ISSN 1995-4255, Contemporary Problems of Ecology, 2010, Vol. 3, No. 4, pp. 369373. Pleiades Publishing, Ltd., 2010.

. Original Russian Text S.A. Ostroumov, G.M. Kolesov, 2010, published in Sibirskii Ekologicheskii Zhurnal, 2010, Vol. 17, No. 4, pp. 525531.

The Role of Biodetritus in Accumulation of Elements in Aquatic Ecosystems

Lomonosov Moscow State University, Department of Biology, Leninskie Gory, Moscow, 119234 Russia E-mail: ar55@yandex.ru b V. I. Vernadsky Institute of Geochemistry and Analytical Chemistry, ul. Kosygina, 19, Moscow, 119991 Russia AbstractBiodetritus that formed over a 7-month period in microcosms with Viviparus viviparus, Unio pictorum, and Ceratophyllum demersum contained a number of elements. This is the first study to determine concentrations of some elements in biodetritus. Neutron activation analysis showed that the elements concentrations decrease in the following order: Ca > Zn > Ba > Br > Ce > Se > Nd > La > U > Hf > Sb > Th > Sm > S > Cs > Au. The data obtained contribute to understanding of the polyfunctional role of aquatic organisms in aquatic ecosystems. DOI: 10.1134/S1995425510040016 Key words: detritus, mollusks, water quality; rare and scattered elements, Viviparus, Unio, Ceratophyllum
a

S. A. Ostroumova and G. M. Kolesovb

Functioning of aquatic ecosystems involves migration of some elements [1, 2] through water column, transfer of elements on the watersediment interface, and biogeochemical flows of elements [113]. Studies of biogenic migration of elements are an important area of biospheric research [113]. Biogenic migration of elements in freshwater and seawater ecosystems is an aspect of water self-purification and determines water quality [1416]. It should be emphasized that the role of aquatic organisms in element migration is complex, involves both uptake and discharge of substances, and affects many other processes in an ecosystem [316]. To analyze how organisms contribute to biogenic migration of elements in an aquatic ecosystem we need data both on accumulation of elements by aquatic organisms and concentrations of those elements in biodetritus [15, 16] that precipitates and adds to sedimentation. In the previous works [15] and [16], we determined concentrations of some elements in mollusk detritus. However, these studies concerned only few elements and did not include data on U, Au, Ce, Se, La, Sb, Hf, Th, Sc, Sm, and Cs. In the literature we have not found data on the concentrations of the elements in detritus produced in microcosms after incubation of the common aquatic species: Viviparus viviparus L., Unio pictorum L., and Ceratophyllum demersum L. The study objective is to analyze biodetritus in microcosms where the three freshwater species are incubated. Element concentrations in the detritus are determined by neutron activation analysis (NAA). The results contribute to understanding of the role of biosediments in distribution of elements in aquatic ecosystems.
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MATERIAL AND METHODS Experiments were conducted on freshwater microcosms composed of three common freshwater species: Viviparus viviparus L., Unio pictorum L., and Ceratophyllum demersum L. maintained in settled tapwater. Ceratophyllum plants had been collected in a pond in the Moskva River floodplain within Moscow City. Viviparus and Unio mollusks had been collected in the upper reaches of the Moskva River, upstream of Zvenigorod town, Moscow oblast. Quantitative characteristics of the microcosms are summarized in Table 1. After the microcosms were made, they were incubated at a room temperature for 7.5 months (late August through mid April) and aerated with aquarium aerators. By the end of the incubation, the mollusks died producing biodetritus that was filtered, dried, powdered, and studied by neutron activation analysis (NAA). The use of NAA in geochemistry was discussed in Kolesov [17]. It had been used to determine element content in mollusk tissues in the study by Ostroumov et al. [18] that confirmed its efficacy in application to biologic material.

Table 1. Microcosm compositions Microcosm Species No. 1 Viviparus viviparus Unio pictorum Ceratophyllum demersum L. (Wet weight) Settled tapwater 39 ind. 12 ind. 2.4 g 3l No. 2 15 ind. 32 ind. 2.4 g 3l

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Samples were pretreated as follows. Detritus was dried at 105C. Fifteen to twenty-five milligram samples, reference samples (KH, ST-1, SGD-1, FFA, RUS-1, Allende, BCR, etc.), and standards were packaged in aluminum bags. The samples were placed in an aluminum box and irradiated for 15 to 20 h in the thermal channel of the nuclear reactor at Moscow Engineering-Physical Institute. Then they were cooled, the aluminum bags were removed, and the samples were put in clean vials to reduce background interference caused by the package. Radiation was measured after 57 and 1530 days with ORTEC high-resolution semiconductor germanium detector and NUC-8192 4096 channel pulse analyzer (EMG, Hungary). Spectra and element concentrations were determined in an automatic mode using software developed in Vernadsky Institute of Geochemistry and Analytical Chemistry. Concentrations of some elements were extrapolated, which is a common and tested practice. The composition of the settled tapwater, used for the microcosms, was determined by inductively coupled
Table 2. Elemental composition of the tapwater used for the microcosms compared to Maximum Allowable Concentrations (MAC) specified in Hygienic Standard GN 2.1 5.689-98, Ministry of Health of the Russian Federation, Moscow, 1998 Element Al B Ba Ca Cd Co Cr Cu Fe K Li Mg Mn Mo Na Ni Pb Si Sr Ti Zn Concentration mg/l 0.06 0.01 0.03 49.4 <0.001 <0.001 <0.01 <0.001 0.007 2.3 <0.01 12.6 0.016 <0.01 10.7 <0.002 <0.005 5.1 0.14 <0.001 <0.001 0.5 0.5 0.1 0.001 0.1 0.05 1 0.3 0.03 0.1 0.25 0.1 0.03 10 7 0.1 1 MAC

plasma atomic emission spectroscopy (ICP-AES) using ICAP-9000 spectrometer (Thermo Jarrell Ash, USA). The results are given in Table 2. Water quality obviously meets requirements specified in Russian hygienic regulations, which is of high importance for long-term incubation experiments. RESULTS AND DISCUSSION The results of the neutron activation analysis are given in Table 3. Concentrations of some elements, e.g., Se, U, Th, Hf, and Au, showed considerable variations complicating the calculations of averages. Calcium content was 15.2 to 15.4%, averaging 15.3%. Average concentrations of elements in detritus

Table 3. Element content in dry weight biodetritus in the microcosms according to NAA, ppm Element La Ce Pr* Nd Sm Eu Gd* Tb Dy* Ho* Er* Tm* Yb Lu Cs Ba Sc Zn Se Sb Th U Br Hf Au Microcosm 1 3.69 8.52 1.1 4.9 1.32 0.2 1.72 0.25 1.45 0.31 0.81 0.12 0.61 0.095 0.26 1530 0.92 1680 13.8 2.33 0.33 4.61 76 0.68 0.27 2 8.96 16.2 1.71 8.18 1.41 0.48 1.74 0.25 1.47 0.32 0.82 0.12 0.62 0.097 1.82 1250 1.69 1310 4.36 1.44 3.16 2.1 75 3.34 0.025 Average 6.325 12.36 1.405 6.54 1.365 0.34 1.73 0.25 1.46 0.315 0.815 0.12 0.615 0.096 1.04** 1390 1305 1495 9.08** 1.885 1.745** 3.355 75.5 2.01** 0.1475**

Note: An asterisk indicates extrapolated values (data from element distribution curve in content: ionic radius/atomic number for rareearth metals coordinates). A double asterisk indicates considerable variation of element concentrations. Further research should yield more accurate data.

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are arranged in decreasing order as follows: Ca > Zn > Ba > Br > Ce > Se > Nd > La > U > Hf > Sb > Th > Sm > Cs > Au. The biodetritus studied is different in its origin from total sediment that accumulates in water bodies and water courses, the latter including both biodetritus and other components, e.g., mineral suspension. It is possible that the element composition of the detritus differs from that of total sediment analyzed by other authors for the same reason. Thus antimony content is higher in the biodetritus than in total sediment [9] amounting to 0.05 to 0.11 ppm dry weight sediment. Zinc content is also higher in the biodetritus than in the total sediment of the Gomti River, a Ganges tributary, India, amounting to 15.72 to 99.35 ppm dry weight sediment [10]. Relatively high zinc content in the biodetritus may be explained by the detritus having been formed by dead organisms that had accumulated the element essential for many enzymes. Note that flows of biosediment formed by aquatic organisms are considerable. Ostroumov [19] estimated that in some aquatic ecosystems mollusk carbon flows were as high as 11.9 kg/m2 a year. Total element flow with bivalves detritus was 1711 tons of carbon and 235 tons of nitrogen a year for a 60 km2 aquatic ecosystem. From the data obtained we estimated the potential of detritus in accumulating immobilized elements for areas that accumulated 1 or 1000 kg dry weight of detritus, respectively (Table 4). It should be underlined that the estimations are only for reference and concern only the potential of detritus to accumulate some elements. The experimental data should not be extended to natural ecosystems. A distinctive feature of the experiment is that the detritus formed from known common organisms (two mollusk and one macrophyte species) over a specific period of time. The element concentrations in the detritus provide data on possible background element content. Further studies of element contents of the detritus are required as its background element content in polluted natural ecosystems may be contaminated because of anthropogenic pollution. Our preliminary tests showed that contamination of water with heavy metals, such as Cr, Co, Zn, Cu, and Cd, elevated their concentrations in biodetritus compared to control samples. In order to obtain reliable estimates and correctly interpret the data on concentration of metals in detritus in a polluted aquatic ecosystem, data on background element composition of detritus are required. In this study we obtained the data for detritus formed by 3 common species of aquatic organisms. Data on element composition of aquatic plants and their detritus have been reported in the literature, but there are no data on composition in mollusk detritus or to which mollusks contributed. It appears that the previ-

Table 4. Rough estimates of biosediment element content according to NAA Element Ca Ba Ce Se La U Sb Hf Th Sc Sm Cs Au Per 1000 g detritus 153 g 1.39 g 12.4 mg 9.08 mg 6.33 mg 3.50 mg 2.00 mg 2.00 mg 1.70 mg 1.40 mg 1.36 mg 1.04 mg 0.148 mg Per 1000 kg detritus 153 kg 1.39 kg 12.4 g 9.1 g 6.3 g 3.5 g 2g 2g 1.7 g 1.4 g 1.4 g 1.04 g 0.1 g

ous publications by Ostroumov (Table 5) are the only works to have explored into the subject. CONCLUSIONS Thus, this is the first study to determine some elements in biodetritus that formed in a controlled experiment incubating three common aquatic species (Viviparus viviparus, Unio pictorum, and Ceratophyllum demersum). The results contribute to understanding the role of the organisms in biogenic migration of the elements. The data obtained help more thoroughly estimate the role of biodetritus of specific organisms as a concentrator of elements in an aquatic ecosystem. A major factor affecting detritus formation by filter-feeders is the rate of filtration determined by the presence and concentration of surfactants, detergents, and other chemicals [20, 21]. In the previous works by Ostroumov, it was shown that detritus production can be affected by pollutants [2022]. Further studies should reveal new relations between water pollution and detritus as an important component of aquatic ecosystemswater bodies and watercourses. Vernadsky wrote: it is hard to overestimate the significance of living organisms They are agents of intensive migration of atoms in the biosphere [2], Life is a living matterbiogenic migration of atoms caused by life is the most important organizational form in the biosphere [2]. The data obtained support these views of Vernadsky, add to our knowledge of the role of biota in biogeochemical processes, elucidate how element composition of biosediment in aquatic ecosystems forms, and reveal interconnections between geochemical and hydrobiological processes in biogenic migration of elements [313, 2337].

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Table 5. Other studies of element composition in detritus of aquatic organisms Species Viviparus viviparus, Unio pictorum, and Ceratophyllum demersum Viviparus viviparus, Unio pictorum, and Ceratophyllum demersum Cardium edule Mytilus edulis Lymnaea stagnalis, Unio tumidus, U. pictorum, Crassiana crassa, Anodonta cygnea Lymnaea stagnalis, Unio tumidus, U. pictorum, Crassiana crassa, Anodonta cygnea Mussels Element U, Au Notes and references Uranium content in the biodetritus varied from 2.1 to 4.61 ppm dry weight detritus, 3.4 ppm on average. Gold content in the biodetritus varied from 0.025 to 0.27 ppm dry weight detritus, 0.15 ppm on average according to our recent results Our recent results

Ce, Se, La, Sb, Hf, Th, Sc, Sm, Cs, and other elements N C C, N, P, Si, Al

C, N, P, Si, Al

Pt, Pd

Biodeposits included 199 tons N over 60 km 2, Laholm Bay, Sweden [19] Biodeposits included 60 to 80.7 g C over 1 m 2 [19] Percent composition of Lymnaea stagnalis pellets: C, 69.74; N, 2.3 to 2.9; P, 0.4 to 0.5; Si, 1.1 to 1.7; Al, 0.054 to 0.059. Cation surfactant TDTAB 2 mg/l and anionic surfactant SDS 1 to 2 mg/l inhibited feeding by L. stagnalis and production of detritus (pellets). The study revealed reduced migration of elements through the mollusks and lowered biosedimentation [15] Percent composition of pellets sampled from a bivalve natural community feeding on natural seston: C, 64.3; N, 2.73; P, 0.39; Si, 1.14; Al, 0.071. A mixed pollutant inhibited feeding by L. stagnalis and formation of detritus (pellets). The study revealed reduced migration of elements in the mollusks and decreased biosedimentation [16] Recent data by Ostroumov

Note: TDTAB, tetradecyl trimethylammonium bromide; SDS, sodium dodecyl methylsulfate.

AKNOWLEDGMENTS We thank Yu. A. Moiseeva, E. A. Solomonova, G. Yu. Kazakov, A. V. Klepikova, and the staff of Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences for their help and fruitful discussion and the reviewer for careful reading and constructive comments. REFERENCES
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