Water Air Soil Pollut (2017) 228: 141 DOI 10.1007/s11270-017-3327-3 Assessing Historical Mining and Smelting Effects on Heavy Metal Pollution of River Systems over Span of Two Decades Magdalena Strzebońska & Elżbieta Jarosz- Krzemińska & Ewa Adamiec Received: 25 November 2016 /Accepted: 2 March 2017 /Published online: 13 March 2017 # The Author(s) 2017. This article is published with open access at Springerlink.com Abstract Research was conducted on the most polluted two-decade legacy of extremely high contamination of river system in Poland, impacted by active and historical the Przemsza river sediments has persisted despite de- mining. Bottom sediment, suspended particulate matter creasing mining and smelting activity in the vicinity. and river water were collected in 2014 from Przemsza river and its tributaries. Sampling points remained the Keywords Historical mining . River bottom sediment . same as those chosen in a 1995 study. This allowed the Suspended particulate matter. Correlation coefficient comparison of heavy metal accumulation in bottom sediment over a span of almost two decades. It was concluded that Przemsza river water and its tributaries 1 Introduction are heavily contaminated with the following (in μg/ dm3): Pb (0.99–145.7), Zn (48–5020), and Cd 0.12– Multiple sources of mostly anthropogenic origin are 12.72). Concentrations of metals in bottom sediment causing pollution of aquatic environments with exceeded the background values by a factor of several heavy metals. The most recognizable are current hundred (100 times for Zn, 150 times for Pb, and 240 and historical mining and smelting industries, indus- times for Cd). The arithmetic mean for metal concentra- trial effluents, leaks from dumping site leakage as tion in fractions <63 μm sampled in 2014 has remained well as common use of fertilizers and pesticides, or comparable to the level found in 1995 (in mg/kg): Zn other surface runoffs. Heavy metals from atmospher- 16,918 and 13,505, Pb 4177 and 4758, and Cd 92 and ic emissions also enter rivers. As indicated by Church 134. It was determined that 20–50% more metals have and Scudlark (1998), they are responsible for the accumulated in suspended matter, rather than in bottom introduction of approximately 7% Cd, 4% Cu, 3% sediment (in mg/kg): 20,498 Zn, Pb 5170, and 164 Cd. Zn, and 2% both Co and Ni into aquatic environ- This exceeds the limits of the most polluted LAWA ments. Since heavy metals are persistent and not Class IV classification. Since the concentrations of Zn, degradable under normal conditions, they pose a Pb, and Cd increase drastically after the outlet of the serious threat to aquatic environment even for hun- Przemsza into the Vistula, it was concluded that river dreds of years after contamination. When introduced Przemsza is the cause of significant degradation of into rivers, they could be transported as compounds Vistula’s bottom sediment and suspended matter. A dissolved in water, be adsorbed onto suspended par- ticulate matter, or be deposited in river bottom sedi- ment. According to Martin and Meybeck 1979,al- M. Strzebońska : E. Jarosz-Krzemińska (*) : E. Adamiec AGH University of Science and Technology, 30 Mickiewicza most 90% of contaminants are incorporated in the Ave., 30-059 Kraków, Poland sediment-associated form rather than aqueous; this e-mail: [email protected] is mostly due to the sorptive nature of fine-grained 141 Page 2 of 11 Water Air Soil Pollut (2017) 228: 141 suspended particles (Miller et al. 2007;Taylorand physico-chemical parameters; for instance, lowering Hudson-Edwards 2008). Most riverbed sediments the pH (as a result of, e.g., active mining) promotes have fractions below 63 μm and are composed main- much easier transport of heavy metals from ly of quartz as well as minor amounts of feldspar and suspended matter into river water causing metals to carbonates. Finer fractions of sediments mostly com- become more available to living aquatic organisms pose of clay minerals, carbonates, or Mn and Fe and to further travel up to the end of the food chain. hydroxides and oxides. The bottom sediment heavy River bottom sediment is commonly considered as metals are not permanently fixed but can be period- a legacy of the past, especially where historical metal ically remobilized, desorpted, or redistributed along mining activity being the contamination source is the river course. Sediments act both as a sink and concerned. Most studies regarding contamination of secondary source of metal contamination in surface aquatic environment with heavy metals sourced from water systems (Singh et al. 2005). The process of active or historical mining activities focus on exam- remobilization of heavy metals from both suspended ination of only bottom sediment (Jabłońska-Czapla particulate matter (SPM) and bottom sediment is et al. 2016; Dadová et al. 2016; Hogarh et al. 2016). potentially more dangerous than the accumulation However, in order to assess other than historical itself. Mobility of contaminates is governed by sources of river contamination and to differentiate changes of various physico-chemical parameters in between historical and present anthropogenic pollu- which pH, redox potential, salinity, or the presence of tion sources, the investigation of suspended particu- complexation substances are of predominant con- late matter should also be considered. cern. For instance, lowering pH by one unit can cause The research involved examining the bottom sed- an increase of metal solubility by a factor of 10 iment, suspended particulate matter, and river water, (Förstner et al. 1990), which for example results in collected from the Przemsza river and its tributaries the dissolution of carbonates and hydroxides. More- in 2014. This is the most severely contaminated over, changing the redox condition from reducing to river in Poland. Its degradation can mostly be attrib- oxidizing also poses a great threat to the river envi- uted to current and historical mining activities. The ronment, since it promotes transformation of stable sampling points remained the same as these were metal sulfides into unstable metal sulfates. The use of chosen during sampling campaign in 1995 and car- river bottom sediment as environmental monitoring ried out by authors (Helios-Rybicka et al. 1998). tool is often difficult as has been indicated by many This allowed for a comparison of heavy metal accu- authors (Regnier and Wollast 1993;Larsenetal. mulation in bottom sediment over a span of almost 1988; Eisma et al. 1989). Suspended particulate mat- two decades. Moreover, an examination of ter on the other hand was reported to be much better suspended particulate matter was carried out in order suited for monitoring purposes (Ji et al. 2016; to differentiate between recent sources of anthropo- Onderka and Pekárová 2008;Lartigesetal.2001; genic pollution and historical ones. Adamiec and Helios-Rybicka 2002). The role of suspended particulate matter in the uptake, release, and transport of heavy metals is obvious. Therefore, 2MaterialsandMethods as stated by Turner and Millward 2002, SPM is a crucial link in heavy metal cycle between the water 2.1 Study Area column, bed sediment, and consequently food chain. Assessing the quality of SPM provides the informa- Przemsza river is one of the most polluted rivers in tion about load of contaminants released from river Poland and consequently in Europe. It comprises of bottom sediment but also from other more recent Biała and Czarna Przemsza and its total length equals point sources of pollution. Contaminants are more 87.6 km. It flows through highly industrialized and likely immobilized in bottom sediment, and they are anthropogenically transformed area of the Upper Sile- regarded as a potential source of contamination, in sia, and it enters the Vistula river near Oświęcim suspended matter; however, they are considered a (Auschwitz) (Fig. 1). real threat (Barbusiński et al. 2012). This component Multitude of factors of both natural and anthro- of the river system is also sensitive to the changes of pogenic origin influences this river’s pollution with Water Air Soil Pollut (2017) 228: 141 Page 3 of 11 141 msza rze scale P a n r a z C rzemsz a³a P a POLAND Bi Silesian Metropolis Warsaw P sampling r z area e m s z a V ISTULA scale CZECH REPUBLIC SLOVAKIA Fig. 1 Research area (Olczyk 2016; source: www.tyflomapy.pl) heavy metals. The most important ones are geolog- Pomorzany—is around 2.5 million tons of ore, and ical formations, lead-zinc and hard coal deposits, soon, the resources will be completely exhausted. mining, industry, urbanization, and air pollution. Geochemical background of Upper Silesia region is Pb-Zn ores are deposited at the depth of 50 to naturally elevated since prehistorical times, and due 400 m and are accompanied by silver and cadmium to weathering, abnormally high concentrations of deposits. This region is one of the biggest areas of Zn, Pb, and Cd were recorded. However, according zinc and lead deposits of so-called MVT (Mississip- to the research of Klimek (1993), concentration of pi Valley type), with parameters similar to deposits these metals spiked up in overbank sediments in the from the Mississippi River valley. The presence of last 100–150 years. It was found that the amount of these deposits led to the influx of population in the Zn,Cd,andPbinthefraction<63μmofoverbank area of Upper Silesia and the rise of the largest and river sediments of the Przemsza river and its tribu- most densely populated agglomerations in Poland. taries were one to two orders of magnitude higher These zinc-lead-silver ores are one of the oldest in when compared to the concentration of these metals Poland.TheywereminedintheareaofBytomfrom determined in the layers of sediments before indus- the Middle Ages, but now, they are mostly of his- trialization (anthropogenic pollution). torical significance. Despite the fact that in this region, there is still 2.2 Materials and Methods approximately 80 million tons of zinc and lead ores, exploitation of only 12.5 million tons of these geo- Samples of river water and bottom sediments were logical resources is profitable (data from 2010).