INFLUENCE OF ANTHROPOGENIC IMPACT ON THE PROCESS OF MANGANESE RELEASE FROM THE SEDIMENTARY STATE UNDER THE ACTION OF POLLUTANTS WITH REDUCING ACTIVITY IN THE CHERNAYA RIVER (Khabarovsk)
Journal: Water Conservation and Management (WCM)
Author: Oleg Kaminsky, Konstantin Makarevich, Diana Andreeva, Irina Sinkova, Olga Khomchenko, Evgeny Kirichenko, Anna Burkova
Print ISSN : 2523-5664
Online ISSN : 2523-5672
This is an open access article distributed under the Creative Commons Attribution License CC BY 4.0, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited
Doi: 10.26480/wcm.01.2025.68.71
Abstract
The article presents the results of the study of seasonal and spatial variations of manganese content in the waters of small rivers in urbanized areas of the south of the Russian Far East, using the example of the Chernaya River draining the vicinity of Khabarovsk, where anthropogenic impact creates reducing conditions in surface waters, leading to the release of significant amounts of manganese (more than 1000 μg/l), presumed to originate from the hydrolytic degradation of ferromanganese nodules in the absence of anthropogenic sources, with the process being most intensive in winter, and wastewater pollutants, indicated by the permanganate index, causing manganese release of 83 μg Mn (summer) to 387 μg Mn (winter) per 10 mg(O2)/l increase, with a maximum recorded content of 1198 μg/l Mn.
Keywords
Manganese, surface water, ferromanganese nodule,
1. INTRODUCTION
In the Earth’s crust, manganese ranks third among the most abundant transition metals (after iron and titanium) (Armstrong, 2008), with chronic exposure to toxic doses, known as manganism, first described by John Cooper in 1837 in two Scottish workers grinding manganese ore who developed paraplegia (Furbee and Dobbs, 2009), as manganese in toxic doses acts as a polytropic poison affecting lung tissue, cardiovascular and hepatobiliary systems, aggravating allergic processes, exhibiting mutagenic activity, and, in excessive drinking water concentrations, causing toxic effects on the pancreas, liver, and skin diseases (Ying et al., 2017), leading the World Health Organization to set a maximum concentration of 0.1 mg/l for drinking water supply systems (Usepa, 2004).
Manganese is an element with variable valence, with conditions in natural biogeocenoses and geological formations typically leading to the formation of manganese (II) and manganese (IV) compounds (Ma et al., 2023), while recent studies have focused on manganese (III) compounds (Shi et al., 2020; Oldham et al., 2017), which are metastable in aqueous solutions but stable in minerals, and at low concentrations, manganese serves as an essential trace element assimilated by aquatic organisms mainly as Mn2+, but at concentrations of 9.4 mg/L, it becomes toxic with a 48-hour LC50, e.g., for Daphnia magna (Howe et al., 2004), entering the body mainly via food and drinking water, necessitating its regular monitoring for human safety (Crapnell and Banks, 2022).
As experimental studies and computer modeling show, dissolved manganese is very mobile in the cationic form Mn2+. In this state, it is less prone to form chelate compounds compared to other trace elements such as Cu, Co, Ni, Pb or Zn (Abbasse et al., 2022; Charriau et al., 2011; Morgan, 2000). As a consequence, manganese in the soluble form is able to remain in the mobile state for a relatively long time and to be transported in water bodies for considerable distances.
Manganese is an example of a metal for which the influence of the content of organic pollutants on its migration activity is particularly significant. This is due to the fact that it actively interacts with the organic component of pollution, participating in redox hydrochemical processes. In this case, it is released from bottom sediments and transformed into the mobile ionic form Mn2+. When water is saturated with oxygen, the opposite process takes place. Manganese undergoes oxidation and transforms into insoluble form MnO2, turning out to be a part of bottom sediments. Significantly, the dissolved oxygen content presents a spatial gradient change (Kaufman et al., 2017, Mader et al., 2018), inducing complex dynamic biogeochemical processes (Meng et al., 2020, Zhu et al., 2020). These processes will change the redox conditions and nutrient distribution, impacting the biotic and abiotic transformation of various elements and compounds (Feng et al., 2023).
Fresh waters in the south of the Russian Far East are characterized by elevated background values of manganese. This is due to the fact that the geochemical peculiarity of this region is the presence of ferromanganese nodules confined to soils and the lower part of the Pliocene clay strata. Accordingly, Khabarovsk and its vicinity are located in the territory of the so-called province of ferromanganese fresh waters (Kulakov, 2013; Novikov et al., 2008). Up to 5000-8000 μg/l of manganese is registered in groundwater not infrequently. This is a significant problem for water treatment of such waters for drinking use (Kulakov 2013).
Most of the literature data on the mobility of various forms of manganese and its migration in watercourses describe the behavior of this element for much smaller concentration ranges than those given above. For example, the upper limit of manganese content in the waters of European rivers rarely exceeds 40 μg/l (Superville et al., 2018). As a result, the conclusions about manganese mobility obtained in such studies cannot be correctly transferred to the concentration range characteristic of Outer Manchuria waters. Unfortunately, to date, the level of study of manganese in surface waters in the territories with ferromanganese nodules is not high enough. In general, articles are limited to the study of groundwater only, where the conditions of hydrochemical processes differ significantly from surface water.
Thus, new migration pathways of heavy metals due to anthropogenic influence are formed in urbanized areas. The study is focused on a comprehensive study of migration pathways of manganese and biogenic elements, as well as identification of additional migration pathways due to anthropogenic-initiated processes in rivers draining urbanized areas. The objective of this study was to investigate the spatial and temporal release of manganese in watercourses of urbanized areas in the presence of ferromanganese nodules.
2. MATERIAL AND METHODS
2.1 Study Area
The Chernaya River drains the territory of Khabarovsk city and its surroundings (Figure 1, Table), with a longer length compared to other small rivers in the area, a river basin area of 255 km², and land use distribution as follows: residential area 7.1%, industrial land 6.7%, agricultural land 48.4%, and conditional natural land 37.8%, subject to various anthropogenic impacts but not receiving industrial wastewater with elevated heavy metals, including manganese, with wastewater in the studied section containing no more than 1.5-2 background values of manganese (10 μg/l (Solovov, 1990)).
2.2 Sites And Sampling
Apologies for missing that. Here’s the corrected version:
The coordinates of the points and their distance from the beginning of the sampling route are given in the table, with sampling points labeled from No1 to No7 for convenience, where wastewater is discharged in the river section bounded by sampling points No2 and No3, meaning two of the seven sampling points (No1 and No2) are upstream of the discharge, and the remaining five are downstream, respectively.
Samples were collected after the field test of the water quality parameters in 1500 ml plastic bottles, which were filled to the total volume and then locked with a cap so that no air space remained inside the bottle; the plastic bottles were first washed thoroughly with soda water, rinsed thoroughly with HNO3 and distilled water before collecting the sample to ensure they were completely free from any undesirable materials according to (APHA, 2017).
2.3 Hydrochemical and Data Analysis
Manganese concentration was determined using Agilent Technologies atomic absorption spectrometer: SpectrAA 240 FS AA (Crapnell and Banks, 2022).
The chemical composition (NH3, Pind, O2) of water was determined in the laboratory of the Collective Use Center of the Institute of Water and Ecological Problems of the Far Eastern Branch of the Russian Academy of Sciences using standard methods of hydrochemical analysis (D, 2012). Sampling was carried out in accordance with regulatory and legal documents in the period 2023-2024 (Gost, 2012; Gost, 2022; RD, 1996).
The number of cultured heterotrophic bacteria was determined by the method of limiting dilutions on agarized nutrient medium (fish-peptone agar diluted 10 times). The total dissolved organic matter content, after separation of suspended solids, was estimated by spectrophotometric method at 254 nm (Shimadzu UV-3600) and expressed as spectral absorption coefficient (SAC254, abs. units) (Thomas and Burgess, 2007).
The data were analyzed in STATISTICA 10 complex.
3. RESULTS AND DISCUSSION
The aim of this experiment is to evaluate the filtration system’s efficacy by comparing water quality before and after filtration. Municipal tap water, river water, and bottled mineral water are examined under an optical microscope, with pH measurements taken using pH paper. Bottled mineral water serves as a reference for comparison. The experimental flowchart is depicted in Figure 8.
The results of the monitoring show that the excess of background values of manganese in the studied watercourse is observed throughout the entire observation period, including both spring-summer and fall-winter periods, with the increase of manganese content below the main place of wastewater inflow ranging from 3 to 12 times, while the maximum recorded content was 1198 μg/l; analysis of the wastewater itself, which induces this release of manganese, showed that it contained no more than 9-17 μg/l manganese. Figure 2A presents data on spatial and temporal dynamics of manganese concentration changes in the waters of the Chernaya River, and Figures 2B, 2C, 2D show the hydrochemical parameters that have the greatest influence on manganese migration. In all presented graphs, we can distinguish 3 plots differing in the dynamics of changes in the registered indicators:
❖ Site (I), enclosed between points No1 and No2, has a length of 2.2 km and is characterized by minimal anthropogenic load and relatively stable values of both hydrochemical indicators and manganese content.
❖ Site (II) is bounded by points No3-No5 and has a length of 3.8 km, characterized by the maximum anthropogenic load, as the wastewater inflow occurs between sampling points No2 and No3, showing the greatest change in both manganese content and hydrochemical parameters, with incoming wastewater increasing the permanganate index by 3 to 11 times, most of the inorganic nitrogen present in the ammonium form (more than 90% of N total), and the oxidation of incoming organic matter consuming significant dissolved oxygen, causing its content to drop 6-20 times, resulting in a pronounced reductive hydrochemical environment favoring manganese reduction and its release from bottom sediments.
❖ At the last section (III), bounded by points No6-No7 and 23.2 km long, stabilization of hydrochemical indicators is noted, with their values returning to the levels typical for the first section, although it is important to note that the manganese content in water at this site either does not significantly decrease or continues its growth.
Analysis of the data obtained during the winter period shows that their dynamics has a number of principal differences from other observation periods. For example, the dynamics of manganese concentration change shows that at site (I) its content is comparable (or even lower) than at the same site in other observation periods. Further, at site (II) there is an expressive increase in manganese concentration by 2-5 times, and at site (III) there is an even greater increase in its content, which reaches 1198 μg/l. The change of other hydrochemical indicators indicates that a pronounced reductive hydrochemical atmosphere of the aquatic environment is formed in the river section after point No3. Unlike other seasons, the dissolved oxygen content remains very low (0.19-0.68 mg/l) not only directly after the wastewater discharge point, but also downstream. Inorganic nitrogen continues to be in a reduced ammonium form. As a result, such a pronounced reducing environment in the watercourse induces the greatest release of manganese in winter.
Thus, the intensity of manganese release in the winter period appears to be the highest. Formation of the maximum registered value occurs due to the increment of manganese content by 1088 μg/l relative to point No1. This increment is associated with the increase of permanganate index values by 28.4 mg O2/l. It follows that in the winter period the increase of permanganate index values for each 10 units additionally releases up to 387 μg Mn.
Analysis of the data obtained in the summer period shows that their greatest dynamics is confined not only to the site of the immediate area of sewage inflow, but also to the last interval of the monitoring area. Discharge of effluents also leads to the formation of a restorative hydrochemical environment. However, in contrast to the winter period, at the last monitoring site (point No7), both the level of water oxygenation (7.80 mg/l) and ammonium nitrogen content (up to 35.4%) return to the initial values (point No1). Thus, in the summer period the expression of reductive hydrochemical processes is much less. The section of the watercourse where such a reducing environment prevails is much shorter. This leads to the fact that manganese release is not so effective: the maximum recorded concentration of 416 μg/l is 3 times less than the winter one, besides, a weakly expressed trend is formed, leading to its decrease to 335 μg/l. Thus, the release of manganese in the summer period is the least intensive. Formation of the maximum registered value occurs due to the increment of manganese content by 178 μg/l relative to point No1. This increment is associated with the increase of permanganate index values by 21.5 mg O2/l. It follows that in the summer period the increase of permanganate index values for each 10 units additionally releases up to 83 μg Mn.
Analysis of the data obtained in spring and autumn periods shows that their dynamics is close to the summer period. At the same time, in the spring period the minimum manganese content (78 μg/l) among the registered values is observed. The formation of oxidizing hydrochemical environment is also observed at the last site. In spite of this, in contrast to the summer period of observations, even a weakly expressed trend of manganese content decrease in the spring and fall period is not traced. Thus, a similar release of manganese is observed in the spring and fall periods. Formation of the maximum registered value occurs due to the increment of manganese content by 312 μg/l (spring) and by 187 μg/l (autumn) relative to points No1. This increment is associated with an increase in permanganate index values of 21.8 mg O2/L (spring) and 12.1 O2/L (fall). This implies that during the spring and fall periods, an increase in permanganate index values for every 10 units additionally releases 143-155 μg Mn.
For the spring observation period, the microbiome pool of this watercourse was additionally studied (Figure 3). The data of the microbiological study agree well with the previously described results of hydrochemical studies. As expected, the river section downstream of the discharge area shows an expressive increase in microorganisms (MO) abundance. Primarily, the number of MOs increases due to the proportion attributable to primary reducing agents such as ammonifying bacteria (AB). There is then a decline in the number of MOs, first in the AB group and then in other groups. In turn, this follows a decrease in the content of the food resource – organic carbon. The decline in this indicator is observed both from SAC254, units abs. and permanganate index measurements. It is important to note that the processing of primary organic carbon from wastewater by the MOs probably leads to the formation of compounds (products of MO life activity) that contribute to the formation of an even more pronounced reducing environment. This agrees well with the data on the dynamics of oxygen content reduction, when the minimum of its concentration falls on the area following the area of active MO activity. The release of compounds easily involved in reductive processes by microflora may contribute to the increase in the intensity of the release process.
4. CONCLUSIONS
Assessing the toxicological danger of manganese release, we can say that the greatest intoxication for hydrobionts is observed in winter months, when the manganese content reaches more than 1000 μg/L. Manganese release is a consequence of the activation of reductive processes under conditions of pollutant input and simultaneously limited oxygen access due to ice cover. The intensity of manganese release is maximized in this case. On average, in the winter period the increase of permanganate index values for every 10 mg(O2)/l additionally releases up to 387 μg Mn.
In the absence of ice cover in spring-summer and fall, the intensity of reduction processes decreases. As a result, manganese release occurs with lower intensity. During the summer period, the intensity is minimal, when on average no more than 83 μg Mn is released with an increase in permanganate index for every 10 mg(O2)/l. During the rest of the warm season (spring and fall), the release of manganese is 143-155 μg for every 10 mg(O2)/l increase in permanganate index.
It should be noted that the effects of anthropogenic influence on the watercourse are quickly enough leveled in spring, autumn, and summer periods. This can be observed at the third section of the sampling route. Characteristic is the decrease of permanganate index value, ammonium nitrogen fraction, as well as total dissolved organic matter content estimated by SAC254 value. These data are in good agreement with the dynamics of decrease in the number of ammonifying and nitrifying bacteria.
It is especially important that even after the oxygenation level in the watercourse returns to stable-high values, there is no dynamics of manganese content decrease due to its oxidation to insoluble form MnO2. This fact is of particular concern, as it demonstrates the possibility of formation of new migration pathways of this element on the territory of this region, initiated by anthropogenic impact.
ACKNOWLEDGMENT
The research was funded by the grant Russian Science Foundation No 24-17-20002, https://rscf.ru/project/24-17-20002/ and contracts with the Government of Khabarovsk Region agreement No 100C/2024.
REFERENCES
Abbasse, G., Ouddane, B., Fischer, J.C., 2002. Determination of total and labile fraction of metals in seawater using solid phase extraction and inductively coupled plasma atomic emission spectrometry (ICP-AES). J. Anal. At. Spectrom., 17, pp. 1354–1358. https://doi.org/10.1039/B203407G
APHA, 2017. Standard Methods for the Examination of Water Quality, 23rd ed. s.l.
Armstrong, F.A., 2008. Why did nature choose manganese to make oxygen? Philos. Trans. R. Soc. B Biol. Sci., 363, pp. 1263–1270. https://doi.org/10.1098/rstb.2007.2223
Charriau, A., Lesven, L., Gao, Y., Leermakers, M., Baeyens, W., Ouddane, B., Billon, G., 2011. Trace metal behaviour in riverine sediments: role of organic matter and sulfides. Appl. Geochem., 26, pp. 80–90. https://doi.org/10.1016/j.apgeochem.2010.11.005
Crapnell, R.D., Banks, C.E., 2022. Electroanalytical overview: The determination of manganese. Sensors and Actuators Reports, 4, 100110. ISSN 2666-0539. https://doi.org/10.1016/j.snr.2022.100110
D 52.24.353-2012 ‘Sampling of land surface water and treated wastewater’
Feng, R., Duan, L., Shen, S., Cheng, Y., Wang, Y., Wang, W., Yang, S., 2023. Temporal dynamics of antibiotic resistance genes in the Zaohe-Weihe hyporheic zone: driven by oxygen and bacterial community. Ecotoxicology, 32(1), pp. 57-72. https://doi.org/10.1007/s10646-022-02616-5
Frisbie, S.H., Mitchell, E.J., Dustin, H., Maynard, D.M., Sarkar, B., 2012. World Health Organization discontinues its drinking-water guideline for manganese. Environ. Health Perspect., 120, pp. 775–778. https://doi.org/10.1289/ehp.1104693
Furbee, B., Dobbs, M.R., 2009. CHAPTER 26 – manganese. In Clinical Neurotoxicology, W.B. Saunders, Philadelphia, pp. 293–301. https://doi.org/10.1016/B978-032305260-3.50032-0
GOST 17.1.5.05-85 ‘Hydrosphere. General requirements for sampling of surface and sea waters, ice, and atmospheric precipitation’ (from 01.01.2023 GOST R 70282-2022).
GOST 31861-2012 ‘Water. General requirements for sampling’ (from 01.01.2023 GOST R 59024-2020).
Howe, P., Malcolm, H., Dobson, S., 2004. Manganese and its compounds: environmental aspects. World Health Organization, No 63.
Kaufman, M.H., Cardenas, M.B., Buttles, J., Kessler, A.J., Cook, P.L.M., 2017. Hyporheic hot moments: Dissolved oxygen dynamics in the hyporheic zone in response to surface flow perturbations. Water Resources Research, 53(8), pp. 6642-6662. https://doi.org/10.1002/2016wr020296
Kulakov, V.V., 2013. Use of in-situ purification of groundwater from iron and manganese (on the example of water supply of Khabarovsk). Vestnik FEB RAS, 2013.
Ma, A., Huang, Y., Mao, S., Li, S., Zhu, Z., Li, M., Liu, H., 2023. Mn(II) curtain, in the riparian sediment at the lower reaches of the Hanjiang River, China. Journal of Hydrology, 625, A130047. https://doi.org/10.1016/j.jhydrol.2023.130047
Mader, M., Roberts, A.M., Porst, D., Schmidt, C., Trauth, N., van Geldern, R., Barth, J.A., 2018. River recharge versus O2 supply from the unsaturated zone in shallow riparian groundwater: A case study from the Selke River (Germany). Science of the Total Environment, 634, pp. 374-381. https://doi.org/10.1016/j.scitotenv.2018.03.230
Meng, L.I., Zuo, R., Brusseau, M.L., Wang, J.-S., Liu, X., Du, C., Zhai, Y., Teng, Y., 2020. Groundwater pollution containing ammonium, iron, and manganese in a riverbank filtration system: effects of dynamic geochemical conditions and microbial responses. Hydrol. Process., 34(22), pp. 4175-4189. https://doi.org/10.1002/hyp.13856
Morgan, J.J., 2000. Manganese in natural waters and earth’s crust: its availability to organisms. In: Metal Ions in Biological Systems. Manganese and Its Role in Biological Processes, 37.
Novikov, V.M., Shkolnik, E.L., Zhegallo, E.A., Orleansky, V.K., 2008. Features of formation of hypergenic iron-manganese nodules (Russian Far East, Vietnam). Pacific Geology, 27(5), pp. 53-64.
Oldham, V.E., Mucci, A., Tebo, B.M., Luther, G.W., 2017. Soluble Mn(III)–L complexes are abundant in oxygenated waters and stabilized by humic ligands. Geochimica et Cosmochimica Acta, 199, pp. 238-246. https://doi.org/10.1016/j.gca.2016.11.043
RD 52.18.595-96 ‘Federal list of measurement techniques allowed for use when carrying out works in the field of environmental pollution monitoring’.
Shi, C., Bangjing, D., Yunbin, Q., Zhihao, C., Zhengkui, L., 2020. Nitrogen loss through anaerobic ammonium oxidation mediated by Mn(IV)-oxide reduction from agricultural drainage ditches into Jiuli River, Taihu Lake Basin. Science of The Total Environment, 700, 134512. https://doi.org/10.1016/j.scitotenv.2019.134512
Solovov, A.P., et al., 1990. Reference book on geochemical searches for minerals. Nedra Moscow.
Superville, P.-J., Ivanovsky, A., Bhurtun, P., Prygiel, J., Billon, G., 2018. Diel cycles of reduced manganese and their seasonal variability in the Marque River (northern France). Science of The Total Environment, 624, pp. 918-925. https://doi.org/10.1016/j.scitotenv.2017.12.189
Thomas, O., Burgess, C., 2007. UV-visible spectrophotometry of water and wastewater, Elsevier. pp. 360.
USEPA, 2004. Drinking Water Health Advisory for Manganese. U.S. Environmental Protection Agency, Off. Water Washington, DC, EPA-822-R-04-003, pp. 1-49.
Ying, S.C., Schaefer, M.V., Cock-Esteb, A., Li, J., Fendorf, S., 2017. Depth stratification leads to distinct zones of manganese and arsenic contaminated groundwater. Environ. Sci. Tech., 51(16), pp. 8926–8932. https://doi.org/10.1021/acs.est.7b01121
Zhu, A., Yang, Z., Liang, Z., Gao, L., Li, R., Hou, L., Li, S., Xie, Z., Wu, Y., Chen, J., Cao, L., 2020. Integrating hydrochemical and biological approaches to investigate the surface water and groundwater interactions in the hyporheic zone of the Liuxi River basin, southern China. Journal of Hydrology, 583, 124622. https://doi.org/10.1016/j.jhydrol.2020.124622
| Pages | 68-71 |
| Year | 2025 |
| Issue | 1 |
| Volume | 9 |
