Pure Appl. Chem. 2017; 89(3): 287–292

Conference paper

Natalia P. Tarasova*, Anna S. Makarova, Evgeniya G. Vasileva and Diana D. Savelova Estimation of the phosphorus loading with consideration for the planetary boundaries (for the Russian Federation as an example)

DOI 10.1515/pac-2016-0904

Abstract: Some scientists believe today that problems related to phosphorus entry into fresh-water bodies may be more important for setting the planetary boundary. Excessive entry of biogenic elements (especially phos- phorus) into water bodies and water streams causes their eutrophication. This process may cause a decrease in the light transmittance of surface water layers and other consequences for ecosystem and humans. In this paper the results of model application for the estimation of the phosphorus content in fresh waters of the Russian Federation regions are presented. The method for the estimation of the phosphorus amount in fresh water was developed on the basis of the dynamic model. Phosphorus loading is most characteristic of regions that have developed types of agriculture which cause increases the rate of mineral phosphorus entry into erodible soil.

Keywords: freshwater eutrophication; ICPC-21; phosphorus; phosphorus loading; planetary boundaries; regional estimation; water quality.

Introduction

In 2009, the “Planetary boundaries” concept was developed for the estimation of the biosphere sustainability under anthropogenic impacts [1]. The “Planetary boundaries” concept is based on the definition of bounda- ries for the safe development of humankind in the functional space limited by the dimensions of our planet [2]. One of the boundaries that was suggested was related to the global cycle of phosphorus. The phosphorus boundary was set on the basis of the state of the ocean waters: its value was set equal to a 10-fold pre-indus- trial amount of phosphorus compounds that enter the World ocean [1, 3] calculated in terms of elementary phosphorus. It was assumed in 2009 that the ingress of phosphorus into the World ocean was three times lower than this value [4, 5]. However, some scientists believe today that problems related to phosphorus entry into fresh-water bodies may be more important for setting the planetary boundary [5]. The economic activities in river catchment areas impact the natural cycle of matter by changing the flows of biogenic elements, thus leading to a decrease in their concentrations in certain areas and to accumulation in other areas. Excessive entry of biogenic elements (especially nitrogen and phosphorus) into water bodies and water streams causes their eutrophication [6–9]. Surface fresh-water bodies and some coastal waters are rather sensitive to eutrophication. The eutrophication of fresh-water body is a process of acceleration of

Article note: A collection of invited papers based on presentations at the 21st International Conference on Phosphorous ­Chemistry (ICPC-21) held in Kazan, , 5–10 June 2016.

*Corresponding author: Natalia P. Tarasova, D. Mendeleev University of Chemical Technology of Russia Miusskya Sq., 9, ­Moscow 125047, Russia, e-mail: [email protected] Anna S. Makarova, Evgeniya G. Vasileva and Diana D. Savelova: D. Mendeleev University of Chemical Technology of Russia Miusskya Sq., 9, Moscow 125047, Russia

© 2017 IUPAC & De Gruyter. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. For more information, please visit: http://creativecommons.org/licenses/by-nc-nd/4.0/ 288 N. P. Tarasova et al.: Estimation of the phosphorus loading algae growth and changes of their species diversity in surface waters due to enrichment of surface waters with biogenic elements [10, 11]. This process may cause a decrease in the light transmittance of surface water layers, degradation of surface algae layers, and deoxygenation, which in turn would cause fish kill and other consequences for ecosystem and humans [11, 12]. The control of eutrophication is an expensive activity [5, 13]. The problem itself is currently regarded as a global one [11, 14, 15] that will probably be escalated due to the growth of population and the corresponding demand for increased supply of food, expansion of agricultural land areas, and application of fertilizers [11, 16, 17]. The eutrophication of water bodies is observed in Russia as well [18]. Development of methods for the estimation of phosphorus loading on water bodies is an interdisci- plinary scientific and practical area of current interest. The modern approaches to the estimation of the impact of chemical compounds on the environment (water, air, soil, biota, etc.) are based on mathematical simulation methods that allow the impact of compounds throughout their entire life cycle to be estimated [19]. The majority of the models are based on linear differential equations that characterize the mass trans- fer between environments and that are converted to matrices in calculation of impacts from static sources [11, 20]. The same principles were used in calculations of phosphorus entry into the environment [11, 21]. The phosphorus impact on the environment is estimated using a mathematical model [19] that relates the amount of a compound entering water bodies from various sources with indicators of the water quality and ecological state of the water body. It should be noted that the phosphorus loading in the territory of the Russian Federation is not believed to be considerable in discussions on the planetary boundaries [22, 23]. However, preliminary calculations presented in [22] have shown that the situation with phosphorus entry into the environment may differ con- siderably depending on the region. To obtain reliable estimates, the calculations have to be detailed at the region level.

The method

The method for the estimation of the phosphorus amount in fresh water was developed on the basis of the dynamic model reported previously [5]. The amount of phosphorus in soil X1 and the amount of phosphorus in water X2 are determined by relationships (1) and (2): dX 1 =−Fk×−XkT × X (1) dt ter1dust 1

where: F is the value characterizing the rate of phosphorus entry into erodible soil, kg per year; X1 is the mass T of phosphorus in soil, kg; kter is the coefficient of phosphorus entry into fresh water, 1/year; k dust is the coef- ficient of transfer with dust, 1/year; dXX 22=×kX− (2) dt ter1τ

where: X2 is the mass of phosphorus in water, kg; τ is the mean residence time of phosphorus in water bodies in the territory in question, years. As one can see from relationship (2), the mass of phosphorus contained in surface fresh waters depends on the phosphorus entry from adjacent territories, water flow that decreases the phosphorus concentration, rate of phosphorus transfer to fresh-water bottom deposits, and phosphorus removal into a sea [5, 24]. The time of phosphorus removal from fresh water [11] calculated for objects in Russian Federation territory [21] was used in the model presented here. It should be noted as a limitation of the model that these calculations do not consider the amount of phosphorus that enters from the water bodies of adjacent regions. N. P. Tarasova et al.: Estimation of the phosphorus loading 289

Fig. 1: Algorithm for the calculation of the phosphorus amount in the catchment area.

The calculation algorithm is presented in Fig. 1. According to [4, 5, 25], the annual global gain in the phosphorus content in agricultural soils amounts to ca. 1010 kg per year. The annual phosphorus gain in erodible soils in the territories of the Russian Federation (RF) regions in question was estimated as the product of the annual global gain in the phosphorus content in agricultural soils by the fraction of agriculturally used area in the corresponding territory [21]. The amount of phosphorus entry into soil, F (kg per year) [13], was the sum of the phosphorus amount annually introduced with mineral fertilizers in each RF region [26] and the phosphorus amount entering with mechanical and chemical denudation, calculated per the fraction of the land area occupied by the terri- tory in question [5, 26]. It has been found [4] that the global phosphorus entry into surface soil layers due to weathering is between 1.5 · 1010 and 2 · 1010 kg per year. By summing up the rates of mechanical and chemical denudation (2 · 1013 kg per year) [27] with the mean content of phosphorus in the Earth crust (0.1 %) [28], it was assumed [29] that the current weathering of phosphorus is 2 · 1010 kg per year [4]. T 9 The mass of phosphorus transferred with dust k·dust X1 is estimated as 10 kg per year on the global level [5, 30]. Similarly to the estimation of mechanical and chemical denudation, the phosphorus transfer with dust is estimated for specific territories of interest based on the fraction of the territories with respect to the total land area [21]. The calculation of the mean residence time of phosphorus in water bodies in the territories of interest, τ (years), has been reported in detail [11, 21]. Let us assume as a first approximation that the annual phospho- rus gain in water bodies is 7.08 * 107 kg per year globally. We take this value as the averaged phosphorus gain obtained using the relationships from [5]. The annual phosphorus gain in water bodies located in the Russian Federation territories of interest was found as the annual global phosphorus gain in the water bodies divided by the total world resources of water and multiplied by the water resources in the region in question [32]. The global volume of surface fresh waters is estimated as 175 · 103 km3 (lakes) and 2 · 103 km3 (rivers), making a total of 177 × 103 km3 [5].

Results and discussion

The results of model application for the estimation of the phosphorus content in fresh waters of the Russian Federation regions are presented in Fig. 2. The concentrations were calculated using data on the mean water volumes in the regions [26]. 290 N. P. Tarasova et al.: Estimation of the phosphorus loading

Fig. 2: Estimated phosphorus concentrations in fresh water in RF regions, mg/L.

These data were compared to the data of field measurements performed in 2014 in the Republic of ­Buryatia and the Leningrad Region [31] (Table 1). In estimation of the impact of phosphorus that enters fresh water bodies, the following norms set in [32] were used (Table 2):

Table 1: Comparison of real data with calculated results.

Objects studied Actual concentration, Calculated mg/L [31] concentration, mg/L

Siberian Federal District, Republic of Buryatia Cross section of Tyya river 0.03 0.04 Verkhnyaya Angara river 0.01 Mysovka river 0.03 Total 0.023 ± 0.02 Northwestern Federal District, the Leningrad Region river 0.04 0.07 Svir’ river 0.02 Chernaya river 0.10 Naziya river 0.02 Total 0.06 ± 0.04

Table 2: The maximum allowable concentrations (MACs) [31].

Indicator Water body type MAC

Na, K, Ca phosphates Oligotrophic 0.05 mg/dm3 Mesotrophic 0.15 mg/dm3 Eutrophic 0.2 mg/dm3 N. P. Tarasova et al.: Estimation of the phosphorus loading 291

The calculated results show that phosphorus loading is most characteristic of regions located in the European part of the country, which matches the ecological situation related to the eutrophication of water bodies in this territory [22], as well as some regions of the Siberian and Far Eastern Federal Districts. Extremely high values (above 20 mg/L) marked maroon in Fig. 2 are characteristic of the Belgorod, Kursk, Lipetsk, Orel, and Tambov regions (Central Federal District) and Karachay-Cherkess Republic (North-­ Caucasian Federal District). This picture is observed due to the high amounts of mineral fertilizers applied per unit area of the region and the high fraction of the region area used as agricultural land. For example, the concentration of phosphorus in the fresh waters of the Lipetsk region was 20 mg/L upon application of 99.5 kg of phosphorus-containing fertilizers per 1 hectare, with the area of agriculture land being 81.4 % of the total area [26]. One of the lowest values (0.05 mg/L) is observed in the region, which is due to the small fraction of agricultural land (~ 19 %) while the amount of mineral fertilizers introduced is 77 kg per 1 hectare [26]. The calculated concentration was up to 36 mg/L in some regions of the Central Federal District. This agrees with the information presented in [32] where it is noted that unsatisfactory protection of water resources negatively affects the hydrochemical composition of water in rivers and water bodies in the Oka river basin, while the majority of small rivers in these regions are liable to degradation under the action of waste waters of agricultural production [32]. The enhanced concentrations of phosphorus (above 0.2 mg/L) in the catchment basins of such regions of the Siberian Federal District as the Kemerovo, Novosibirsk, Omsk regions, the Altai Territory, and the Zabai- kalye Territory are due to the fact that the mean fraction of territories occupied by agriculture in these regions is 40 % of the total territory. A similar picture is observed in the Primorye Territory and the Amur Region [26].

Conclusions

The method developed for estimation of phosphorus impact on fresh waters takes into account the entry of phosphorus from adjacent lands, the water balance of the region, the rates of phosphorus transfer into fresh-water bottom deposits and phosphorus removal into the sea, as well as phosphorus removal with water catchment. Using this model, an estimate of phosphorus impact on the fresh waters of RF regions was obtained. Phosphorus loading is most characteristic for regions of the European part of the country, as well as certain regions of the Siberian and Far-Eastern Federal Districts, which is due to the developed agriculture in these territories.

Acknowledgments: This research was supported by the Russian Science Foundation, grant 15-17-30016.

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