The LIFE Pilica integrated project tackles these challenges by strengthening the capacity to implement key remedial measures from the Vistula River Basin Water Management Plan
promoting sustainable water management and ecosystem restoration
covering 183,000 km² (59% of Poland’s surface area)
is a vital environmental and economic region
spanning 9,251 km² across five voivodships
funded by the European Union’s (EU’s) LIFE program
aims to improve water quality in the Pilica catchment by implementing the River Basin Management Plan (RBMP)
It joins other EU water integrated projects
uniting stakeholders like local authorities
and environmental experts to address water ecosystem pressures
Specific measures involve improving rural wastewater management
and supporting blue-green infrastructure to manage non-point pollution in rural and urban areas
Challenges include coordinating efforts across diverse regions and ensuring stakeholder collaboration
LIFE Pilica takes part in the development of strategic documents on water management
and engages communities through education and awareness campaigns
This collaborative approach ensures sustainable and widely supported water quality improvements
the project aims to achieve 60% of environmental objectives in the basin
reduce blue-green algal blooms in Sulejów Reservoir by 25%
and increase ecosystem services like tourism by 20%
Public awareness of RBMPs is expected to rise by 30%
These efforts align with the EU’s Biodiversity Strategy for 2030
and restoring biodiversity through improved hydrodynamics and ecological continuity
the project impacts local economies and public awareness
it promotes sustainable water management practices
Long-term sustainability is ensured through education
ensures lasting improvements in water quality and biodiversity in the Pilica catchment
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Metrics details
The levels of polychlorinated dibenzo-p-dioxins (PCDDs)
polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the Pilica River and Sulejów Reservoir were found to be 46% higher during the flood season than during stable flow periods
PCDD/PCDF and dl-PCB mass loads increased by 5- to 12-fold and by 23- to 60-fold for toxic equivalency (TEQ) during flooding
The Sulejów Reservoir was found to play a positive role in reducing PCDD
PCDF and dl-PCB transport within the study period
with reductions ranging from 17 to 83% for total concentrations
Wastewater Treatment Plants (WTPs) were not efficient at mass concentration removal
with small displaying the least efficiency
WTPs discharge pollutants into the aquatic environment
they also produce sludge that requires disposal
PCDFs and dl-PCBs may be removed using phytoremediation
two efficient phytoremediators of organic pollutants
on polluted substrate resulted in a mean decrease in PCDD + PCDF + dl-PCB TEQ concentrations: 64% for cucumber and 69% for zucchini in sludge-amended soil
and by 52% for cucumber and 51% for zucchini in sediment-amended soil
riverine ecosystems are subject to strict monitoring
Poland is obliged to implement the objectives of the EU Water Framework Directive (2000/60/EC) regarding community action for water policy
and the chemical and biological status of water resources
Good river water status can be achieved by eliminating or reducing emissions from the most serious pollutants
the Water Framework Directive (2000/60/EC) and the Directive of the European Parliament and Council (2013/39/EU of 12 August 2013 amending Directive 2000/60/EC and 2008/105/EC) regarding priority substances in the field of water policy (Directive EQS) list 45 substances representing a serious threat to aquatic environments and to humans: these need to be removed from aquatic environments
Three groups of pollutants on the list are PCDDs
PCDFs and dl-PCBs allows them to bind to the organic and mineral particles in the river; in this bound form
they are transported along the river continuum and deposited downstream
which serve as long-term sources of pollutants
indicate that a thorough assessment of the condition of the environment is required before the degree of contamination can be reduced or reversed within the catchment scale
together with a quantification of the environmental problem
A broad spectrum of analyses is performed to determine the concentration of the given pollutant and its toxicity with regard to the individual components of the ecosystem (identification of threats); the results would clarify the interactions and processes that evaluate the levels of pollutants (analysis of cause-effect relationships)
The findings are then used to improve the quality of the environment (developing methods and tools for reduction of identified threats)
this study not only assesses the concentration and toxicity of PCDDs
PCDFs and dl-PCBs in the riverine environment
also defines their roles in the ecosystem and identifies the processes determining their concentrations
Its findings indicate opportunities for their safe removal
The contaminated sediment can be remediated by the development of environmental biotechnologies
such as microbial remediation and phytoremediation: these being the removal or detoxification of pollutants with the use of microbes or plants
The River Continuum Concept1 indicates that ecological processes occurring along the course of a river demonstrate continuity and geomorphological
The same is true for pollutants migrating along the river system: their levels should be interpreted across a broad space-time context which considers both the role of the catchment and the river itself
as well as the impact of present and past sources of pollution
Although the results obtained within our study highlight the positive influence of the Sulejów Reservoir with regard to pollution
they also clearly show the problems faced by the Pilica River and it reservoir associated with PCDD
As the quality of the sediment and water in the reservoir is determined by processes occurring across the whole catchment-river-reservoir system
the final dynamics and distribution of PCDDs/PCDFs and dl-PCBs are shaped by a complex interaction between the level of pollution and the existing biogeochemical (biological
chemical and physical) and hydrological processes related to the water cycle within a specific system
further analyses were performed to determine the impact of hydrological conditions and point sources of pollution on the concentrations
toxicity and distribution of PCDDs/PCDFs and dl-PCBs along the Pilica River continuum
Such drastic changes will dramatically increase the chance of extreme floods and droughts
and pose a serious threat to sustainable development
Since water is the primary medium responsible for the transport of matter
nutrients and pollutants from the catchment
their concentrations and loads will change dramatically in inland waters
It is worth to note that Polish emissions of PCDDs/PCDFs to air from residential combustion contributed to more than 70% of the total load from this source within the Baltic Sea catchment
Emissions to air are indicated to be an important source of the loads of these compounds to land and water ecosystems via dry and wet deposition and their further flushing to rivers during intensive rains
our study examined how the hydrological conditions prevailing in the Pilica River and its catchment influence the mass concentration
TEQ and distribution of PCDDs/PCDFs and dl-PCBs along its continuum
The study was conducted in three different sets of hydrological conditions occurring in the river: a period of extreme flow during spring flooding
one of stable flow and another of low flow during the dry season
Despite the strong influence of hydrological conditions on the noted values
PCDDs/PCDFs and dl-PCBs concentrations have not been related to the content of mineral
organic and total matter in the water samples nor the biogenic compounds such as phosphorus and nitrogen (Table 2SI)
stable and low water flow) on the spatial dynamics of PCDDs
PCDFs and dl-PCBs in the Pilica River along the river continuum from upland to downstream: A1–A3 – total concentrations; B1–B3 – TEQ concentrations
The role of hydrological factors (high
stable and low water flow) on total PCDD + PCDF + dl-PCB and total TEQ loads transported along the continuum of the Pilica River at Sulejów
stable flow conditions promote sedimentation and deposition of pollutants in the river and reservoir sediments
thus reducing the concentrations of studied compounds transported via water
thus preventing pollutants from being scoured from the river catchment and transported to the river ecosystem
and report a 49% reduction of TEQ concentrations of dl-PCBs in sediments within a 40-km natural meandering section of the Pilica River covered with a riparian vegetation community
A greater knowledge of such relationships will allow a better understanding of the functioning of complex river ecosystems and enable their efficient management
thus minimizing the transport and accumulation of micropollutants in the sediments of rivers
One example of these sources is that of outflows from WTPs
this analysis alone does not fully reveal the risks posed by the introduction of treated sewage into rivers
as wastewater may also contain several unmonitored pollutants
It should be emphasized that no current national legislation defines the permitted concentrations of PCDDs
PCDFs and dl-PCBs in wastewater discharged into rivers
Only Article 41 of the Polish Water Law Act requires that the sewage introduced into the water
but it does not regulate the limits for PCDDs + PCDFs
Regulation (EC) No 166/2006 of the European Parliament and the Council (18 January 2006) concerning the establishment of a Register of European Pollutant Release and Transfer
and amending Council Directive 91/689/EEC and 96/61/EC (amended) does set such limits (Regulation EC No
It specifies that the maximum PCDD + PCDF TEQ dose introduced through WTPs into the water column cannot be greater than 0.0001 kg/year
smaller WTPs are not monitored for concentrations of PCDDs + PCDFs
as this provision applies only to the largest WTPs: those with a population equivalent (p.e.) of more than 100,000
It is therefore important to determine both the range and variability of the PCDD
PCDF and dl-PCB concentrations within treated wastewater outflows from WTPs
as well as their impact on river water quality
PCDFs and dl-PCBs in treated wastewater coming from particular WTPs in the Pilica River catchment (Poland) classified into three categories of size: small
medium-sized and large WTPs: (A) concentrations of PCDDs
PCDFs and dl-PCBs (n = 2) (B) TEQ concentrations of PCDDs
PCDFs and dl-PCBs in treated wastewater coming from the three groups of WTPs size: small (n = 14)
medium-sized (n = 6) and large (n = 8) located in the Pilica River catchment: (A) mean (+/−SD) concentrations; (B) mean (+/−SD) TEQ concentrations
the TEQ values fell within a narrower range than the total concentrations
PCDFs and dl-PCBs (n = 2) (A) and PCDDs TEQ
PCDFs TEQ and dl-PCBs TEQ (n = 2) (B) in outflowing wastewater from small
medium-sized and large WTPs located in the Pilica River catchment (Poland)
PCDFs TEQ and dl-PCBs TEQ (B) in outflowing wastewater from small (n = 14)
medium-sized (=6) and large (n = 8) WTPs located in the Pilica River catchment
The highest load was generated by large WTPs. These discharge mean values of 748 +/− 404 µg of PCDD + PCDF + dl-PCBs to the river per day; while the small and medium WTPs discharged 31.6 +/− 30.1 and 57.6 +/− 19.4 µg per day, respectively. The same trends were seen for the sum totals of PCDDs, dl-PCBs and PCDFs (Fig. 6)
The mean TEQ loads increased together with WTP size, ranging from 1.45 +/− 0.58 µg/day for small WTPs, through 6.12 +/− 1.29 µg/day for the medium-sized WTPs, up to 56.1 +/− 16.8 µg/day for large WTPs (Fig. 6)
total PCDFs and total dl-PCBs were found to have a similar pattern
with the lowest loads observed for small WTPs and the highest for large WTPs
the concentrations obtained in our present study are relatively low to moderate
such comparison is complicated by the lack of detailed results
especially those regarding concentrations and loads of PCDDs/PCDFs at WTP outlets
There is a clear need for more research into the fate of PCDDs
PCDFs and dl-PCBs during wastewater treatment; such knowledge will improve the quality of water ecosystems though the design of more effective methods for their removal (e.g
PCDFs and dl-PCBs into the aquatic environment
WTPs also produce sewage sludge as the end product
This sludge is typically stored within the area of the WTP or disposed of in landfills or incinerators
over 31% of generated sludge is subject to storage and 14.5% to temporary storage (Statistical Yearbook of Environmental Protection
Our findings suggest that it may be possible to use the contaminated reservoir sediments and sewage sludge as fertilizer
This is supported by the fact that they are generally rich in organic carbon and macronutrients
One of the key elements of ecohydrology is the improvement of the environment through the use of ecosystem biotechnologies derived using specialized knowledge about naturally-occurring processes such as phytoremediation
Thanks to this considerable potential to sequester pollutants
the Cucurbitaceae represent an effective tool in the phytoremediation of PCDDs
Reduction of total PCDDs + PCDFs + dl-PCBs and TEQ concentrations in soil amended with sewage sludge (A1; A2) or bottom sediments (B1; B2) using cucumber (Cucumis sativus L.) and zucchini (Cucurbita pepo L.)
demonstrated a strong influence of sewage sludge on the plant metabolic activity
POx activity significantly increased to 149
265 and 234% of control values in variant amended with 3
GST demonstrated a statistically significant increase being 123
α-Tocopherol showed increased concentrations in the variants
however significant changes were observed when the highest dose of sewage sludge was applied
Obtained results demonstrated zucchini to be more sensitive to the applied doses of sewage sludge or sediments than the cucumber proving the validity and necessity for accurate and correct selection of plant species used for phytoremediation purposes
Pilica River catchment (central Poland) with the location of water (blue)
sediment (orange) and wastewater (red) sampling stations
was created by damming the Pilica River in Smardzewice (Central Poland) at km 137
The reservoir served as a water supply until the end of 2012
the reservoir is used to ensure constant river flow
the minimum width in the dam region is 1 km
Two grams of each representative sample was used for further determination of PCDD/PCDF and dl-PCB content
River water samples were collected during the following conditions:
During high water flow (May 2010) in the Pilica River: Under these conditions
water level exceeded the flood alarm level at the water gauge in Sulejów (230 cm
and the corresponding discharge Q = 79.7 m3/s) and the discharges at the Sulejów and Spała stations amounted to 216 m3/s and 180 m3/s (Table 2SI)
During serene water flow (September 2010): Under these conditions, the discharges at the Sulejów and Spała stations amounted 38.3 m3/s and 54.6 m3/s, respectively (Table 2SI)
3) During low water flow (October 2012): The discharges at the Sulejów and Spała stations amounted to 17.6 m3/s and 23.9 m3/s, respectively (Table 2SI)
More information regarding the monitoring stations and the physical and chemical parameters during different flow conditions is given in Table 2SI
Two sets of samples were collected from each WTP in 2010: once during flooding in the spring and again during stable water flow in the summer
The samples were collected directly from the wastewater outflow into the Pilica River or its tributaries as described in River water
All samples were applied to soil at doses of 3
These were chosen to represent the maximum dose of sludge permitted on one occasion per year (3 t/ha) and over three years (9 t/ha)
as indicated by Polish Ministry of Environment Regulations (Polish Journal of Laws of 2015
4% and 8% of the total dry weight of the sample
Control samples consisted of vegetable potting soil obtained from Hollas Sp
Pasłęk (Poland) with no sludge or sediments
9 and 18 t/ha) was prepared in three replicates in polypropylene pots (capacity ca
500 cm3) and planted with zucchini and cucumber
‘Atena Polka’) and cucumber (Cucumis sativus L
‘Cezar’) seeds were germinated in Petri dishes for seven days
Seedlings at the same stage of growth and of the same size were then planted into pots containing control soil
soil amended with sewage sludge or soil amended with sediment: nine plants were used per variant - three pots were used for each type of soil
and three seedlings were planted in each pot
The plants were cultivated for a four-week period in a growth chamber under the following conditions: a temperature of 23+/−0.5 °C
16-hour light/8-hour dark cycle with 250 µmol m2/s photon flux density during the light period and 60% relative humidity
soil mixed with sewage sludge or sediment were collected twice during the experiment: at the beginning
to assess the initial concentration of PCDDs
to assess the removal efficiency of the compounds
Detailed analytical method used for the determination of PCDDs
Detailed procedure for solid (sediments and soil) and liquid (water and wastewater) samples is described in section “Field studies - Pilica River catchment”
The sample of sediment or soil (2 g) was spiked with isotopically-labeled standards (Cambridge Isotopes Laboratories
Extraction was performed with toluene using a Dionex 200 Accelerated Solvent Extractor (150 atm
Potential interference was removed with the use of neutral
and elution was performed using hexane (200 mL)
The obtained extracts were concentrated to 100 μL
initially by rotary evaporation and then under a gentle stream of nitrogen; the hexane was then replaced with nonane
PCDF and dl-PCB levels were determined using isotope dilution
high-resolution gas chromatography (HRGC) and high-resolution mass spectrometry (HRMS) using an HP 6890 N Agilent Technologies Gas Chromatograph coupled with a high-resolution mass spectrometer (AutoSpec Ultima)
The GC equipment was operated in the splitless injection mode
The oven temperature was as follows: 150 °C for 2 min
The injector temperature was set to 270 °C
The mass spectrometer was operated under positive electron ionization conditions: 34.8 eV electron energy at a resolving power of 10,000 with an ion source temperature of 250 °C
helium (flow rate 1.60 mL per min) was used
Samples consisted of 2.00 L of water or wastewater
These were spiked with isotopically labeled standards (Wellington Laboratories)
The samples were then cleaned overnight in sealed semipermeable polyethylene membrane tubes (wall thickness 80.0 μm) using hexane (100 mL) Obtained dialysate was purified using a silica gel column coated with sulfuric acid and alumina
The final eluate was spiked with precision and recovery solution (20.0 μL) (Cambridge Isotopes Laboratories
USA) and evaporated to 20.0 μL in a gentle stream of nitrogen
PCDF and dl-PCB levels were determined by isotope dilution gas chromatography–mass spectrometry (ID-GC/MS–MS) on a Thermo Scientific GCQ-1100/ Trace2000 system equipped with Xcalibur data acquisition and analysis software
Congeners were separated on a DB5MS J&W capillary column (30.0 m × 0.250 mm i.d.) of 25-μm film and DB17 (30.0 m × 0.250 mm i.d.)
A sample of 2.50 μL volume was introduced into a SSL injector at 260 °C
The temperature profile of the GC oven was as follows: 130 °C for 3 minutes
50 °C per min to 180 °C 2 °C per min to 270 °C
The result uncertainty was expressed as extended measurement uncertainty for k = 2 at a confidence level of 95%
The glassware used in the field and laboratory were cleaned with detergent
The glassware was additionally cleaned with acetone and hexane before use
The Teflon containers used in the field were also cleaned with detergent
QA/QC was ensured with the use of certified calibration standards
Each analytical batch included a method blank
Artifacts were assessed using a reagent blank while precision was confirmed by duplicate analyses
PCDFs or dl-PCBs were used to determine recoveries and to verify accuracy
CRM-490 fly ash Municipal waste and 1939a Polychlorinated Biphenyls in River Sediment A were used as standard reference materials
Detection levels for sediment and soil samples ranged from 0.11 to 0.84 pg/kg for PCDDs
Detection levels for water and wastewater samples ranged from 0.44 to 1.41 pg/L for PCDDs/PCDFs
PCDF and dl-PCB pollution of both the Pilica River and Sulejów Reservoir
with the determining role of hydrological conditions prevailing in the river itself and its catchment on the quoted concentrations
The values recorded during the flood season were around 46% higher than observed during the period of stable flow
the loads of the studied compounds transported during the flood increased from 5- to 12-fold in the case of the total concentration and from 23- to 60-fold in the case of Toxic Equivalency (TEQ)
The primary cause of such significant differences is the form of the hydrological conditions prevailing in the river itself and its catchment
The obtained results highlighted also the positive role of Sulejów Reservoir in reduction of the transported PCDD
In this case the obtained results demonstrated decreases in the studied compounds concentrations ranging from 17% to 83% for total values
this positive role may change over time e.g
and under reduced pollutant load or turbulent flow the sediments accumulated at the bottom of reservoir may act as a source of the studied compounds
The analysis demonstrated also that all 14 studied WTPs do not purify wastewater in a sufficient extent
PCDF and dl-PCB concentrations were observed in the small WTPs
an opposite situation was observed when the obtained values were calculated into loads discharged to the Pilica River and its tributaries
the highest loads were generated by large WTPs
discharged the smallest loads of studied compounds into the recipients
PCDF and dl-PCB into the aquatic environment
they also produce sewage sludge as the end product of the treatment process
There is also a need to utilize river and reservoir sediments contaminated with PCDD
PCDF and dl-PCB as an effect of their discharge via i.e
the contaminated sewage sludge and sediments served as the basis for the laboratory experiments aimed at assessing the effectiveness of cucurbits in removing PCDD
The obtained results revealed that these pollutants may be removed by using the contaminated sewage sludge and sediments as plants fertilizer
Application of cucumber (Cucumis sativus L.) and zucchini (Cucurbita pepo L.) resulted in a decrease in PCDD
PCDF and dl-PCB TEQ concentrations by an average of 64% (for cucumber) and 69% (for zucchini) in soil fertilized with sludge and 52 and 51% (for cucumber and zucchini
respectively) in soil fertilized with sediments
demonstrating a positive influence of the applied plants on the soil quality
The use of both field and laboratory studies, presented in the article, constitutes an example of a holistic, ecohydrological approach to addressing the problem of PCDD, PCDF and dl-PCB pollution within the river catchment (Fig. 1SI)
Insight into the role of complex interactions occurring in the catchment
allows enhancement in our understanding of hydrological and ecological processes to protect water resources
Such approach is intended to secure the ecosystem well-being for future generations and in this way brings benefits for society
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The field research was conducted within the framework of the National Science Centre
and of the Polish Ministry of Science and Higher Education Project No
The laboratory scale experiments have been founded under the Ministry of Science and Higher Education programme under the name “Iuventus Plus” for the years 2015–2017: Project No
and the project funded by the National Science Centre granted on the basis of the decision number DEC-2013/09/D/ ST10/04043
Data analysis and manuscript preparation was performed within the Kosciuszko Foundation scholarship programme for the year 2018 (A comparative study of the pollution status of two rivers located in catchments of different anthropogenic impact: the case of the Pilica and Hudson river)
European Regional Centre for Ecohydrology of the Polish Academy of Sciences
Faculty of Biology and Environmental Protection
Department of Plant Physiology and Biochemistry
Research design and field and laboratory data collection: U.M.
W.A.; analysis and interpretation of data: U.M.
Zi.M.; writing and revising of the manuscript: U.M.
The authors declare no competing interests
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations
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DOI: https://doi.org/10.1038/s41598-019-55973-3
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