroxylammonium chloride and 0.175 M
sodium citrate is effective to extract an oxide fraction in oxic sediment. After treatingwith this solution as described above, the M n and Al concentrations were determined.
These plots produced a strong linearity, as shown in Fig. 3.
The slopes and intercepts of the linear regression lines in Figs. 2 and 3 are listed inTable 1. The terrigeneous fraction in the S P M was estimated using these values and the
Al concentration in the hypolimnion.
Distribution of suspended particulate element
Aluminum and titanium
Vertical distributions of suspended particulate elements in 1989 and 1990 are shownin Figs. 4 and 5, respectively. Curves A and B i n the figures show the profiles before andafter the corrections for terrigeneous fraction. Unless specifically stated, the values re‑ferred to hereafter have been corrected.
Transactions of The Research Institute of
Oceanochemistry Vol. 9, No.I, April. 1 9 9 6

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C)
W T (°

゜
゜
10

20 30

2 r

August,4・

1990

Fe ( μM )10 20 30゜

M n (μM)
10 20 30゜‑=‑日 6
＾
5
Q.,

8

=10
と

12
14
C)
W T (°

゜
゜
10

2,

41

20 30

Fe ( μM )10 20 30゜

M n (μM)
10 20 30

゜

July,
1989

‑=‑日 6
＾
s
g8
10
12
14
Fig. 1 Vertical distribution of dissolved Fe and M n on 19 July 1989 and 3 August 1990.

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海 洋 化 学 研 究 第 9 巻第 1 号 平 成 8 年 4 月

6

50

(4
K
u
)
2

(
h
u
) 25
e
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0
2

0
2

ロ
ロ

上

S

ー5

ー5

K(︶．
ュー

5

5
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．

1

K(︶5
ュ1
s
J

0
5

0
0

K(︶．
ュー

岳
と

0
0
2

゜

0.5

0
1

゜
゜
810

。
。

K(︶
ュ0 5

10
15
Al ( μM )

.
1

wu

゜
5

ロ
・

。
。

20

Fig. 2

．
．
．
．
i-i~o
゜
0
0

ロ

5

゜

ロ

10
15
Al ( μM )20

Correlations between particulate elements and Al concentrations.
● :Epilimnion in July 1989, 0 : Hypolimnion in July 1989 ， ：Epilimnion in August 1990, and:Hypolimnion in August I990. The lines in the figure were obtained by the linear least squares■□

method with the data in the epilimnion (data of ▲ were not used in the calculation because of fearof contamination). The line of Ti was for the data in whole water column.
Transactions of The Research Institute of
Oceanochemistry Vol. 9, No.I, April. 1 9 9 6(13)

Fig. 2 (continued)

80

200

▲

訟

60

＾
苔
,,̲, 40

150

8

＾
弓
0100

▲

←
..

C

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20

50

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30

゜

゜
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l

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し

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0

l

5

l

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15
Al ( μM )

20

o

l

0

5

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15
Al ( μM )20

Particulate Al and Ti are often used as a tracer for terrigeneous S P M , because they
are not reactive in natural water with a circurnneutral p H (Brewer et al., 1980; Stabel,1985). In the present work, the particulate Al concentration was utilized in the correction
for the terrigeneous matter. A s shown in Figs.4 and 5, the distribution profiles of total
particulate Al and Ti resembled with each other, being at high concentrations in the epil‑
imnion and low in the hypolimnion. Plots of Ti against Al showed a good linearity for thedata sets, not only in the epilimnion but also in whole water column (Fig. 5). These
results suggest that Al and Ti are not reactive in anoxic water, and proved that the correc‑
tion for terrigeneous fraction using these elements is appropriate even in the water.
Iron and manganese
Both the Fe and M n concentrations peaked below the thermocline and increased
with depth near the bottom. Manganese reached a m a x i m u m at depths of 8 m in 1989 and6 m in 1990. Iron peaks were rather diffuse compared with those of M n , and were at 9.5
m (1989) and 7.5 m (1990) depths. A s discussed in detail in our previous report (Sugiyama(14)

海 洋 化 学 研 究 第 9 巻第 1 号 平 成 8 年 4 月

0.04

(K
︶
ュ0 2

u
w︒

。
〇

5
10
Al ( μM )15

Fig. 3 Correlations between particulate M n and Al concentrations after extraction treatment ofoxide fraction. The line in the figure was obtained by the linear least squares method.
Table I Parameters for linear regression line of plots of elements against Al concentrations([element]= a x [Al]+ b) shown in Figs.2 and 3.

ab(mol/mol‑Al)(mol/1)Fe

2.51xlff1‑4.67 X lff7

0.994

M n

3 .3 0 X J0‑3

1.22 X 10‑4

0 .9 8 8

M g

1.02 x I0 I

‑6.95 X 10‑8

0.989

Ca

2.61 X 10‑2

5.IOxIO7

0.843

Sr

2.20 X 10 47.38 X 10‑I O

0 .9 5 9Ba

7.27 X 10‑4

5.77 X 10‑9

0 .9 4 3V

8.46 X 10・
4‑3.30 X 10・'

0 .9 6 5Cu

2.58 X J0・
4

7.97 X 10・
4

0 .8 7 7Zn

2 .19 X 10‑.l‑7.67x 10・・
1

0.878

Ti

1.45 X 10‑2

8.80 X JO‑J

0.926

Element―――*r: correlation coefficient.

Transactions of The Research Institute of
Oceanochemistry Vol. 9 , No.l, April. 1 9 9 6

r*

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Z n (nM)

80

40

W T (0C )Al ( μM )

゜゜ ゜
‑40

5

10

15 0

10

pH

30

20

6

7

8

，

2

4

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gs 8

‑、6
日

10
12

14
Sr (nM)

‑2.5

0

゜

‑25

2

I B¥

4

V (nM)

B a (nM)

5

2.5

゜
25

50

C u (nM)゜

10 ‑10゜

IA I IBl I A

5I I B/IA¥ A I I BI

‑5

10

20

‑=‑E 6
ヽ

>

8

10
12
14
Fe ( μM )

゜゜
‑10

10

M n ( μM )20 ‑0.50

0.5

M g ( μM )

1

‑1

2

4

I BI I A

I I

B/9 A

゜
1

I I BlC a ( μM )

2

¥A

•I

゜

I I Bl1

2¥A‑=‑!E 6
＾

>

8

IO

12
14
Vertical distribution of suspended particulate elements on 19 July 1989.
(A): Total particulate concentration, (B): Particulate concentration corrected using relationshipFig. 4

described in Figs. 2 and 3.
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海 洋 化 学 研 究 第 9 巻第 1 号 平 成 8 年 4 月

Z n (nM)
40 80

Al ( μM )5 10 15

゜ ゜
゜
I
‑40

2

゜

100 150

゜

lA

11 A

I I

Sr (nM)
0 2.5 5

B a (nM)
‑25
25 so

B

W T (0C)
10 20 30Ti (nM)50

4日‑ヽ 、 6

g5 8
10

12
14
‑2.5

゜
2

A

゜

I I BI IA

V (nM)C u (nM)
5 10 ‑10
10 20

゜

‑5

I I

fj

I

¥

A

゜

I I B

4

日 6
＾
C

I:

>

12

14
‑10

Fe ( μM )M n ( μM )0 1 0 20 ‑0.5 0 0.5 1

゜
2

4

B

I A

II

B ¥ A

‑1

M g ( μM )
0
1 2

IIB I

‑1

C a ( μM )
0
1 2

I A

＾
‑=E‑! 6
g5 8
10
12

14
Fig. 5

Vertical distribution of suspended particulate elements on 3 August 1990.

(A): Total particulate concentration, and (8): Particulate concentration corrected using relation‑
ship described in Figs. 2 and 3.
Transactions of The Research Institute of (17)Oceanochemistry Vol. 9, No.I, April. 1 9 9 6

and Hori, 1994), these Fe and M n peaks were due to the hydrous Fe and M n oxides
accumulated at the depths of the respective redox boundaries for these elements. W e
named these boundaries Fe203/Fe2+ and Mn02/Mn2+ redox fronts, respectively.
The increase in Fe concentration near the bottom suggests the formation of FeS
precipitate, as reported by Kawashima et al. (1985). In 1982, they measured dissolved Fe
and sulfide concentrations at the same area as studied in our present work, and confirmedthat the bottom water was saturated for FeS based on the calculation of ion product of[Fe2+][S．
汀
In contrast, M n S was inferred not to be precipitated in the bottom water. If both
FeS and M n S were formed, the ratio of [Mn2+] / [Fe2+] should be at the level from 4.4 x 101]/[H+], K.n
Mn~=
to 2.4 x 104 from the solubility products of the sulfides{K.n= [ M勺 [HS・sp
sp,MnS
0.40 ‑ 1.5 (Emerson et al., 1983; Dyrssen and Kremling, 1990), and K,p,Fes = 9.1 x 10‑3 ‑6.3 x 10‑5 (Davison, 1991)}. However, [dissolved Mn]/[dissolved Fe] values in the present
work ranged from 1.0 to 4.7 in the bottom water and were m u c h lower than the above
ratio. Kawashima et al. (1985) also gave the same conclusion from the very low ion
product of [Mn2+][S勺 in lake water compared to the solubility of M n S.
The behavior of M n near the bottom was affected by the precipitation of FeS. In
Fig. 6, various elements'concentrations were plotted against those of Fe in the bottom
layer (10‑12.5 m depth in 1989, and 8‑12 m depth in 1990) where FeS precipitate wasconsidered to be f o m記 d. The good linearity of the M n against Fe plots suggests that M n
was associated with FeS particles. Davison and Dickson (1984) also reported that Mn/Fe
ratios in FeS particles were similar to each other owing to M n adsorption onto the sulfide
in anoxic hypolimnion. The iron sulfide minerals, pyrite (FeS2) and mackinawite (FeS),
are known to adsorb M n ions well in laboratory experiments (Komicker and Morse, 1991;
Morse and Arakaki, 1993).
Magnesium, calcium, strontium, vanadium, and barium
The concentrations of Mg, Ca, Sr and V were almost constant in the upper layer ofthe hypolimnion, but increased with depth near the bottom. Calcium has been reported tobe contained abundantly in FeS‑rich particles in anoxic water (Davison et al., 1992).
Moreover, M g and C a are known to be adsorbed onto pyrite and mackinawite (Komicker
and Morse,1991; Morse and Arakaki, 1993). In the present work, the above elements,
especially C a and Sr, were also strongly correlated with Fe concentrations, as shown in
Fig. 6. Therefore, these elements are suggested to be removed by FeS particles near thebottom.
The distribution profile of B a was specific compared to the other alkaline earth
elements. The B a concentration reached a m a x i m u m just below the thermocline. This(18)

海 洋 化 学 研 究 第 9 巻第 1 号 平 成 8 年 4 月

20 I
‑

゜

15

゜゜゜
呂
‑ 10 ゜

80
60

。
。
。

．
..
゜
.
．
・'
．
｀
．
゜
゜
．．
＾
弓
望
．゜ ゜ ＾
。 ゜
゜
゜
゜
゜
＾
40
゜ ,̲百

5

゜゜

C

5

20

15

8

10

6

.̲, 5

4

品

>

2

‑5

0.8

4

0.6

3

g::1. 0.4

゜

￨

i= 2
ヽ

）

0.2

1

リ

‑0.2

゜

‑1

0.4

0.2

゜

g 0.3

z＾
:
::1.

::I.

゜

10
15
F e ( μM )20

,̲, 0.1'‑" 0.2

芝

差
0.1

7

Iy . ,
5

10
15
Fe ( μM )

L

゜
゜

20

5

Fig. 6 Correlations between corrected particulate elements and Fe concentrations near the bottom.

0 : 19 July 1989 and ● :3 August 1990. The line in the figure was obtained by the linear leastsquares method.

Transactions of The R e 匹 arch Institute of
Oceanochemistry Vol. 9, No. l, April. 1 9 9 6(19)

peak was already reported to be due to the adsorption of B a ions onto hydrous M n oxide
formed at the M n 0 2 / M n2+ redox front in our previous paper (Sugiyama and Hori, 1994).
Barium also increased in the bottom water, but its correlation with Fe was very weak.
Copper and zinc
The distribution profiles of C u and Z n were different from that of any element
aforementioned. These concentrations started to increase with depth from just below thethermocline, and were almost uniform near the bottom. Accordingly,the concentrations
were scarcely dependent on those of Fe, as shown in Fig. 6. The mean concentrations of
dissolved C u and Z n in the southern basin of Lake Biwa are 7.8 x 1炉 M and 1.2 x 10‑sM ,respectively (Matsui et al., 1987). In the hypolimnion at the dredged area of the lake, H S‑
concentration was reported to reach a 2 x 1炉 M level in summer (Kawashima et al.,1985). Solubility products K,p for C u S and ZnS are 6.3 x 10‑23 and 1.6 x 10‑11, respectively(Smith and Martell, 1976). Therefore, since the p H value in the present hypolimnion wasaround 7.0 (Fig.4), it is inferred that both C u S and ZnS particles were formed in the water,
as in some other lakes (Davison et al., 1992; Balistrieri et al., 1992b). Even if C u was
dissolved as C u+ ion in the anoxic hypolimnion (Balistrieri et al., 1992), the solubility
product K,p for Cu2S, 2.2 x 10‑35 (Dyrssen and Kremling, 1990), is m u c h lower than thevalue of [mean dissolved Cu]2[HS‑J/[H+].
CONCLUSION
Near the top of the anoxic hypolimnion, Fe and M n oxides are significant for theremoval of trace elements. In previous papers (Sugiyama and Hori, 1994 and 1995), w e
discussed h o w the dynamics of barium was associated with M n oxide accumulation at thelayer. Behaviors of P and C o were reported to be linked to the formation of Fe oxides(Kawashima et al., 1985; Balistrieri et al., 1992). However, in its highly reductive deep
layer, FeS precipitate was confirmed in the present work to play the role of an effective
scavenger of metal ions. This was clearly indicated by the results that distributions of M n ,Mg, Ca, Sr and V correlated well with that of Fe near the bottom.
S o m e elements were scarcely affected by either geochemical process mentioned
above. Both C u and Z n were precipitated as their o w n sulfides, because of their moreslight solubility than that of FeS. Particulate Al and Ti were not geochemically‑reactive
even in the anoxic water, and these profiles were affected by the terrigeneous fraction
alone.

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海 洋 化 学 研 究 第 9 誉第 1 号 平 成 8 年 4 月

Acknowledgements‑The authors wish to thank Professor M . Kawashima, Facultyof Liberal Arts and Education, Shiga University, for his kind cooperation in the collectionof samples. T h e authors are also indebted to Professor M . Matsui, Institute for Chemical
Research, Kyoto University, for the use of the facilities in his laboratory.
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