Vol. 35 No. 4 2009 2

POLISH ACADEMY OF SCIENCES INSTITUTE OF ENVIRONMENTAL ENGINEERING COMMITTEE OF ENVIRONMENTAL ENGINEERING

ARCHIVES OF ENVIRONMENTAL PROTECTION

vol. 35 no. 4 2009 2

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 2009

CONTENTS

The Occurrence of Selected Trace Elements in Grain Fractions of Dust Emitted from Power, Coke and Cement Plants – Jan Konieczyński, Katarzyna Stec ...... 3 Measurements of Aerosol Size Distribution in Urban Areas of Upper Silesia – Krystian Skubacz ...... 23 Environmental Levels of Nitro-PAHs in Total Suspended Particulate Matter in Upper Silesia (Poland) – Marzena Zaciera, Wojciech Mniszek, Jolanta Kurek ...... 35 The Influence of Air-Conditioning System and Presence of Students on the Aerosol Concentration in the Auditorium – Bernard Połednik, Marzenna Dudzińska, Mariusz Skwarczyński ...... 45 Study of Aluminium Sulphate Complexes of Surface Water and Fractionation of Aluminium from Bottom Sediment – Marcin Frankowski, Anetta Zioła-Frankowska, Jerzy Siepak ...... 55 Occurrence Study of Agro-Chemical Pollutants in Waters of Supraśl Catchment – Katarzyna Ignatowicz ...... 69 Changes of Physicochemical Parameters and Phytoplankton in Water of a Submountain Dam Reservoir – Effect of Late Summer Stormflow – Ewa Szarek-Gwiazda, Grażyna Mazurkiewicz-Boroń, Elżbieta Wilk-Woźniak . 79 The Structure of Macrozoobenthos Assemblages in the Area of Sewage- Treatment Plant in Jurata – Jastarnia (The Puck Bay Coastal Zone) – Krystian Obolewski, Anna Jarosiewicz ...... 91 Sewage Sludge and Foam Management in Enhanced Biological Nutrients Removal Plant (EBNRP) – Jan Suschka, Eligiusz Kowalski ...... 105 The Effect of Microwave Radiation on Waste Treatment in a Reactor with a Biofilm – Marcin Zieliński, Mirosław Krzemieniewski ...... 119 Hydrochemical Conditions for Localization of Small Water Reservoirs on the Example of Kluczbork Reservoir – Mirosław Wiatkowski ...... 129 Changes in Water Quality of Zagreb Water-Pumping Sites – Mladen Zelenika, Božo Soldo, Bojan Đurin ...... 145 Profile Differences of Zinc, Copper, and Nickel Contents in Forest Soils on South-Podlasie Lowland – Dorota Kalembasa, Marcin Becher, Krzysztof Pakuła ...... 159 Contents of vol. 35 (2009) ...... 165 Authors Index of vol. 35 (2009) ...... 170

PL ISSN 0324-8461 3

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 3 - 21 2009 PL ISSN 0324-8461

THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS OF DUST EMITTED FROM POWER, COKE AND CEMENT PLANTS

JAN KONIECZYŃSKI1*, KATARZYNA STEC2

1 Institute of Environmental Engineering of the Polish Academy of Sciences ul. Skłodowskiej-Curie 34, 41-819 Zabrze, Poland 2 Institute of Glass, Ceramics, Refractory and Building Materials, Refractory Materials’ Branch ul. Toszecka 99, 44-101 Gliwice Poland Corresponding author e-mail: [email protected]

Keywords: Trace elements, respirable dust, emission factors, air contamination, technical methods of dust emission reduction, the effect of dust emitting sources on people.

Abstract: The emission of dust from power and industrial sources introduces a lot of contaminants into the air, including compounds of trace elements contained in fuels and raw materials. They are contained in respirable dust particles, creating hazard to human health. The results of investigations into the occurrence of selected trace elements in PM1, PM2.5 and PM10 fractions of dust emitted from coal-fired boilers equipped with air protection devices such as cyclone, electrofilter, wet and dry-scrubbing FGD plant have been presented. Dust emitted from a coke battery (battery heating) and rotary kiln for cement manufacture was also subjected to research. The research material was taken by means of a cascade impactor, enabling a fraction of different grain size dust to be separated from a stream of dust collected in an electrofilter. The ICP-AES method (of atomic emission spectrometry (AES) with plasma excitation) was used to determine the trace elements after prior mineralization of samples by microwave method. The results of measurements and analyses were presented by determining the ranges of trace elements occurrence in flue dust and emission factors in PM2.5. It was found out that big utility boilers and rotary kilns in the cement industry which are equipped with air protection devices meeting BAT requirements do not contaminate the air with dust and dust-related trace elements in the amounts that could create hazard. Excessive emission of dust, including a respirable fraction is still observed in the case of municipal heating plants equipped solely with mechanical dust separators (cyclones). Coke battery heating does not pose danger due to small range of influence.

INTRODUCTION

Poland and many countries belonging to the former eastern block saw their economies’ restructuring, which caused liquidation or reduction of the technologically outdated and power-consuming branches of industry. The changes resulted in the emergence of new branches or modernization of raw materials branch and power industry, which have maintained their important position in the national economy and have good prospects. There 4 JAN KONIECZYŃSKI, KATARZYNA STEC is a need to investigate the emission of dust and other contaminations from the currently operating units in power plants and municipal heating plants burning hard and brown coal, coke industry and cement industry. The previous studies are no longer useful due to technological progress and changes to the raw materials’ base. Examples of changes which have taken place in the power industry include the improvement of coal quality, low-emission combustion technologies, flue gas desulfurization and high-efficient electrofilter; in the coke industry liqidation of outdated production facilities, better airtight sealing of coke batteries, waste gas dedusting as well as coke dry cooling, in the cement industry – widespread application of the dry production method, partial replacement of coal with waste fuel, higher efficiency of flue gas cleaning. The aim of investigations is to provide information on the size and characteristics of the emitted dust, which is necessary to evaluate the threat to populations in industrial areas. In particular, it is important to investigate the share of respirable fraction dust and the content of trace elements compounds, including heavy metals. Twelve of them have been identified as hazardous air pollutants. They include: Sb, As, Be, Cd, Cl, Cr, Co, Pb, Mn, Hg, Ni and Se. Emitted into the air from natural and anthropogenic sources, they are subject to wet or dry deposition, exerting a harmful influence on biological functions in the human organism, where they penetrate chiefly through respiratory tracks, but also via the alimentary system, participating in particular links of food chain. The amount of emission is recorded on a national, continental and global scale, which requires continuous updating.

AIR CONTAMINATION WITH TRACE ELEMENTS’ COMPOUNDS

Most trace elements are chemically very active and their low concentrations play an important role in the development and functioning of human organisms. However, in the case of higher concentrations they may inhibit biological processes or become toxic compounds. The higher solubility of a given metal salts, the higher probability of metal toxicity increase, which may lead to acute as well as chronic poisoning both as a result of exposure at a workstation and in the polluted environment. Harmfulness of trace elements contaminating the environment in great measure results from their biochemical and biological properties, which influence the following phenomena: − susceptibility to bioaccumulation: − from water environment, e.g. Hg, Cd, Pb, Cu, Zn, Sr; − from the soil, e.g. Cd, Zn, B, Sn, Cs, Rb; − concentration in biolites due to geological processes, e.g. Ba, Be, V, Se, B, Ge, Rb, La, Ce, Pb, F, Zn, U; − absorption from alimentary system, e.g. Hg, Cd, I, Zn, B; − penetration through placenta to fetus, e.g. Cd, Hg, Pb, Zn; − penetration through the biological barrier blood-brain, e.g. Hg, Pb, B, Al; − formation of connections with sulfidrilic groups of proteins, e.g. Hg, Pb, Se, Cd; − damaging of nucleic acids’ chain (especially RNA and DNA), e.g. Cu, Zn, Cd, Hg, Ni [7]. THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 5

The harmful effect that trace elements, in particular heavy metals which are natural micro-components of the earth crust, exert on biological functions is enhanced by their ability to move and accumulate between particular environment components. In most cases, trace elements are contained in the emitted dust, less frequently they occur as vapors or volatile compounds of these elements. Deposition processes usually take place when aerosols with metals contained in them are washed out with rainfall or when they drop due to the gravity force. In densely populated, urbanized and industrialized areas the size of contamination emissions is mainly influenced by anthropogenic sources – facilities in which mineral resources and fossil solid fuels are used and processed. The dust emitted due to mechanical processes: grinding, classification, mixing and transport most frequently do not differ from the processed raw materials in terms of chemical composition. On the other hand, in high-temperature processes fine grains are enriched with trace elements. Vapors of some of them after cooling condense mainly on the finest dust particles, the specific surface area of which is the biggest [15]. This frequently results in the enrichment of fine particles by trace components’ condensation, which has been confirmed on many occasions [3, 8, 16]. Dust emission from anthropogenic sources in Poland has been systematically abated due to economy modernization and improvement of waste gas dedusting technology. The structure of dust emission given in Table 1 [6] is characteristic of the countries which have recently followed the path of market economy.

Table 1. Emission of dust according to the type of activity in Poland in 2006

Type of activity Emission in thousands of Mg Total 447.5 Combustion processes in the sector of energy production and transformation 45.2 Combustion processes in the municipal and housing sector 179.0 Combustion processes in industry 49.1 Production processes 17.6 Extraction and distribution of fossil fuels 36.5 Road transport 55.3 Other vehicles and devices 12.7 Waste management 17.3 Agriculture 32.5 Other sources 3.2

Anthropogenic dust is mainly composed of mineral particles with the dimensions ranging from 0.1 to 100 µm – these are chiefly products of combustion processes (ash, soot, metal salts etc.) and other high-temperature processes (metallurgy, lime and cement industry etc.).

Fine particles of anthropogenic origin which form suspended dust (PM10) pose the biggest threat to human health as they occur in high concentrations in densely populated 6 JAN KONIECZYŃSKI, KATARZYNA STEC areas characterized by high industrial activity and due to the accumulation of metals having toxic properties and dangerous organic compounds, chiefly polycyclic aromatic hydrocarbons and dioxins. The major reason, however, is respirable fraction (PM2.5) contained in suspended dust, which creates health hazard [2]. The inhaled dust deposits in pulmonary alveoli and penetrates into the blood. This is estimated to be the cause of many general diseases, lung function deficiencies, asthma, bronchitis and different lung, heart and other organs diseases. Children, who use up 50% more air than adults per body mass, are particularly exposed. In the USA children account for 25% population, but the share of children in asthma incidence reaches 40% (according to EPA) [2]. It is estimated that every year 15 000 infants die there for this reason [14]. The emission of selected trace elements in Poland is recorded and similarly to dust emission, it is observed to be falling (Tab. 2), which concurs with the global tendency (Fig. 1) [19].

Fig. 1. Changes in the global emission of heavy metals [Mg/a]

In consequence, the relationship between the emission of dust and trace elements from anthropogenic sources reveals the effect that main economy branches using or processing big streams of resources and raw materials exert on the air quality. That is why utility, industrial and municipal boilers and coke and cement industry facilities have been chosen as the subject of investigations. The importance of these branches is confirmed by figures: Polish power industry uses 53.1 million Mg/a of hard coal and 60.2 million Mg/a THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 7

Table 2. Total emission of heavy metals in Poland in 2006 according to the type of activity

Specification As Cd Cr Cu Hg Ni Pb Zn Emission [Mg] Total 46.3 42.2 46.8 344.7 21.3 177.5 524.2 1303.2 Including: Professional power 2.8 0.2 3.5 8.9 8.3 7.3 10.7 26.1 houses and CHPs District heat plants 1.4 2.2 1.9 7.7 0.8 7.5 13.6 55.1 Municipal heat plants 1.0 1.6 1.4 6.0 0.2 5.4 10.4 41.5 Housing and services 13.1 20.1 15.6 68.9 1.0 66.2 115.9 465.2 Combustion processes in industry, boilers, turbines 1.1 1.7 1.4 6.0 0.5 7.4 10.4 42.0 and engines Production processes 1.0 2.6 9.3 18.3 1.4 6.8 90.1 171.4 Road transport 0.0 0.3 2.0 2.9 0.0 4.9 17.5 0.0 Waste incineration 0.0 0.1 0.0 0.1 0.1 0.0 1.4 0.9 of brown coal, coke industry products 9.7 million Mg/a, and the cement industry – 14.7 million Mg/a (the data provided by [5]). Owing to the development of dedusting and waste gas cleaning technologies, the excessive air contamination, among others with dust and trace elements compounds contained in dust particles, may be effectively prevented. However, even the most effective dust removal devices are not perfect: separation efficiency for a given type of device drops as the dust particles decrease. As a result, when the total efficiency of electrofilter exceeds 99%, separation efficiency of dedusting a fraction with particle size distribution below 0.4 mm does not exceed 95%. In consequence, the mass fraction PM2.5 in the emitted dust increases even up to 50%. The efficiency of capturing a number of trace elements (in solid phase) is close to the total dedusting efficiency. In the case of some elements (manganese, beryllium, chromium), enrichment is not high, slightly higher enrichment has been observed for antimony, lead, nickel and selenium, whereas the highest level of enrichment was found in the case of arsenic and cadmium [21]. In fly ash captured in a bag filter, more trace elements were found compared to flue dust arrested in an electrofilter [4]. A relative drop in the efficiency of fine fractions dedusting is lower in the case of bag filters. However, even when PTFE membranes are applied, the efficiency of filtration drops as grain size decreases [1]. Widespread application of flue gas desulfurization has also contributed to dust emission reduction. An FGD plant, most frequently using the wet lime method, placed behind the electrofilter, at the same time serves as the second stage dedusting, the total efficiency of which reaches 80%. Behind the FDG plant the mass fraction PM2.5 exceeds 90%, and the mass share of submicron fraction increases to 50%. However, this only refers to residual emission of flue gas, which accounts for maximum 0.05% of the total amount of ash produced in the process of coal combustion. Dust penetrating through FGD plant contains a considerable fraction (ca 50%) of gypsum and calcium. There is a proposal to call it fly dust, which better corresponds to the actual state than fly ash. Its composition slightly depends on the composition of coal mineral substance and the content of ash in coal [17]. Nevertheless, trace elements deposited on fine dust 8 JAN KONIECZYŃSKI, KATARZYNA STEC particles penetrate and escape into the air [18]. The emission factors for low volatility elements depend directly on the efficiency of flue gas dedusting and desulfurization [23]. In the assessment of the impact exerted by power facilities using hard or brown coal, the emission of PM2.5 fraction is of great importance due to the content of dangerous substances: PAH (Polycyclic Aromatic Hydrocarbons), dioxins and heavy metals, and due to this dust ability to penetrate into an organism via the respiratory tract. With reference to utility and heating boilers, it may be stated that the application of an effective electrofilter and wet desulfurization radically reduces threat caused by the emission of trace elements [17, 20].

ASSUMPTIONS OF THE STUDY

The proved harmfulness and even toxic effect that the compounds of trace elements, in particular heavy metals, have on people, encourage investigations into the occurrence of these substances in dust emitted from power and industrial facilities. This refers to installations which have maintained their strong position in the national economy after a change of the economic system in Poland. They include utility boilers and municipal heating plants based on hard and brown coal combustion, coke and cement industry. The previous national studies devoted to these problems are out of date now due to restructuring changes in the economy, economic progress and change of raw materials base. The assessment of the size and character of emission has been based on measurements and investigations into selected representative installations by analyzing the dust samples taken during full-scale industrial technological processes in production facilities. In hard or brown coal-fired power and heating plants the air quality is influenced by fuel circulation, which includes fueling, flue gas desulfurization and cleaning, removal of fly ash, slag from under the boilers and waste from flue gas desulfurization installations. Waste gas emission is of crucial importance due to the size of stream and height of chimney dischargers, enhanced by the effect of dynamic and thermal upheaval. Application of dedusting devices (electrofilters and bag filters) the efficiency of which exceeds 99% allows dust concentration in waste gas to be reduced to maximum 50 mg/m3. In power plants which annually burn several to several dozen millions Mg of coal, the removed waste gas is cleared of sulphur dioxide by wet or dry scrubbing method, which results in a further reduction of dust concentration to several mg/m3. The amount and composition of the compounds of selected trace elements contained in dust emitted from coal-fired boilers have been assessed by measuring basic parameters of waste gas as well as the amount and composition of dust penetrating through dedusting and desulfurization installation, at the sample-taking point (Tab. 3) placed behind these installations, before the waste gas is introduced into the atmosphere by chimney dischargers. In the coke industry the flue gas from coke gas combustion for coke battery heating is emitted in an organized way through a chimney discharger having the height of several dozen meters. Considerable noxiousness for the environment is caused by emission, which results from the fact that the coke process is not fully hermetized. The amount and composition of the compounds of selected trace elements contained in dust emitted from coke battery heating have been assessed by measuring basic parameters of flue gas as well as the amount and composition of dust at the sample-taking THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 9

Table 3. Characteristics of the investigated power/heating plants

Facility Type of Type of furnace Power Fuel Flue gas Flue gas cleaning boiler dedusting DD1 η [%] FGD2 η [%] P3 P3

Heating WLM 5 mechanical 5.8 MWt hard coal Cyclone 89 none plant Nowy stocker P Wirek

PEC WR 25 mechanical 32 MWt hard coal EF P 99 none Gliwice stocker

PEC WP 70 pulverized-fuel 81 MWt hard coal EF P 99 none Gliwice fired furnace, tangential furnace

Power BP 1150 pulverized-fuel 360 MWe hard coal EF 99.6 wet lime P 95 plant Opole fired furnace, tangential furnace Power BB 1150 pulverized-fuel 360 brown EF 99.6 wet lime P 95

plant fired furnace, MWe coal Bełchatów tangential furnace

Power OP 380 pulverized-fuel 120 MWe hard coal EF 99.6 dry- 87 plant fired furnace, scrubbing > Siersza tangential furnace FW P 99.6 Power- OPG 230 pulverized-fuel steam: hard coal EF P 99 none heating fired furnace, 230 Mg/h waste plant Nowa tangential furnace gases

DD1 – dedusting device, FGD2 – flue gas desulfurization plant, 3P – sample-taking point point (Tab. 3) before the outlet where flue gas is introduced into the atmosphere through chimney dischargers. In the cement industry the main source of flue gas emission is a rotary kiln, where a raw mix is heated, carbonates decompose, and calcium oxide reacts with acid oxides and material sintering, which results in clinker synthesis. Furnace gases cleaned in high- efficient electrofilters, with the content of dust reaching a maximum of several milligrams in a cubic meter, escape into the atmosphere through a high chimney discharger. Grinding of sintered clinker with additives is the last procedure. Waste gas from mills is cleaned in high efficiency bag filters, and next introduced into the atmosphere through a low or medium height chimney discharger. The residual emission of dust produced in the process of clinker grinding as well as packaging and shipment of cement is of marginal significance. The amount and composition of the compounds of selected trace elements contained in dust emitted from a rotary kiln for clinker have been assessed by measuring basic parameters of waste gas as well as the amount and composition of dust passed through an electrofilter at the sample-taking point placed behind the dedusting system, before the outlet where waste gas is introduced into the atmosphere through a chimney discharger.

AIM AND SCOPE OF THE STUDY

The aim of the study [11] is to extend knowledge on the sources and size of emission of selected trace elements that have been identified as dangerous air pollutants in Poland, 10 JAN KONIECZYŃSKI, KATARZYNA STEC which in consequence will allow basing the national register of these substances’ emissions on scientific grounds, thus making the continental and global inventory more precise. In particular, the aim of investigations is to identify a potential threat posed to people by respirable dust containing these substances, emitted from selected industrial facilities. The scope of the study includes selected trace elements in flue gas emitted by power boilers fired with hard and brown coal, from coke production installations (coke battery) and cement production facilities (rotary kiln). They include: antimony, chromium, cadmium, cobalt, manganese, nickel, lead, selenium and strontium.

CHARACTERISTICS OF THE INVESTIGATED INSTALLATIONS

Characteristics of the investigated power facilities Investigations were carried out for utility power plant and municipal heating plant widely used in Poland. They include the following boilers, listed according to the increasing degree of emission reduction: − hard coal-fired boiler with a mechanical stocker and cyclone for flue gas dedusting (Nowy Wirek heating plant), − hard coal-fired boiler with a mechanical stocker and electrofilter for flue gas dedusting (PEC Gliwice WR 25), − hard coal-fired boiler with a pulverized coal furnace and electrofilter for flue gas dedusting (PEC Gliwice WP 70), − hard and brown coal-fired boilers with a pulverized coal furnace and electrofilter for flue gas dedusting as well as wet lime FGD plant (Opole and Bełchatów power plants), − hard coal-fired boiler with a pulverized coal furnace and electrofilter for flue gas dedusting as well as dry scrubbing FGD plant and a bag filter to purge flue gas of dry desulfurization products (Siersza power plants), − boiler fired with hard coal and waste gases with a pulverized coal furnace and gas burners equipped with electrofilter for flue gas dedusting (Nowa power- heating plant). The characteristics of these installations have been given in Ta- ble 3.

Characteristics of coke installations The coke battery number 5 at Coke Plant Przyjaźń in Dąbrowa Górnicza was subjected to investigations. At that time it was the most modern coke battery in Poland. Coke Plant Przyjaźń is the second biggest Polish coke plant, producing over 25% of coke in Poland, its annual production capacity reaching 2.5 millions Mg of coke. The characteristic of this facility has been given in Table 4.

Characteristics of cement production installations Dyckerhoff Polska Sp. z o.o. belongs to Buzzi Unicem Group, which has a leading position among building materials producers around the world. In Poland, where it sells over a million Mg of cement annually, it is included in the group of ten biggest cement producers. The investigations were carried out in a modern Cement Plant Nowiny near Kielce, belonging to Dyckerhoff Polska Sp. z o.o. The characteristics of this installation have been given in Table 5. THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 11

Table 4. Characteristics of coke battery number 5 in Coke Plant Przyjaźń

Specification Unit Size Number of chambers piece 2 x 38 Dimensions of cold chamber: length, 15040 height, [mm] 5500 width 410 Chamber capacity [m3] 33.91 Capacity of coal charge in chamber [m3] 30.3 Dry coal charge in chamber [Mg] 21.63 Coking cycle [h] 15–16 Yield from 1 Mg of dry charge: dry coke, anhydrous tar, 767.1 crude benzol, [kg/Mg] 36 010.4 crude gas 3 3 Wd = 17.6 MJ/m (conventional) [m /Mg] 355.0 Dry coke produced in chamber [Mg] 16.59 Daily production of dry coke [Mg] 1924.4 Annual production of dry coke [Mg] 702400

Table 5. Technical and technological data of rotary kiln in Cement Plant Nowiny (Dyckerhoff)

Specification Unit Size Length [m] 65 Diameter [m] 4.6 Slope [%] 3 Kiln revolutions [rev./min] 2.5 Production of clinker [Mg/d] 2100 Fuel: coal, [Mg/h] 12 heavy oil 6 Stream of gases thousands of m3/h 3200–3700 Initial temperature of gases [K] 1473–1673 Oxygen content in gases [% vol.] 8.5–11 Dedusting device electrofilter Dust emission [kg/h] 1.14–2.33

METHODOLOGY

Measurement of the emitted dust grain size composition and sample taking Grain size composition of the emitted dust was measured by determining the mass of dust arrested in particular stages of the cascade impactor, introduced into the flue gas conduit behind the dedusting device. A six-stage impactor Andersen Mark III with a final filter which captures the finest dust grains was used. The masses of separated grain fractions were measured by means of Mettler Toledo scales with 2 μg accuracy. In order to average the results for each facility and to compare granulometric composition of dust measured 12 JAN KONIECZYŃSKI, KATARZYNA STEC in particular facilities, the results of all measurements were referred to the same, unified fraction ranges: < 1, 1–2.5, 2.5–10 and > 10 μm. The method of measuring, interpreting the results and determining the emission factors of dust granular sizes has been described in a publication devoted to similar investigations [13].

Determination of trace elements in dust Before trace elements were determined by ICP AES method, the samples were pulped in a mineralizer with focused microwave energy. Filter papers with the examined dust were 3 placed inside a reaction vessel and 15 cm of HNO3 was added. After closing the vessel, the microwave system worked for 60 minutes, using 600 W output. The process temperature was 483 K, pressure in the autoclave was 15 bar. Next the samples were transferred to an induced plasma spectrometer with optical detection. During the analysis, optimized measurement parameters were applied to the spectrometer.

RESULTS

Emission factors EFPM1, EFPM2.5 and EFPM10 from the investigated facilities On the basis of the measured mass streams of the total emitted dust and fuel or fuel chemical energy consumed as well as the product obtained (coke, cement), the emission factors EFPM1, EFPM2.5 and EFPM10 in kg/Mg were calculated. The emission factors are given in Table 6.

Table 6. Emission factors EFPM1, EFPM2.5 and EFPM10 from the investigated plants EF EF EF Facility PM1 PM2.5 PM10 [kg/Mg] Heating plant Nowy Wirek WLM 5 1.809 2.925 7.983 PEC Gliwice WR 25 0.124 0.223 0.344 PEC Gliwice WP 70 0.106 0.217 0.818 Power plant Opole BP 1150 0.023 0.046 0.197 Power plant Bełchatów BB 1150 0.042 0.060 0.130 Power plant Siersza OP 380 0.002 0.004 0.120 Cement Plant Nowiny BDL 0.020 0.078 Coke Plant Przyjaźń 0.009 0.019 0.028 [kg/GJ] Power-heating plant Nowa OPG 230 0.013 0.018 0.088

BDL – below detection limit

Concentration of selected trace elements in the emitted dust When measuring the emitted dust granular composition by means of a cascade impactor, 340 samples were obtained for trace elements determination. The mass of individual samples was small: from a part to a few mg. In order to ensure a necessary concentration of analytes, the samples containing grains within a similar diameter range: 0–1 mm, 1–2.5 mm and > 2.5 mm were mineralized jointly. The concentration of the investigated trace elements in granulometric compositions of the emitted dust has a very wide range. As an example, a full range of the measured concentrations [ppm] and a range limited to values THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 13 found in 80% of the examined samples of dust emitted from boilers have been presented in Table 7.

Table 7. A full range of concentrations measured [ppm] and a range limited to values found in 80% of samples of dust emitted from the investigated boilers

Average Median Minimum Maximum P P Element 10 90 concentrations [ppm] Cd 7.16 BDL BDL 44.10 BDL 28.03 Co 23.48 12.81 BDL 82.08 BDL 65.13 Cr 1169.59 575.49 51.99 7184.12 68.31 2054.30 Mn 648.96 246.08 BDL 3179.94 68.86 1450.62 Ni 2449.76 1048.33 BDL 16374.83 160.67 6177.76 Pb 74.94 30.06 4.66 514.04 6.71 235.66 Sb 63.77 BDL BDL 421.04 BDL 270.79 Se 353.09 149.84 BDL 2366.48 BDL 696.15

BDL – below detection limit

Emission factors of selected trace elements from the tested facilities The measured concentrations of selected trace elements were used to calculate emission factors of these substances from the examined installations. To this end, we used the emission factors of dust WPM2.5 (Tab. 6) determined on the basis of measurements taken in the investigated installations and the data on the content of a given trace element related to

PM2.5 fraction in the emitted dust, expressed in mg/kg. Trace elements content was calculated by multiplying PM2.5 mass fraction in a unit of total dust mass by the concentration of a given trace element in PM2.5 fraction contained in the emitted dust composition. The obtained results for five boiler installations have been given in Table 8. On the basis of dust emission factors and elements contents in PM2.5 fraction, the emission factors (EFi) for particular trace elements in respirable fraction – PM2.5 emitted by boiler installations, coke battery heating facility and a rotary kiln (Tab. 9) were calculated. Emission factors

Table 8. Contents of selected trace elements in PM 2.5 emitted from the investigated boilers

Heating plant PEC Gliwice PEC Gliwice Power plant Power plant Element Nowy Wirek WR 25 WP 70 Opole Siersza WLM 5 BP 1150 OP 380 contents [μg/g] Cd BDL 7.14 BDL 7.45 BDL Co 16.42 22.49 1.62 12.31 0.31 Cr 547.49 393.53 217.15 102.79 22.31 Mn 347.39 74.35 68.05 191.23 16.92 Ni 712.61 610.12 331.07 137.46 63.84 Pb 35.80 16.80 4.79 30.53 3.90 Sb 118.21 23.92 8.77 BDL BDL Se 151.21 84.13 19.33 45.14 BDL

BDL – below detection limit 14 JAN KONIECZYŃSKI, KATARZYNA STEC for Nowa power-heating plant were not determined as its boiler fired with such fuel has an individual character. Due to lack of more space in this study, data on trace elements’ concentration in granular fractions of the emitted dust and mass granular fractions in a unit of total dust mass have not been included.

Table 9. Emission factors of selected trace elements contained in PM2.5 emitted from the investigated plants Element Plants Heating PEC PEC Power Power plant Power Cement Coke plant Gliwice Gliwice plant Bełchatów plant Plant Plant Nowy WR 25 WP 70 Opole BB 1150 Siersza Nowiny Przyjaźń Wirek BP 1150 OP 380 WLM 5 [mg/Mg] Cd 0.0 1.6 0.0 0.3 0.4 0.0 0.0 0.3 Co 48.0 5.0 0.4 0.6 0.7 0.0 0.4 3.1 Cr 1601.4 87.8 47.1 4.7 145.4 0.1 6.2 92.4 Mn 1016.1 16.6 14.8 8.8 59.2 0.1 4.6 33.5 Ni 2084.4 136.1 71.8 6.3 325.7 0.3 9.9 185.0 Pb 104.7 3.7 1.0 1.4 0.7 0.0 0.7 6.5 Sb 345.8 5.3 1.9 0.0 0.9 0.0 0.1 6.7 Se 442.3 18.8 4.2 2.1 22.6 0.0 1.0 13.6

DISCUSSION

In this study it has been assumed that the tested plants affect the environment due to the emission of this part of dust which is not arrested in flue gas dedusting installations and escapes into the air, carrying the deposited contaminants, among others trace elements. That is why the determined emission factors of dust and selected trace elements as well as technical factors influencing their size are noteworthy. Respirable dust is especially important due to its effect on people. It was found out that boilers fired with hard coal and not equipped with FGD plant emit dust with 12% to 20% of PM1 fraction. PM2.5 fraction accounts for 20–35%. In flue gas from boilers fired with brown coal, the 1PM and PM2.5 fraction is the biggest, reaching 32% and 46% respectively. The application of a filter bag in the case of dry-scrubbing desulfurization method considerably reduces the PM1 fraction to 1% and PM2.5 to 2%. A boiler fired with coal and metallurgical gases, equipped with an electrofilter (Nowa power-heating plant) was also subjected to investigations – it was found that PM1 and PM2.5 fractions were similar to those in the above discussed first group of boilers. This results from the dominant fraction of mineral substance contained in coal in the formation of fly ash in such a furnace. Flue gas emitted due to battery coke firing is produced as a result of refined coke gas combustion. PM1 and PM2.5 fractions are high, reaching 31% and 67% respectively. It should be emphasized that flue gas from battery firing is not dedusted. Flue gas from a rotary kiln in a Cement Plant is produced as a result of hard coal and used car tyres burning, which are utilized in this way, thus reducing the consumption of coal. Flue gas contains fly ash produced in the process of coal and tyres burning, as well as particles of clinker – a product and small amounts of pulverized mineral resource. THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 15

Flue gas is dedusted by means of a high-efficient electrofilter. 2.5PM fraction reaches 25%, while PM1 fraction is very small (below 1%). The determined emission factors refer to different installations, which vary in their effect on the environment. Particularly important are emission factors from power and heating boilers which are used throughout the country and considerably affect the condition of air. It is easy to notice that big power boilers equipped with FGD plant are characterized by low dust emission factors. FGD plants provide the second stage of dedusting and together with electrofilters furnished behind the boiler effectively reduce dust emission. Application of a bag filter in desulfurization installations using dry-scrubbing method reduces the emission factors of PM1 and PM2.5 (respirable dust) to a very low value. Also boilers equipped with wet FGD installations have low PM1 and PM2.5 emission factors. A comparison of emission factors determined for a boiler equipped with a mechanical stocker, dedusted with a cyclone (heating plant Nowy Wirek WLM 5) and for a boiler with a mechanical stocker, dedusted by means of an electrofilter (PEC Gli- wice WR 25) confirms a possibility to radically reduce dust emission with an electrofilter installed on a boiler with mechanical stocker. PM2.5 emission factor is 13 times lower after a cyclone has been replaced by an electrofilter. Emission factors of dust from a rotary kiln in the Cement Plant, which is fired with coal and used car tyres prove that modern electrofilters effectively protect the air against contamination. Respirable dust emission factors are low. Low emission factors of dust produced in the process of coke battery firing indicate that emission from this source has a slight local effect. In order to assess the scale of hazard to population due to emission of dust containing dangerous substances, the emission factors of selected trace elements from the tested facilities have been calculated. Similarly to the emission factors of dust granular compositions, considerable differences are observed in the case of emission factors for selected trace elements, depending on the type of furnace and air protection devices furnished on the boilers. The emission factors range from tenth parts of mg to a few grams in relation to 1 Mg of fuel burnt. For obvious reasons the highest values of emission factors have been recorded for a boiler with a mechanical stocker, where flue gas is dedusted by means of a cyclone. Much lower emission factors are recorded in the case of boilers equipped with electrofilters, low emission factors – for dust boilers with electrofilters and dry-scrubbing FGD plant, and the lowest – in the case of dust boilers with electrofilters and dry-scrubbing FGD plant with a bag filter. For the elements considered dangerous, the emission factors of respirable dust PM2.5 [mg/Mg] have the following ranges: antimony 0–346; cadmium 0–1.6; chromium 0.1–1601; cobalt 0–48; lead 0–105; manganese 0.1–1016; nickel 0.3–2084 and selenium 0–442.

Emission factors of PM2.5 produced in the process of coke battery firing are quite high considering the fact that gaseous fuel is burnt. On the other hand, one should bear in mind that flue gas emitted by a battery is not dedusted.

Emission factors of PM2.5 produced in the process of clinker firing are quite low for chromium, manganese and nickel, their values reaching: 6.2; 4.6 and 9.9 mg/Mg of clinker. 16 JAN KONIECZYŃSKI, KATARZYNA STEC

EVALUATION OF POTENTIAL THREATS CAUSED BY THE EMISSION OF TRACE ELEMENTS CONTAINED IN RESPIRABLE DUST

When considering a potential threat posed by trace elements contained in respirable dust, a number of sources, i.e. dust emitting installations, activities of these sources and the prospects of their presence in the changing economies should be taken into account. There is a high probability that in Poland coal will continue to be used in professional and municipal power houses until the second half of the century. Power plants which burn hard coal are located throughout the country and several million people live within their range of influence. Coke plants are located in the central part of the Silesian Province, and the production of coke will probably decrease. Coke plants emit dust through medium height emitters or are a source of small range disorganized emission. The prospects of cement industry are stable. Due to high efficiency of flue gas dedusting the effect of modern cement plants on the environment is not big. That is why in the evaluation of potential hazards to the population; the attention was focused on boiler houses fired by hard coal.

To this end, calculations of PM1 and PM2.5 dust emissions from power plants, combined heat and power plants (CHP) and municipal heating plants were made on the basis of dust emission factors (Tab. 6) and previously described studies [12]. The aim of calculations is to prove that widespread application of modern flue gas dedusting electrofilters and wet FGD in power plants and CHP plants as well as replacing the cyclones with flue gas dedusting electrofilters in municipal heating plants may considerably reduce the emission of respirable dust and trace elements contained in it. The calculations have been based on the following assumptions: − boilers in all power plants and CHP plants are equipped with EF and wet FGD plant

and show PM2.5 emission factor equal to the one determined for power plant Opole;

− boilers in all municipal heating plants are equipped with cyclones and show PM2.5 emission factor equal to the one established for heating plant Nowy Wirek WLM 5 (option 1);

− boilers in all municipal heating plants are equipped with EF and show PM2.5 emission factor equal to the one determined for PEC Gliwice WR 25 (option 2). The results of calculations given in Table 10 prove that out-of-date solutions in a form of boilers with a mechanical stocker and cyclone working as a dedusting device result in PM1 and PM2.5 emissions disproportionate to the amount of coal burnt. PM1 and

PM2.5 emissions from these boilers are 9 and 7.5 times higher compared to the emissions in the subsector of power plants and CHP plants, burning nearly 9 times bigger amounts of coal.

Table 10. Estimated PM1 and PM2.5 emissions from power plants and CHPs in Poland after applying more effective technologies of air protection

Annual (2004) Annual emission [Mg] Air protection Type of source consumption of coal installation PM PM in millions of Mg 1 2.5 Utility boilers and CHPs 50.90 EF + wet FGD 1170.8 2341.5 Municipal heating plants 5.97 C 10799.7 17462.3 Option 1 Municipal heating plants 5.97 EF 740.3 1331.3 Option 2 THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 17

Practical application of emission factors also enables an annual assessment of the emission of a selected element from a particular boiler installation. To this end, model calculations have been made. Table 11 quotes the calculated emission of selected elements from a boiler equipped with a mechanical stocker (WLM 5) and cyclone working as a dedusting device (using the example of heating plant Nowy Wirek) and from a pulverized-fuel fired boiler (BP 1150) equipped with EF as a dedusting device and wet FGD plant (example – power plant Opole). The conducted simulation of calculations has shown that basic (and obsolete in actual fact) boiler equipment with air protection devices results in excessive emission of dust and its dangerous components. As a result, a small boiler burning 15 000 Mg of coal in a season contaminates the air much more than a big boiler burning 600 000 Mg of coal. It has to be added that the calculations were based on the emission factors which were measured for technical conditions and fuel used in the above mentioned facilities. Table 11. Seasonal emission of selected trace elements from two boilers with the older and technologically advanced installations of air protection

WR 25 BP 1150 Coal consumption [Mg/h] 5 200 Calorific value [MJ/kg] Pollutants 21 23 Boiler efficiency* [%] 82 91.7 Emission of selected pollutants [mg/GJ]** [kg/season] [mg/GJ]** [kg/season] Cd 0 0 0.013 0.180 Co 2.286 0.720 0.026 0.360 Mn 48.386 15.242 0.383 5.280 Ni 99.257 31.266 0.274 3.780 Pb 4.986 1.571 0.061 0.840 Sb 16.467 5.187 0 0 Se 21.062 6.635 0.091 1.260 * – boiler efficiency is a measure of losses in the process of converting the chemical energy contained in fuel to heat energy, ** – chemical energy of fuel

The calculations refer to a period of 3000 h, which corresponds to a heating season. They confirm the conviction that obsolete boiler installations need to be promptly withdrawn and prove that the emission factors of dust and trace elements contained in it, which have been determined on the basis of measurements and analyses, allow us to initially estimate the size of the investigated substances’ emission in the scale of the country and the effect of a particular type of emission source on the emission size. They may be used to assess the level of dangerous substances in the air and amounts of dangerous substances absorbed by people via respiratory tract. In order to initially estimate the degree of people’s exposure to the harmful or dangerous components of respirable dust, calculations were made on the basis of these substances’ contents in dust (Tab. 8) and the level of respirable dust measured in a big town 18 JAN KONIECZYŃSKI, KATARZYNA STEC

in the Upper-Silesian Agglomeration. In a heating season the high level of PM2.5 in the air is influenced by the emission of dust from numerous sources, also from municipal heat plants and professional power plants. Three options have been considered. In the option A an identical, definite amount of heat for the heating needs of a town is provided by a local heating plant using boilers with mechanical stockers equipped with cyclones as dedusting devices; boilers used in the option B are similar, but equipped with electrofilters; and in the option C the heat is supplied by a CHP plant using a boiler with a pulverized-fuel fired furnace equipped with an electrofilter and wet FGD plant. For the purposes of evaluation it is important to estimate correctly the level of respirable dust from the considered boilers in the ground layer of air. For this purpose, the measurement and computational data from our own research and literature sources were used. In the previously unpublished investigations which were carried out in Bytom in the Upper-Silesian Agglomeration, a maximum annual concentration of PM2.5 in the air, caused by the emission of dust from the local heating plant in this town was determined. It reaches 0.2795 mg/m3. These boilers with mechanical stockers are equipped with cyclones, so they correspond to the option A [13]. If these boilers were equipped with electrofilters in place of cyclones, and the activity of the sources, fuel, technical parameters of the heating plant as well as the conditions of waste gas emission and diffusion in the air did not change, then it might be assumed that in the option B the annual concentration of PM2.5 in the air due to dust emission from a modernized local heating plant in this town would amount to 0.0213 mg/m3 (compare

PM2.5 emission factors in Table 6). The emissions and environmental impact of PM10 and trace elements from a modern coal-fired power plant equipped with ESP and wet FGD plant [17]. The option C evaluated the effect of a boiler with a pulverized-fuel fired furnace, electrofilter and FGD plant, which works in a combined system, produces heat (thus replacing the complex of local heating plant) and additionally produces electric energy for other recipients. It was assumed that the dust emitted from this boiler is responsible 3 for 0.01 μg/m maximum annual concentration of PM2.5 in the air on the territory of the discussed town [17]. To be precise, it has to be added that in the above quoted publication the concentration of dust is PM10, in which the fraction of PM2.5 is more than 90%. On the basis of the presented data, an average amount of PM2.5 absorbed by a town inhabitant in a heating season may be estimated. If during 24 h the amount of inhaled air is 7 m3, and the heating system works at full power for 125 days, then in subsequent options the intake of

PM2.5 will reach 0.2446 mg (option A), 0.0186 mg (option B) and 0.0086 mg (option C). It must be remembered that in the option C only ca 30% of the boiler’s capacity produces heat – the remaining power is used to produce electric energy for other recipients. If the existing outdated boilers are replaced by modern boilers with EF and FGD with required power, then the amount of PM2.5 will be thirty times lower. With regard to the amounts of selected trace elements in the inhaled air, it has to be stated that they are very small. This is confirmed by the example of nickel contained in

PM2.5 emitted from a boiler in the option A. The measured amount of nickel: 712.61 mg/g is the highest among all the examined elements in the considered three types of boiler installations. (Tab. 8) The concentration of nickel in the air due to boiler emission in the option A reaches 0.1992 ng/m3, and a seasonal intake absorbed by a town inhabitant is 0.1743 mg. In the case of the remaining technical options and elements, the amounts are smaller. THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 19

With reference to human health hazard, an important factor taken into consideration is the number of particles. According to the literature data [17], one gram of fly ash from coal combustion is composed of 6.35·1010 particles. Hence, the seasonal amounts in mg which have been previously calculated for the three options, if expressed as a number of particles, are as follows: 15.5·106 option A 1.18·106 option B and 0.55·106 option C.

Certainly, this does not change the fact that the estimated amounts of PM2.5 from power installations which are the subject of investigations are a small fraction of mass or the number of respirable dust particles inhaled by the population. Nevertheless, fly ash produced in the process of coal burning is 100 or even 1000 times more enriched with some trace elements compared to their average concentration in the earth crust. The presence of numerous toxic substances in dust is probably accompanied by the synergic effect. Respirable dust comes from many sources, which should be subject of further investigations. A big role in the level of respirable dust is played by secondary dusting, which should be limited by taking better care of roads and streets. In the case of building, leveling and road works, waste utilization, mineral resources mining and other activities, the reduction of dust emission may be offered by technical, technological and logistic solutions as well as better organization of works.

CONCLUSIONS

It has been found out that big utility boilers equipped with air protection devices, fulfilling BAT requirements do not introduce dust and dust-related trace elements into the air in the amounts which could be considered dangerous. Municipal heating plants using only mechanical dust collectors (cyclones) continue to pose danger. The conducted computational simulation has shown that this results in an excessive emission of dust and its dangerous components. Application of electrofilters in place of cyclones in municipal heating plants may bring about a radical reduction of respirable dust emission and multiple reductions of selected trace elements. It has been found out that rotary kilns used in the cement industry, which are equipped with air protection devices and fulfill BAT requirements, do not introduce dust and dust-related trace elements into the air in the amounts that pose threat to humans. The calculated amounts inhaled via respiratory tract by people living within the range of influence of the outdated municipal heating plants may pose threat, given the synergic effect related to the simultaneous presence of dangerous substances. We should also take into consideration the emission due to coal burning in house stoves, which are quite common in unmodernized parts of towns. New coke plants fulfill the air protection requirements related to emissions due to battery heating.

REFERENCES

[1] Bologa A., H-R. Paur, H. Seifert, K. Woletz: Novel wet electrostatic precipitation for sub-micron particles, [in:] ‘DustConf’, International conference in Maastricht, 2007. [2] Fernandez A., J.O.L. Wendt, N. Wolski, K.R.G. Hein, S. Wang, M.L. Witten: Inhalation health effects of fine particles from the co-combustion of coal and refuse derived fuel, Chemosphere, 51, 1129–1137 (2003). 20 JAN KONIECZYŃSKI, KATARZYNA STEC

[3] Giere R., L.E. Carleton, G.R. Lumpkin: Micro- and nanochemistry of fly ash from a coal-fired power plant, American Mineralogist, 88, 1853–1865 (2003). [4] Goodarzi F.: Characteristic and composition of fly ash from Canadian coal-fired power plants, Fuel, 85, 1418–142 (2006). [5] Central Statistical Office, Environment 2006, Warsaw 2006. [6] Central Statistical Office, Environment 2008, Warsaw 2008. [7] Kabata-Pendias A., H. Pendias: Biogeochemia pierwiastków śladowych, Wydawnictwo Naukowe PWN, Warszawa 1999. [8] Karayigit A.I., Y. Bulut, X. Querol, A. Alastuey, S. Vassilev: Variation in fly ash composition from the Soma Power Plant, Turkey, Energy Sources, 27, 1473–1481 (2005). [9] Klejnowski K., W. Rogula-Kozłowska, A. Krasa: Struktura aerozolu atmosferycznego w Aglomeracji Górnośląskiej. Udział PM2,5 w PM10 w Częstochowie, Zabrzu i Katowicach w latach 2005–2007, [in:] Ochrona powietrza w teorii i praktyce, J. Konieczyński (red.), IPIŚ PAN, vol. 2, pp. 23–36, Zabrze 2008. [10] Konieczyński J., J. Żeliński: Ocena zagrożenia powietrza pyłem z obiektów energetyki zakładowej i komunalnej w woj. śląskim, Politechnika Śląska w Gliwicach, Gliwice 2003. [11] Konieczyński J. i współpracownicy: Właściwości pyłu respirabilnego emitowanego z wybranych instalacji, Raport końcowy z projektu badawczego MNiSW nr N207 041 31/1671, Zabrze 2008. [12] Konieczyński J., J. Kopyczyńska: Zastosowanie BAT i MECT do ograniczania uciążliwości źródeł energetycznych, [in:] Ochrona powietrza w teorii i praktyce, J. Konieczyński (red.), IPIŚ PAN, vol. 1, pp. 47–59, Zabrze 2008. [13] Konieczyński J., J. Żeliński: Granulometric composition of dust emitted from boilers with circulating fluidized beds, Archives of Environmental Protection, 35, 1, 3–11 (2009). [14] Laden F., L. Neas, D. Dockery, J. Schwartz: Association of fine particulate matter from different sources with daily mortality in six U.S. cities, Environmental Health Perspectives, 108, 941–947 (2000). [15] Mattigod S., D. Rai, J.E. Amonette: Concentrations and distribution of major and selected trace elements in size-density fractionated fly ashes, Biogeochemistry of Trace Elements in Coal and Coal Combustion Byproducts, Kluwer Academic Plenum Publishers, New York 1999. [16] Mazur J., J. Konieczyński: Distribution of trace elements in granulometrc fractions of fly ash emitted from power stations, (in Polish) Gliwice 2004. [17] Meij R., N. Winkel: The emissions and environmental impact of PM10 and trace elements from a modern coal-fired power plant equipped with ESP and wet FGD, Fuel processing technology, 85, 641–656 (2004). [18] Nielsen M.T., H. Livbjerg, C.L. Fogh, J.N. Jensen, P. Simonsen: Formation and emission of fine particles from two coal-fired power plants, Combustion Science and Technology, 174, 79–113 (2002). [19] Pacyna J.M, E.G. Pacyna: An assessment of global and regional emissions of trace metals to the atmosphere from anthropogenic sources worldwide, Environmental Reviews, 9:44, 12, pp. 269–298 (2001). [20] Suarez A.E., J.M. Ondov: Ambient aerosol concentration of elements resolved by size and by source: Concentration of some cytokine-active metals from coal- and oil fired power plants, Energy Fuels, 16, 562–568 (2002). [21] Swaine D.J., F. Goodarzi: Environmental aspects of trace elements in coal, Kluwer Academic Publishers, The Netherlands, 1995. [22] U.S. EPA: Hazardous Air Pollutants – HAP’s, Study of hazardous air pollutant emissions from electric utility steam generating units – Final Report to Congress, EPA-453/R-98-004a (February 1998), Utility Air Toxics Study, Exec. Summ. At ES-4. [23] Weber G.F.: A comprehensive assessment of toxic emissions from coal-fires power plans, Phase I.U.S. Department of Energy, 1996.

Received: 6 May, 2009; accepted: September 9, 2009.

WYSTĘPOWANIA WYBRANYCH PIERWIASTKÓW ŚLADOWYCH WE FRAKCJACH ZIARNOWYCH PYŁU EMITOWANEGO Z INSTALACJI ENERGETYCZNYCH, KOKSOWNICZYCH I PRODUKCJI CEMENTU

Emisja pyłu ze źródeł energetycznych i przemysłowych powoduje wprowadzenie do powietrza wielu zanieczyszczeń, w tym związków pierwiastków śladowych zawartych w paliwach i surowcach. Znajdują się one w ziarnach pyłu respirabilnego, co stwarza zagrożenie dla zdrowia ludzi. Przedstawiono wyniki badań nad występowaniem wybranych pierwiastków śladowych we frakcjach PM1, PM2,5 i PM10 pyłu emitowanego THE OCCURRENCE OF SELECTED TRACE ELEMENTS IN GRAIN FRACTIONS... 21 z kotłów spalających węgiel i wyposażonych w urządzenia ochrony powietrza takie jak cyklon, elektrofiltr, instalacje odsiarczania spalin metodą mokrą wapniakową i metodą półsuchą. Badano też pył emitowany z baterii koksowniczej (opalanie baterii) i z pieca obrotowego do wypalania cementu. Materiał badawczy został pobrany za pomocą impaktora kaskadowego umożliwiającego wydzielenie ze strumienia spalin odpylonych w elektrofiltrze frakcji pyłu o różnej wielkości ziarna. Do oznaczenia pierwiastków śladowych: Cd, Co, Cr, Mn, Ni, Pb, Sb i Se wykorzystano metodę atomowej emisyjnej spektrometrii o wzbudzeniu plazmowym (ICP-AES) po uprzedniej mineralizacji próbek metodą mikrofalową. Przedstawiono wyniki pomiarów i analiz określając zakresy występowania pierwiastków śladowych w emitowanym pyle i wskaźniki emisji w PM2,5. Stwierdzono, że kotły energetyczne o dużej mocy i piece do wypalania klinkieru w przemyśle cementowym wyposażone w urządzenia ochrony powietrza odpowiadające wymogom BAT nie wprowadzają do powietrza pyłu i pier- wiastków śladowych związanych z pyłem w ilościach stanowiących zagrożenie. Nadal nadmierną emisję pyłu, w tym frakcji respirabilnej, wykazują komunalne obiekty energetyczne stosujące jedynie odpylacze mecha- niczne (cyklony). Opalanie baterii koksowniczych nie stanowi zagrożenia ze względu na niewielki zasięg oddziaływania. 22 23

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 23 - 34 2009 PL ISSN 0324-8461

MEASUREMENTS OF AEROSOL SIZE DISTRIBUTION IN URBAN AREAS OF UPPER SILESIA

KRYSTIAN SKUBACZ

Główny Instytut Górnictwa Plac Gwarków 1, 40-778 Katowice, Poland e-mail: [email protected]

Keywords: Roads, ultrafine particles, fine particles, coarse particles, size distribution.

Abstract: Deposition of aerosols in the respiratory tracts depends on their size distribution. Investigation of such distribution has therefore great meaning for appropriate assessment of risk caused by hazardous pollutants that appear in environment both as a result of human activities like industry, emission from motor vehicles, municipal emission due to house furnaces and natural phenomena. The results of screening measurements of size distribution performed in several places located on highly populated areas in Upper Silesia, Poland are described in this paper. The applied equipment makes it possible to cover the range from several nanometers up to 20 µm, practically all particles that belong to the respirable class. Obtained results prove that a lot of particles having a size of the order of submicrons are produced close to high density traffic roads. This concentration strongly changed in time.

INTRODUCTION

Deposition of aerosols in the respiratory tract is mainly controlled by similar phenomena to those occurring during air filtration with fibrous filters. Therefore, diffusion, gravitational sedimentation and inertial impaction should be taken into consideration to explain the major transport mechanisms. Certainly, this process is influenced not only by physical aerosol properties but also by the breathing patterns and flow field in respiratory airways. The total deposition, as reported by Heyder et al. [4], increases with increasing breathing rate as a result of inertial impaction, especially for particles greater than 4 µm in diameter and mouth-breathing. Sedimentation has greater significance for aerosols below this diameter and longer residential time in the respiratory system. The third phenomenon, diffusion, is getting the dominant mechanism for particles not greater than 0.1 µm. Particles, which were not removed from the respiratory tracts by the clearing process, influence people and animals by penetrating into lymphatic pathways and connective tissues. Therefore, investigation of their size distribution is crucial for appropriate assessment of risk caused by hazardous pollutants that appear in environment both as a result of human activities like industry, emission from motor vehicles, municipal emission caused by household furnaces and natural phenomena. Radon and its progeny can serve as an example of natural hazards. Radon can penetrate from soil into buildings causing serious problems in some countries because of high- 24 KRYSTIAN SKUBACZ level radiation risk to inhabitants. After decaying of radon such isotopes as polonium- 218, lead-214, bismuth-214 and polonium-214 are generated. They are called short-lived radon daughters because their half-time, being less than 30 minutes, is short in relation to half time of radon equal approximately to 3.8 days. At the very beginning these isotopes occur as free atoms, ions or clusters that contain additionally vapors of gases (unattached fraction). Then, within 1–100 s, the radon progeny attach to ambient aerosols forming radioactive aerosols (attached fraction). This process is strongly affected by concentration and size distribution of ambient aerosols [10, 11]. Deposition of radioactive aerosols in the respiratory tracts and their radiotoxicity depends on half-time, aerosol size and total alpha radiation energy released by short-lived radon daughters. During decay of these isotopes beta and gamma radiation occur as well. This radiation however can be neglected because of its considerably lower, in relation to alpha radiation, linear energy transfer to tissue (absorbed energy per unit distance). As a result tissue damage due to alpha radiation is 20 times greater. According to the dosimetric model by Jacobi and Eis- feld [7] the greatest dose related to the unattached fraction of polonium-218 is absorbed in the tracheobronchial region (2–4 bronchi generation). Such isotopes as lead-214 and bismuth-214 occur mainly as attached fraction and affect at most the bronchi generations from 10 to 14. However, the influence of short-lived radon daughters on effective dose is commonly expressed as a combined effect. In the publication of the International Com- mission on Radiological Protection [6] the conversion coefficient is defined as effective dose per alpha radiation energy released by all these isotopes contained in unit volume and per exposure time. Such coefficient is a measure of hazardous effect of short-lived radon daughters on humans and depends strongly on aerosol size, breathing rate and breathing way. As it was proved, the most hazardous radioactive aerosols have a size

100

)] -3 J·h·m

10 Conversion coefficient [Sv/( 1

1 10 100 1000 10000

Aerodynamic diameter [nm]

Fig. 1. Dependence of conversion coefficient on particle diameter and breathing pattern: mouth-breathing (1.70 m3/h), mouth-breathing (1.20 m3/h), mouth-breathing (0.75 m3/h), nose-breathing (0.75 m3/h) from top to bottom curve respectively MEASUREMENTS OF AEROSOL SIZE DISTRIBUTION IN URBAN AREAS OF UPPER SILESIA 25 on the order of nanometers or near to the upper limit of respirable particles equal to 10 µm (Fig. 1). Measurement of radioactive aerosols and their size distribution is based on commonly applied methods, such as impactors and diffusion battery screens that are combined with such radiometric methods as alpha spectroscopy where the alpha radiation is spectrometrically detected to identify isotopes [12]. In the present publication, results of screening measurements of aerosol size distribution are discussed. Three sites were located in an urbanized region of Upper Silesia (Poland) and the last one far from roads and highly populated areas. Applied measuring devices made it possible to investigate the particles size distribution from several nanometers up to 20 µm. Such range covers practically all respirable class of aerosols. The respirable particles belong to one of the three categories mentioned in the EN 481 standard [14]. According to the definition this category consists of particles that reach the alveoli. Fifty percents of the particles with an aerodynamic diameter of 4 μm belong to the respirable fraction and their dimensions can reach approximately 10 μm. Particles of the thoracic class are able to pass the larynx, and 50% of the in-air-suspended particles with an aerodynamic diameter of 10 μm belong to this class. The largest diameter however can reach approximately 30 μm in this case. The broadest, so-called inhalable class, is composed of particles that can be inhaled by nose or mouth. Particles with aerodynamic diameter greater than 100 μm are not included in the inhalable convention. Another more detailed classification corresponds to the particles below 10 µm in size (PM10). Particles that are less than 0.1 μm in diameter are commonly defined as ultrafine, these with diameters ranging from 0.1 µm to 2.5 µm as fine, and these from 2.5 µm to 10 μm as coarse [2, 5, 8]. Sometimes an additional definition of “supercoarse particles” is applied, for particles that are greater than 10 μm in size [5].

MEASURING SITES

Measurements were performed in four sites. Two locations were close to busy roads, the third one occurred at a distance of 1.6 km from the road No. 81, but still in the urbanized region of Upper Silesia. The last one was far from highly populated and industrial areas. The detailed description of these measurement points is as follows: − Paderewski housing estate, Katowice. There are many-storied buildings with asbes- tos cover. The high-way no A4 runs at a distance of over a dozen meters from this measurements point (N 50º 14’ 47’’, E 19º 01’ 43’’). − Road No. 81, near Woszczyce, a town located between Mikołów and Żory. The measurement point was at a distance of several meters from this road (N 50° 04’ 28’’ E 18° 44’ 42’’). − Jesionka pond (south of Palowice and west of Mikołów). The location was 1.6 km North-West of the previous measurement point at the road No. 81 (N 50° 04’ 57’’, E 18° 43’ 35’’). − Hills near Racławice, a little town at a distance of tens of kilometers north of Kra- kow. This location was far from roads and densely populated areas (N 50º 11’ 28’’, E 19º 41’ 39’’). 26 KRYSTIAN SKUBACZ

MEASUREMENT METHODS

The SMPS and APS particle spectrometers manufactured by TSI (USA) were applied to perform measurements of aerosol size distributions (Fig. 2). The first one has a measuring range from several nanometers to 1000 nm, and the APS device from 540 nm to about 20000 nm. The SMPS spectrometer consists of the 3080 electrostatic classifier, DMA 3081 or DMA 3085 differential mobility analyzer and WCPC 3785 particle counter. An impactor located at the inlet removes any particles larger than its cut-point size and is used additionally to measure the flow rate. The cut-point size of the chosen impactor (orifice diameter of 0.071 cm) was above 1000 nm.

Fig. 2. Measurement site in close proximity to the busy road No. 81 near Woszczyce

According to investigations made by Wiedensohler and Fissan [15], there is no equilibrium of electric charge in ambient air. On the other hand, the measurement relies on separation of particles taking into account their electrical mobility and the non-equilibrium conditions could result in erroneous evaluation of concentration. Therefore, aerosols have to enter a 85Kr Bipolar Charger (Fig. 3), which exposes the aerosol particles to a high concentration of bipolar ions. The particles and ions undergo frequent collisions due to the random thermal motion of the ions and reach a state of equilibrium, in which the particles carry a bipolar charge distribution. Then aerosol particles flow to the Electro- static Classifier that extracts a known size fraction of particles from the incoming polydisperse aerosol. A main part of the classifier is the differential mobility analyzer that has an inner cylinder with negative voltage while the outer cylinder is grounded. The electric field causes positively charged particles to be attracted to the negatively charged cylinder and only particles with strictly defined size range are able to reach a small slit located at the bottom of this cylinder and reach the particle counter. This narrow size range depends on electrical mobility of particles, flow rate and Classifier geometry. There are two types of the differential mobility analyzer, the Long DMA (DMA 3081) with measurement range from about 10 nm to 1000 nm and the Nano DMA (DMA 3085) with measurement range from about 2 nm to 150 nm. The voltage of the DMA cylinder can be changed automatically by the condensation particle counter or manually by controls located at the Electrostatic Classifier. MEASUREMENTS OF AEROSOL SIZE DISTRIBUTION IN URBAN AREAS OF UPPER SILESIA 27

Electrostatic Classifier (Model 3080)

85 - Krypton Impactor Incoming air

Heat exchanger

Measurement Q, T, P negative rod DMA 3081

Pump Filter DMA 3081:

Pump Filter to WCPC 3785

Fig. 3. SMPS spectrometer, classification of submicrometer particles (Q – flow rate, T –temperature, P – pressure)

It should be mentioned that only a part of incoming sample air (polydisperse flow) is analyzed. The excess air (excess flow) is driven out of DMA, filtered and returned back as so called “sheath flow”. This additional air ensures laminar flow along the cylinder and allows avoiding erroneous size analyzing. The ratio of the sheath flow to polydisperse flow rate on the Electrostatic Classifier is normally set to 10:1. To achieve the best reso- lution, the sheath flow rate and the excess flow rate must equal each other, and also the polydisperse flow rate and the monodisperse flow rate (air that leaves DMA through the small slit located at the bottom) must also equal each other. These particles which reach the slit are transferred to a condensation particle counter to determine the particle concentration. Particles are detected optically by laser beam and photodetector that are parts of the particle counter. The detection however is possible when particles have an optically detectable size, typically 2 to 3 micrometers. Therefore, aerosols with fewer diameters have to grow to this size. The mechanism used to grow particles in the particle counter is heterogeneous condensation, whereby particle growth is promoted by the presence of condensation nuclei. This process was supported by distil- lated water but sometimes butyl alcohol is applied instead. The smallest size of incoming 28 KRYSTIAN SKUBACZ particles that can be detected this way depends on the ratio of the actual vapor partial pressure and saturation partial pressure. The lower particle detection size, particle diameter at which 50% of particles are detected, is 5 nm for the applied particle counter (3785 WCPC). The upper concentration limit is equal to 20000 particles/cm3 for a single-count mode, when every particle is detected separately, and 107 particles/cm3 for a photometric mode, when the count value, according to special calibration procedure, is calculated based on the concentration of particles measured. Ultrafine particles are partially caught by each tube which connects spectrometer modules. Therefore, an appropriate correction should be made taking into account the connection length and air flow rate. This correction is possible thanks to the software that governs and supports the measuring process. The APS spectrometer is a simpler device specifically designed to perform aerodynamic size measurement in real time using low particle accelerations. Aerodynamic diameter is the most important size parameter because it determines a particle’s airborne behavior. Time-of-flight particle sizing technology involves measuring the acceleration of aerosol particles in response to the accelerated flow of the sample aerosol through a nozzle. In this case the sheath flow of filtered air is applied as well. This flow is reunited with sample flow at the accelerating orifice nozzle to confine the analyzed particles to the center stream and accelerates the air flow around the particles. As a result small particles, due to lower inertia, reach higher velocity than larger particles. The aerodynamic size of a particle determines its rate of acceleration, with larger particles accelerating more slowly due to increased inertia. As particles exit the nozzle, the time of flight between two laser beams is recorded and converted to aerodynamic diameter using a calibration curve. Information connected to particle detected, is stored to one of 52 channels that the total measurement range is divided by. The measurement range is from 0.5 µm to 20 µm. Smaller particles, 0.3 µm to 0.5 µm, are detected as well but the totalized counts are stored to only one channel.

RESULTS

Chosen statistical characteristics of aerosol size distributions are presented in Tables 1–4.

There are count median diameter (Md), count mean diameter ( d ), aerosol concentration

(C), mass median diameter (Mdm), mass mean diameter ( dm ) and aerosol mass concentration (Z). Differences between d and dm quantities lie in the weighting mode that is performed in relation to the number of particles or mass of particles:

(1)

where ni is the number of particles, mi is mass of particles in the i-th channel with the mid-point diameter of di. The channel width depends on the number of channels in the measuring device and its measuring range. Measurement points in the Paderewski housing estate and at the road No. 81 were located close to places where heavy traffic occurs as opposed to Jesionka pond and hills in the vicinity of Racławice. There were performed over a dozen of measurements of aerosol size distribution a day. Some statistical characteristics related to these measure- MEASUREMENTS OF AEROSOL SIZE DISTRIBUTION IN URBAN AREAS OF UPPER SILESIA 29 ments are reported in Tables 1–4 and averaged distributions are illustrated on Figures 4–7. The vertical lines on these plots indicate the measurement range of the SMPS and APS particle spectrometers.

Table 1. Statistical characteristics of aerosol size distribution, the Paderewski housing estate

M d C M d Z Quantity d dm m [nm] [nm] [particles/cm3] [nm] [nm] [μg/m3]

SMPS, DMA-3085: 4–100 nm Mean 15 28 15297 83 79 0.7 Fluctuation [%] 56 32 91 1 1 58 SMPS, DMA-3081: 102–531 nm Mean 161 196 8011 335 337 47.7 Fluctuation [%] 6 4 10 2 1 7 APS: 542–19810 nm Mean 626 710 240 965 2660 74.0 Fluctuation [%] 1 1 6 24 18 12 SMPS + APS: 4–19810 nm Mean 47 92 23548 626 1740 122.3

Table 2. Statistical characteristics of aerosol size distribution, road No. 81

M d C M d Z Quantity d dm m [nm] [nm] [particles/cm3] [nm] [nm] [μg/m3]

SMPS, DMA-3085: 4–100 nm Mean 5 12 112266 77 74 1.0 Fluctuation [%] 42 36 81 6 6 29 SMPS, DMA-3081: 102–531 nm Mean 172 205 7543 323 335 48.8 Fluctuation [%] 4 3 9 2 1 6 APS: 542–19810 nm Mean 583 680 194 965 2706 54.3 Fluctuation [%] < 1 1 4 39 10 12 SMPS + APS: 4–19810 nm Mean 6 25 120002 531 1570 104.0 30 KRYSTIAN SKUBACZ

Table 3. Statistical characteristics of aerosol size distribution, Jesionka pond

M d C M d Z Quantity d dm m [nm] [nm] [particles/cm3] [nm] [nm] [μg/m3] SMPS, DMA-3081: 11–100 nm Mean 28 36 8987 69 67 0.6 Fluctuation [%] 6 6 17 1 11 9 SMPS, DMA-3081: 102–531 nm Mean 178 217 6709 360 369 56.1 Fluctuation [%] 2 3 1 75 12 APS: 542–19810 nm Mean 583 706 141 1114 3106 46.4 Fluctuation [%] 1 < 1 9 20 11 9 SMPS + APS: 4–19810 nm Mean 80 123 15837 494 1598 103.1

Table 4. Statistical characteristics of aerosol size distribution, hills in the vicinity of Racławice

M d C M d Z Quantity d dm m [nm] [nm] [particles/cm3] [nm] [nm] [μg/m3] SMPS, DMA-3085: 4–100 nm Mean 54 52 2920 83 83 0.3 Fluctuation [%] 10 10 13 < 1 < 1 3 SMPS, DMA-3081: 102–531 nm Mean 262 278 2154 400 402 33.0 Fluctuation [%] 4 3 4 1 < 1 4 APS: 542–19810 nm Mean 673 806 201 1486 2732 104.0 Fluctuation [%] 1 3 7 32 33 36 SMPS + APS: 4–19810 nm Mean 92 173 5275 1037 2158 137.4

] 16000 m c / 3 s

e C = 23548 particles/cm 12000 3

ticl Z = 122.3 g/m r a

p d = 92 nm [

d 8000 d m = 1740 nm g 3 o

l p = 1.2 g/cm

d / 4000 N d

0 1 10 100 1000 10000 Aerodynamic diameter [nm] Fig. 4. Averaged aerosol size distribution, the Paderewski housing estate MEASUREMENTS OF AEROSOL SIZE DISTRIBUTION IN URBAN AREAS OF UPPER SILESIA 31

2500 ] 0 2000 C = 120002 particles/cm3 0 3 Z = 104.0 g/m 1500 d = 25 nm 0 d m = 1570 nm 1000 3 0 p = 1.2 g/cm 500 dN/d log d [particles/cm 0 1 10 10 100 1000 0 0 0 Aerodynamic diameter [nm] Fig. 5. Averaged aerosol size distribution, road No. 81

] 12000

10000 C = 15837 particles/cm3 8000 Z = 103.1 g/m3 6000 d = 123 nm d m = 1598 nm 3 4000 p = 1.2 g/cm

2000 dN/d log d [particles/cm 0 1 10 100 1000 10000

Aerodynamic diameter [nm]

Fig. 6. Averaged aerosol size distribution, Jesionka pond ] 4000

C = 5275 particles/cm3 3000 Z = 137.4 g/m3 d = 173 nm

2000 d m = 2158 nm 3 p = 1.2 g/cm 1000 dN/d log d [particles/cm 0 1 10 100 1000 10000

Aerodynamic diameter [nm] Fig. 7. Averaged aerosol size distribution, hills in the vicinity of Racławice

Total aerosol mass concentration (liquid and solid aerosols) was equal to 122 µg/m3, 104 µg/m3, 103 µg/m3 and 137 µg/m3 respectively in the Paderewski housing estate, road No. 81, Jesionka pond and hills near to Racławice. The highest value was measured 32 KRYSTIAN SKUBACZ therefore far from roads and urbanized areas. It is due to the occurrence of particles greater in size and not by their greater concentration. The count mean diameter and aerosol concentration was for these locations respectively 92 nm, 23548 particles/cm3 and 25 nm, 120002 particles/cm3, and 123 nm, 15837 particles/cm3 and 173 nm, 5275 particles/cm3. Therefore, the aerosol concentration in Woszczyce was 23 times greater than in Racła- wice. Simultaneously, the count mean diameter is considerably less in comparison to aerosols which occur in Racławice and the mass distribution is shifted to lower values. It proves that close to the road mainly ultrafine particles occur. The measure of fluctuations is a ratio of mean value and standardized deviation (Tabs 1–4). Measurements performed on hills in the vicinity of Racławice are time-stable. Bigger changes are related only to mass concentration due to fluctuation of concentration of particles with the diameter over 1 µm. On the contrary, close to the road No. 81 strong fluctuations of count diameter and particle concentration correspond to ultrafine particles below 0.1 µm and for diameter over 0.5 µm are less than 5% (Tab. 2). Dynamics of these processes shows that cars produce mainly ultrafine particles and their concentration corresponds to changeable traffic intensity during measurements and a kind of passing vehicles. Such ultrafine particles can be produced by diesel engines as reported by Burtscher [2] and Maricq [8]. There is an interesting problem of risk assessment caused by human activities related to motor traffic. Such evaluation is based often on measurements of PM10 and PM2.5 dust concentration that corresponds to solid particles with diameter up to 10 µm and 2.5 µm respectively. These routine measurements are very important in the existing monitoring system. There is no possibility, however, to measure contribution of both dangerous ultrafine particles and coarse particles with diameter close to 10 µm, and additionally liquid particles are excluded from such measurements. Such procedure can lead to underestimation of hazards especially close to the roads. Structure of aerosols influences also occurrence of other pollutants in the air. For example, such radionuclides as short-lived radon daughters are caught by ambient aerosols forming radioactive aerosols. Corresponding probability of this process is greater for particles greater in size. On the other hand, contribution of ultrafine particles in the formation of radioactive aerosols increases as their concentration rises. Therefore, there is no simple relationship between radioactive and ambient aerosols. However, in the case of aerosols emitted by cars, the situation is something different. Strong changes of aerosol concentration prove that these hazardous pollutants are generated simply by sources and their interaction with ambient aerosols does not have such critical meaning as for radon daughters. It is possible in some cases to assess risk connected to interaction of aerosols with different sizes as, for example, for radon daughters (Tab. 5). The recommended conversion coefficient, according to legal requirements [3], corresponds to size of 0.5 μm and nose-breathing rate of 0.75 m3/h. Then its value is equal to 1.1 Sv/(J·h·m-3) and mean annual doses can reach 71 μSv (maximal value 178 μSv) assuming 50% of equilibrium and basing on concentration measurements of polonium 218Po, 2.62 Bq/m3 (0.024 do 6.59 Bq/m3), performed in open air in Upper Silesia. However, close to busy roads, the aerosol structure can be disturbed and many ultrafine and fine aerosols occur in air resulting in increasing of the conversion coefficient. Taking into account the aerosol size distribution close to the road No. 81 and count mean diameter of 25 nm, the corresponding conver- MEASUREMENTS OF AEROSOL SIZE DISTRIBUTION IN URBAN AREAS OF UPPER SILESIA 33 sion coefficient is about 10 times greater – 11 Sv/(J·h·m3) and the mean annual dose could reach 710 μSv (maximal value 1780 μSv) under assumption that count mean sizes of radioactive and ambient aerosols are close to each other. That is slightly less than 1 mSv limit for members of the public [3]. This example shows how risk assessment could change taking into account the aerosol size distribution.

Table 5. Short-lived radon daughters, conversion coefficient and effective doses

Conversion coefficient Annual effective dose [μSv] Isotope -3 [Sv/(J·h·m )] minimum maximum average 218Po 1.1 0.5 178 71 218Po 11.0 5.0 1780 710

Assumptions: equilibrium factor is equal to 50%, annual time to 8760 hours, count mean sizes of radioactive and ambient aerosols are close to each other. The conversion coefficient, 1.1 Sv/(J·h·m-3) is recommended by legal requirements, and the second one, 11.0 Sv/(J·h·m-3), corresponds approximately to the count mean size of 25 nm as measured close to the road No. 81 in the vicinity of Woszczyce; both conversion coefficients were evaluated assuming the nose-breathing rate of 0.75 3m /h.

CONCLUSIONS

Performed measurements of aerosol size distributions in Upper Silesia prove that a lot of ultrafine particles can be produced as a result of heavy traffic. Total aerosol mass concentration in the air was comparable for all sites. The highest value was found far from busy roads, in a slightly affected by human activity area close to Racławice. The aerosol size distribution was very stable there taking into account ultrafine particles. Some changes, however, due to big particles could be observed in relation to both mass mean diameter or mass median and mass concentration. On the contrary, the amount of ultrafine particles, below 0.1 µm increased strongly, even by about twenty times, in sites located close to busy roads, while concentrations of larger particles, over 0.5 µm, were well comparable. Strong fluctuations of count, median diameter and aerosol concentration take place in these locations as well due to ultrafine particles. It proves that ultrafine particles, below 0.1 µm, occurred mainly close to roads as a result of heavy traffic. Exposition to the respiratory tracts depends on aerosol penetration ability and then on their size distribution as well. Presently such risk assessment relies on PM10 or PM2.5 dust monitoring. The occurrence of big amount of ultrafine particles produced by cars may not result in observable increase of dust concentration and this way the risk can be underestimated. The contribution of ultrafine particles, below 0.1 µm to the total mass was in the order of only 1%. Therefore, measurements of size distribution can contribute to appropriate risk assessment. Evaluation of risk caused by short-lived radon daughters can be an example here. The conversion coefficient for particles with diameter of 0.5 μm is equal to 1.1 Sv/(J·h·m-3) but for particles with diameter of 25 nm is ten times greater reaching value of about 11 Sv/(J·h·m-3) that corresponds to ten times greater dose absorbed by human beings. It is sure that for other pollutants occurring in ground layer of atmospheric air the situation looks like for radon progeny. 34 KRYSTIAN SKUBACZ

There is more and more evidence that some health effects are related to the ultrafine particles because they penetrate cell membranes, blood and brain inducing, for example inheritable mutations [1, 9, 13]. That is the reason why the protection against these particles is getting more and more important.

REFERENCES

[1] Brown D. M., M. R. Wilson, W. MacNee, V. Stone, K. Donaldson: Sizedependent proinflammatory effects of ultrafine polystyrene particles: a role for surface area and oxidative stress in the enhanced activity of ultrafines, Toxicology and Applied Pharmacology, 175, 191–199 (2001). [2] Burtscher H.: Physical characterization of particulate emissions from diesel engines: a review, Aerosol Science, 36, 896–932 (2005). [3] Decree of Polish Cabinet of 18 January 2005 on dose limits of ionising radiation, The Polish Law Journal, no 20, pos. 168, 2005 (Polish). [4] Heyder J., J. Gebhart, W. Stahlhofen: Generation of aerosols and Facilities for Exposure Experiments, Inhalation of Aerosols: Particle deposition and Retention, Ann Arbor Science Publishers Inc, Michigan 1980, pp. 65–103. [5] http://www.epa.gov. [6] International Commission on Radiological Protection: Human respiratory tract model for radiological protection, ICRP Publication 66, Oxford Pergamon Press, Oxford 1994. [7] Jacobi W., K. Eisfeld: Dose to tissues and effective dose equivalent by inhalation of 222Rn, 220Rn and their short-lived daughters, Gesellschaft für Strahlen und Umweltforschung MBH, Institut für Strahlenschutz, Germany GSF-Report S-626, Munch-Neuherberg 1980. [8] Maricq M.M.: Chemical characterization of particulate emissions from diesel engines: A review, Aerosol Science, 38, 1079–1118 (2007). [9] Oberdörster G., Z. Sharp, V. Atudorei, A. Elder, R. Gelein, W. Kreyling, C. Cox: Translocation of inhaled ultrafine particles to the brain, Inhalation Toxicology, 16, 437–445 (2004). [10] Reineking A., J. Porstendörfer: ”Unattached” fraction of short-lived Rn decay products in indoor and outdoor environments: an improved single-screen method and results, Health Physics, 58, 715–727 (1990). [11] Skubacz K.: Short-lived radon daughters, [in:] Hazards caused by natural radioactive sources in mining industry, Główny Instytut Górnictwa, Katowice 2007, pp. 157–180 (Polish). [12] Skubacz K.: Measurement of unattached fraction and size distribution of short-lived radon daughters, [in:] Hazards caused by natural radioactive sources in mining industry, Główny Instytut Górnictwa, Kato- wice 2007, pp. 297–319 (Polish). [13] Somers C.M., B.E. McCarry, F. Malek, J.S. Quinn: Reduction of particulate air pollution lowers the rist of heritable mutations in mice, Science, 304, 1008–1010 (2004). [14] Standard EN 481: Workplace atmospheres – Size fraction definitions for measurement of airborne particles, 1993. [15] Wiedensohler A., H.J. Fissan.: Aerosol Charging in High Purity Gases, Aerosol Science, 19, 867–870 (1988).

Received: March 6, 2009; a ccepted: August 13, 2009.

POMIARY ROZKŁADÓW ZIARNOWYCH AEROZOLI NA ZURBANIZOWANYCH TERENACH AGLOMERACJI ŚLĄSKIEJ

Depozycją aerozoli w układzie oddechowym zależy od rozkładu ziarnowego aerozoli. Badanie rozkładu ma zatem duże znaczenie dla właściwej oceny zagrożenia spowodowanego przez szkodliwe substancje pojawiające się w środowisku bądź to w następstwie ludzkiej aktywności takiej jak produkcja przemysłowa, komunikacja i paleniska domowe bądź też w wyniku naturalnych procesów. W pracy opisano i oceniono wyniki pilotażowych pomiarów rozkładów ziarnowych aerozoli wykonanych w kilku miejscach zlokalizowanych na terenach zurbanizowanych. Zastosowana aparatura pomiarowa umożliwiała wykonanie badań rozkładów ziarnowych w szerokim zakresie od kilku nanometrów do 20 µm obejmującym praktycznie całą frakcję cząstek respirabil- nych. Uzyskane rezultaty wskazują, że w miejscach położonych blisko dróg o dużym natężeniu ruchu pojawiają się duże liczny nanometrowych aerozoli, których liczba ulega w czasie dużym wahaniom. 35

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 35 - 43 2009 PL ISSN 0324-8461

ENVIRONMENTAL LEVELS OF NITRO-PAHs IN TOTAL SUSPENDED PARTICULATE MATTER IN UPPER SILESIA (POLAND)

MARZENA ZACIERA*, WOJCIECH MNISZEK, JOLANTA KUREK

Institute of Occupational Medicine and Environmental Health (IOMEH) ul. Kościelna 13, 41-200 Sosnowiec, Poland * Corresponding author e-mail: [email protected]

Keywords: Nitro-PAHs, total suspended particulate matter (TSP), ambient air particulate.

Abstract: Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) may be formed during combustion of Diesel and gasoline fuel and may be produced in gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs) with oxides of nitrogen. These compounds can form a significant fraction of the mainly direct-acting mutagenic compounds present in extracts of ambient air particles. Using own analytical method of nitro-PAHs determination, concentrations of total PAHs, nitro- and dinitro-PAHs in urban and non-urban area of three cites of Upper Silesia in Poland were measured. The dependence between concentration of PAHs and nitro-PAHs in urban and non-urban area as well as their distribution depending on roadway distance were searched. The study showed a significant influence of road transport on the levels of nitro-PAHs concentration.

INTRODUCTION

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) can be numbered among the most dangerous chemical substances for human health due to their mutagenic and carcinogenic potency [22, 25]. These compounds are mainly produced during a gasoline and diesel fuel combustion. They are also formed during a nitration of PAHs by nitric acid or through addition of nitrogen monoxide or dioxide to PAH free radicals [1, 8]. Many of them are highly persistent in the environment; however, their concentrations are low (compared to unsubstituted PAHs). Nitro-PAHs are adsorbed onto airborne particles and can be transported for long distances from their original source. Inhalation of particulate matter is the main way of exposure to nitro-PAHs. Compared to PAHs, their nitro derivatives gain an increased attention due to 200000 times higher mutagenic and 10 time’s higher carcinogenic properties. Such predominant mutagenic potency of nitro-PAHs is visible even at their environmental trace levels in bioassays utilizing human cells [2, 7, 8]. Many three-, four- and five-ring structures of nitrated PAHs have been found in the extracts of diesel engine exhaust particles [8]. The most abundant nitro-PAHs formed in diesel exhaust are: 1-nitropyrene, 2-nitrofluorene and 3-nitrofluoranthene [2, 9]. It was shown that the main portion of direct-acting mutagenicity of Diesel and air particulates is associated with nitro-PAHs [7]. The concentration of 1-nitropyrene is much lower in gasoline exhaust than in diesel exhaust, when the concentration of isomers of dinitropyrenes is on the same level. In con- 36 MARZENA ZACIERA, WOJCIECH MNISZEK, JOLANTA KUREK nection with health effects, nitrated PAHs, especially 2-nitrofluorene and 1-nitropyrene, are treated as “markers” of exposure to diesel exhaust [2, 8, 9]. The presence of nitro-PAHs in the air has been investigated in numerous studies [2, 3, 21–23, 26, 29]. Based on these results, it can be stated that the concentration of nitro- PAHs in the air is very low, but such tendency could be due to the analytical problems in determination of nitro-PAHs concentrations. Several methods for determining nitro-PAHs have been elaborated and described [2, 3, 7, 22, 29]. Most of them are based on the conversion of nitrocompounds into their

Table 1. Physical and chemical properties of selected PAHs nitro derivatives CAS Melting Boiling Solubility Molecular Compound name Structural formula Registry point point in organic mass number [oC] [oC] solvents methanol, carbon disulfide, pyridine, cycloheksane, 1-nitronaphthalene 86-57-7 173.17 56 304 chloroform, ether, benzene, methylene chloride methanol, 9-nitroanthracene 602-60-8 223.23 141 – methylene chloride methanol, 2-nitrofluorene 607-57-8 211.22 156–158 326 benzene methylene chloride, 1-nitropyrene 5522-43-0 247.26 153–155 472 methanol, benzene methanol, 6-nitrochrysene 7496-02-8 273.3 220 – methylene chloride methanol, benzene, 3-nitrofluoranthene 892-21-7 247.26 157–159 – methylene chloride methylene chloride, 1,3-dinitropyrene 75321-20-9 292.25 – – methanol, benzene methylene 1,6-dinitropyrene 42397-64-8 292.25 300 – chloride, toluene methylene 1,8-dinitropyrene 42397-65-9 292.25 – – chloride, benzene ENVIRONMENTAL LEVELS OF NITRO-PAHs IN TOTAL SUSPENDED PARTICULATE... 37 amine or amide derivatives [21–25]. The method of nitro-PAHs determination in their familiar form developed by Bamford et al. [2] requires the use of expensive equipment. An own method of nitro-PAHs determination in their familiar form has been elaborated in Chemical Hazard Department of IOMEH [27, 28]. This method was used to check a concentration of these compounds in the air of urban and non-urban areas in Poland. Techniques of extraction and fractionation, primarily used for mutagenicity tests, were applied and adapted for the determination of nitro-PAHs in the air; this method is generally described in materials and methods. Literature review allowed for the selection of several nitro-PAHs, which are contaminants of ambient air and are present in diesel exhaust. The physical and chemical properties of selected nitro-PAHs are shown in Table 1 [2, 8, 9, 14, 15, 18, 23, 24, 30]. Most of the listed compounds are classified as possibly carcinogenic to humans, toxic and dangerous for human health and the environment [10, 11, 15, 19, 20].

MATERIALS AND METHODS

The study was carried out in three cities: Sosnowiec (urban area), Tucznawa and Lagisza (non-urban areas), located in Upper Silesia, the most polluted region in southern Poland. For the urban area, the sampling points were placed near bus stops and crossroads, where a high degree of urbanization was combined with a high emission of air pollutants from vehicle engines. The average traffic density at sampling points was about 8000 vehicles (cars, trucks and buses) per 24 hours. In the case of non-urban area, the sampling points were situated 1, 30 and 100 m from the road in the vicinity of detached houses with gardens. At all points, the samplings were performed in daytime (from 8 AM till 2 PM). A 50 mg sample of total suspended particulate matter (TSP) was collected on glass fiber filter (11 cm diameter) using Staplex high volume sampler. The flow-rate was 400– 500 dm3/min. The total volume of sampled air was 150–190 m3. Particulate matter samples were extracted using Soxhlet apparatus with 100 cm3 of dichloromethane (DCM). The extract was fractionated on a glass column packed with silica gel using the following solvents: cycloheksane, dichloromethane in cycloheksane and dichloromethane (with different volume for two fractions). The separated fractions contained: first – aliphatic hydrocarbons, second – PAHs, third – mononitro-PAHs, and fourth – dinitro-PAHs [13, 16, 17]. Each eluate was evaporated to dryness. The following nine nitrated polycyclic aromatic hydrocarbons were determined: 1-nitronaphthalene, 9-nitroanthracene, 2-nitrofluorene, 1-nitropy rene, 3-nitrofluoranthene, 1,3-dinitropyrene, 1,6-dinitropyrene, and 1,8-dinitropyrene. Gas chromatography with electron ionization mass spectrometry GC/MS (EI) analyses were carried out using Hewlett-Packard 5890 II Plus gas chromatograph interfaced with HP 5972A mass detector. The gas chromatograph was equipped with HP-5MS column. The following chromatographic conditions were set: − oven temperature was programmed: at 50°C (2 min.); increasing temperature 10°C/min to 280°C; − injector temperature: 290°C; − detector temperature: 280°C; − injection volume: 1×10-6 dm3, splitless; − carrier gas: helium. 38 MARZENA ZACIERA, WOJCIECH MNISZEK, JOLANTA KUREK

RESULTS AND DISCUSSION

The elaborated method was selective and linear for determination of nitrated polycyclic aromatic hydrocarbons – Table 2 shows the basic parameters for this method. GC-MS chromatogram of the sample collected in Sosnowiec is shown in Figure 1. Recovery of standards of nitro-PAHs from sample was in the range of 72–79%. The results from the GC-MS analyses are shown in Table 3.

Table 2. Qualifier ions, selectivity, linearity and determination limit values for the method of nitro-PAHs determination by gas chromatography with mass spectrometry detection

Determination MSD Retention time Correlation factor Compound name limit value Qualifier ions [min] (analytical curve) [ng/m3] 1-nitronaphthalene 115 127 15.57 0.998 0.09 2-nitrofluorene 165 211 21.17 0.999 0.09 9-nitroanthracene 223 176 21.49 0.998 0.09 3-nitrofluoranthene 247 200 25.10 0.998 0.08 1-nitropyrene 247 201 25.69 0.998 0.09 1,3-dinitropyrene 292 200 29.44 0.998 0.45 1,6-dinitropyrene 292 200 30.28 0.997 0.46 1,8-dinitropyrene 292 200 30.91 0.999 0.45

Table 3. Ranges and medians of nitro-PAHs and total PAHs concentrations in airborne particulate matter (PM) identified in analyzed samples [ng/m3]

Compound name/ 1-nitro 2-nitro 9-nitro 3-nitro 1-nitro 1,3-dinitro Total sampling location naphthalene fluorene anthracene fluoranthene pyrene pyrene PAHs urban area 1 m range 0.12–0.97 4.4–21.16 0.67–5.33 0.64–4.37 < 0.09–1.81 < 0.45–0.46 75.1–158.1 from road median 0.64 12.62 1.66 1.23 0.73 0.23 106.7 n = 6 not-urban area 1 m range n.d. – 1.11 0.22–0.46 n.d. – 0.31 n.d. – 0.66 n.d. – 0.10 < 0.45 7.8–16.6 from road median 0.43 0.27 0.11 0.48 0.05 < 0.45 9.9 n = 10 30 m range n.d. – 1.89 0.19–0.78 n.d. – 0.28 n.d. – 0.57 n.d. – 0.10 < 0.45 5.1–10.2 from road median 0.59 0.38 0.22 0.51 0.06 < 0.45 8.6 n = 6 100 m range n.d. – 0.71 0.18–0.54 n.d. – 0.65 n.d. – 0.66 n.d. – 0.10 < 0.45 11.4–30.6 from road median 0.59 0.32 0.24 0.59 0.05 < 0.45 13.0 n = 8 n.d. – not detected ENVIRONMENTAL LEVELS OF NITRO-PAHs IN TOTAL SUSPENDED PARTICULATE... 39

1-nitropyrene

Fig. 1. GC-MS chromatogram of mononitro-PAHs fraction from airborne sample collected in urban area

Concentration of PAHs and their nitrated derivatives in urban area were about 10 times higher than concentration of these compounds in non-urban areas. The performed study showed a decrease of total PAHs concentration in a distance of 30 m from roadway. Distribution of air pollutants from “linear” emission sources, such as road traffic, depends on many different factors. Function of pollutants concentration vs. distance from road predominantly is not linear. This distribution depends mainly on wind velocity and its direction, traffic density, thermal convection and from others. In this research this function was not precisely studied, only general observations were made. Concentration of benzo(a)pyrene in urban area was between 7.21–17.69 ng/m3 (median 9.86 ng/m3), while in non-urban area was between 0.21–2.80 ng/m3 (median 0.8 ng/m3). The level of PAHs

Fig. 2. Median of nitro-PAHs concentrations in urban and non-urban area 40 MARZENA ZACIERA, WOJCIECH MNISZEK, JOLANTA KUREK concentration is very important, because of formation more carcinogenic compounds, such as oxy- and nitro- derivatives of PAHs. This study shows presence of nitro-PAHs in urban as well as non-urban areas. The concentrations of nitro-PAHs in urban area were ten times higher than in non-urban area (with the exception of 1-nitronaphtalene).

Fig. 3. Correlation between median of nitro-PAHs and distance from roadway

There was no correlation between concentration of nitro-PAHs and distance from the road (Fig. 3). 2-nitrofluoren was in the highest concentration in the air of urban area, where intensity of the traffic (especially diesel fuel powered vehicles) was high. Some studies showed 2-nitrofluorene as dominant substance in diesel exhaust, which may exceed the concentration of 1-nitropyrene by a factor of 9.8 [8, 9]. The level of exposure to 2-nitrofluorene is significant because this compound is possibly carcinogenic to humans – group 2B (according to IARC). The concentrations of dinitropyrenes were below detection limit in almost all analyzed samples (the only exception was for the sample from urban area, where 1,3-dinitropyrene was detected at a concentration of 0.46 ng/m3). The literature review shows that dinitropyrenes were not detected in air particulate materials [2], as well as Diesel, gasoline, ambient particulate extracts [22] and other studies [13, 26] either. Other nitro- PAHs were above the detection limit (Tab. 2). Participation of individual compounds in total mass of nitro-PAHs in urban and non-urban areas is shown in Figure 4.

CONCLUSIONS

The aim of the study was to determine the level of nitro-PAHs in the air of three towns of Upper Silesia region taking into account the intensity of traffic. Nitro-PAHs levels were investigated using the own method elaborated at IOMEH, which allows to determine traces of nitro-PAHs in their familiar form, without converting nitrocompounds into their derivatives. Samples were collected at locations where the intensity of road transport was significant (urban area) and at locations where influence of road transport was unimportant (non-urban area). Concentration of PAHs and their nitrated derivatives were about ten times higher in urban area than in non-urban area; especially the concentration of 2-ni- ENVIRONMENTAL LEVELS OF NITRO-PAHs IN TOTAL SUSPENDED PARTICULATE... 41

Not-urban area

Urban area

Fig. 4. Participation of individual compounds in total mass of nitro-PAHs trofluoren was significant. High emission of nitro-PAHs compounds in urban area can be caused by diesel fuel powered buses and trucks, which are the primary source of nitro- PAHs exposure in urban area [2, 8, 9]. It can be assumed that a majority of engines in old vehicles are technically in bad condition and have been used for many years, burning a high amount of diesel fuel (about 30 dm3 per 100 km). The performed study showed a presence of nitro-PAHs in ambient air. The exposure to mutagenic nitro- and dinitro- PAHs in ambient air causes human health hazard. For this reason the monitoring of nitro- PAHs levels in ambient air is very important. It is also necessary to take on some activities to reduce PAHs emission – the basic precursor of nitro-PAHs.

Acknowledgement This study was supported by the Polish Ministry of Science and Higher Education (research grant 2 P05D 03629). 42 MARZENA ZACIERA, WOJCIECH MNISZEK, JOLANTA KUREK

REFERENCES

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[26] Yaffe D., Y. Cohen, J. Arey, A.J. Grosovsky: Multimedia Analysis of PAHs and Nitro-PAH Daughter Products in the Los Angeles Basin, Risk Analysis, 21, 2, 275–294 (2001). [27] Zaciera M., W. Mniszek: Oznaczanie nitrowych pochodnych WWA w powietrzu, [in:] Mikrozanieczysz- czenia w środowisku człowieka, M. Janosz-Rajczyk (ed.), Wydawnictwa Politechniki Częstochowskiej, Częstochowa 2004. [28] Zaciera M.: Metoda oznaczania nitrowych pochodnych WWA w powietrzu, [in:] Ochrona powietrza w teorii i praktyce, J. Konieczyński (ed.), vol. 1, pp. 309–316, Zabrze 2006. [29] Zielińska B., S. Samy: Analysis of nitrated polycyclic aromatic hydrocarbons, Anal. Bioanal. Chem., 386, 883–890 (2006). [30] Zwirner-Baier I., H.G. Neumann: Polycyclic nitroarenes (nitro-PAH) as biomarkers of exposure to diesel exhaust, Mutat. Res. (Wöurzburg), 441 (1), 135–144 (1999).

Received: October 22, 2008; accepted: July 29, 2009.

ŚRODOWISKOWE NARAŻENIE NA NITRO-WWA OZNACZANE W PYLE CAŁKOWITYM W POWIETRZU GÓRNEGO ŚLĄSKA (POLSKA)

Nitrowe pochodne wielopierścieniowych węglowodorów aromatycznych (nitro-WWA) mogą powstawać podczas spalania paliwa w silnikach Diesla i w silnikach benzynowych oraz mogą powstawać podczas reak- cji WWA z tlenkami azotu zachodzących w fazie gazowej. Związki te mogą być odpowiedzialne głównie za aktywność mutagenną pyłu zawieszonego w powietrzu. Stosując alternatywną do obecnych metodę oznaczania nitro-WWA w powietrzu, zbadano poziomy stężeń dla sumy WWA, nitro-WWA i dinitro-WWA w obszarze miejskim oraz pozamiejskim w trzech miastach Górnego Śląska w Polsce. Znaleziono zależność pomiędzy stężeniem WWA i nitro-WWA w obszarze miejskim i poza miejskim jak również zbadano rozprzestrzenienie się tych związków w zależności od odległości od drogi. Badania wykazały znaczący wpływ środków transportu drogowego na poziomy stężeń nitro-WWA w powietrzu. 44 45

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 45 - 53 2009 PL ISSN 0324-8461

The influence of air-conditioning system and presence of students on the aerosol concentration in the auditorium

Bernard PoŁednik*, Marzenna DudziŃska, Mariusz SkwarczyŃski

Lublin University of Technology, Faculty of Environmental Engineering ul. Nadbystrzycka 40B, 20-618 Lublin, Poland * Corresponding author e-mail: [email protected]

Keywords: Indoor generated aerosols, air conditioning system, aerosol number concentration, students’ health, auditorium.

Abstract: The indoor aerosols that are, among others, generated by air-conditioning systems are especially significant in school facilities. The measurements carried out in the new, air-conditioned auditorium have shown that the aerosol concentrations are strongly dependent on the operation of the air-conditioning system and the presence of students. The aerosol concentration was approximately 5 times higher when the air-conditioning (AC) system was switched on. An increased air movement inside the auditorium and the connected with it resuspention of the particles settled on the indoor surfaces could be responsible for this fact. It could also result from the ineffective operation of the AC filters. The presence of students in the auditorium caused an increase of the coarse aerosol particles irrespectively of the AC system operation. The results of aerosol particle monitoring should be taken into consideration while controlling the AC processes in order to ensure the desired indoor air quality in this type of facilities.

Introduction

Until the late 1990s aerosols of ambient origin were assumed as the main source of indoor air contamination. However, it has been observed that in many cases the concentrations of indoor generated aerosols are significantly higher than those of infiltrated ambient aerosols [1, 7]. The main sources of indoor generated aerosols are building materials, furnishings, equipment and room occupants [2, 9, 11]. Additionally, when buildings are air-conditioned (AC) the AC systems could also introduce aerosols to the indoor air [8]. The presence of aerosol particles in the indoor air is not desired and is a reason for many nuisances. The naturally occurring gravitational or electrostatic deposition of these particles may in many cases lead to the deterioration of the indoor surfaces and appliances. Aerosol particles present in the indoor air have been also recognized as a significant cause of health problems. It is well established that various respiratory symptoms and diseases are associated with exposures to these particulates [5, 18, 20]. The issue of indoor aerosols has become especially important in school buildings. This is related to the fact that students spend a considerable portion of their time in school facilities and these aerosols 46 Bernard PoŁednik, Marzenna DudziŃska, Mariusz SkwarczyŃski may adversely affect their health as well as their academic performance [3, 13, 14]. Par- ticular attention should be paid to school buildings with AC systems, due to the fact that those systems may be responsible for generating additional aerosols [5, 8]. Until very recently most indoor aerosol studies were carried out either for naturally or mechanically ventilated buildings. Ventilation systems were examined to establish how they protect the indoor environment against outdoor particles, or how indoor-generated particles are distributed by these systems. This paper deals with the influence of the AC system operation on the aerosol particle concentration in an occupied and an unoc- cupied school auditorium. According to the literature, only a few researches have been conducted on the aerosol particle concentrations in air-conditioned classrooms, however, the occupancy of the classrooms has not particularly been taken into account [5, 8, 10]. It seems important to consider the varying classroom occupancy during the measurements as it may have a significant impact on the indoor conditions and the obtained results.

Materials and methods

The particle number concentration measurements were performed in a new air-conditioned auditorium at the Lublin University of Technology (LUT). The auditorium with seats for 186 people (Fig. 1) is located on the first floor of the LUT building and has a volume of approximately 1200 m3 (average dimensions – 20 x 15 x 4 m). It has 8 double pane air tight windows (2.6 x 3 m) and a carpeted floor. The auditorium was ventilated with a total supply of 1.6 m3/s of conditioned outdoor air (50%) and recirculated air (50%). The air conditioning system provided mechanical ventilation, cooling or heating and humidity control inside the auditorium and comprised of a supply-exhaust air handling unit with a rotary heat exchanger, a heat pump, a water heater and a humidifier.

B A

Fig. 1. The scheme of the auditorium with the measurement point A – scene, B – occupation zone The influence of air-conditioning system and presence of students on... 47

The auditorium was irregularly occupied from Monday to Friday, usually from 8 a.m. to 8 p.m. according to the schedule of the LUT courses. After each 45 or 90-minute lecture there were 15-minute breaks during which the students moved in and out of the room. Sizes and concentrations of aerosol particles were determined in the middle of the occupied zone by means of a laser particle counter ROYCO 243A with iso-Diluter D50 (Pacific Scientific Instruments, USA). The samples were collected at 60-second intervals with a 15-minute delay time. The counter categorized the collected particles into four size ranges: 0.3–0.5, 0.5–5, 5–10 and >10 μm. Signal to Noise Ratio was 1.6:1 at maximum sensitivity (0.3 μm). The air temperature and relative humidity were measured using the thermohigrometer LB-701 (LAB-EL, Poland). The inaccuracy of the measured parameters was 0.2°C and 2% respectively. The experiments were carried out during the lectures for the following conditions established in the auditorium: − 60 students were present in the auditorium and the AC system was either switched on or switched off, − 45 or 90 students were present in the auditorium and the AC system was switched on, − 44 or 84 students were present in the auditorium and the AC system was switched off. The number of students present in the auditorium varied (max. 90) and the AC system was switched on. Detailed information on the individual measurement conditions is specified with reported results. The research was conducted for several weeks in the springtime 2008 (March – April).

Results and discussion

In order to ascertain how the switched on/off AC system in the auditorium influences the aerosol particle concentrations, the results of measurements from two subsequent days when the AC system was either switched on or off for the entire day were analyzed. During those days the lectures in the auditorium started at 8:15 a.m. and lasted until 8:00 p.m. Table 1 presents the basic statistical information about the measured aerosol number concentrations in both days.

Table 1. Twelve-hour data* for the measured aerosol particle number concentrations, in [particles/m3]

Particle size AC on/off AC off AC on [μm] means’ ratio 0.3–0.5 (1.92/1.77 (1.20-2.78)) × 107 (6.47/4.99 (3.58-11.71)) × 107 3.37 0.5–5 (8.53/7.37 (5.08-13.25)) × 106 (3.12/2.27 (1.38-6.39)) × 107 3.66 5–10 (2.65/2.83 (0-8.65)) × 104 (1.63/1.50 (0.11-3.14)) × 105 6.15 > 10 (3.18/1.77 (0-10.59)) × 103 (1.38/1.24 (0-3.18)) × 104 4.34

* – arithmetic mean/median (range)

The graphs a and b in Figure 2 illustrate the mean concentrations of the measured particles during the lectures which took place between 12:15 p.m. and 2:00 p.m. with 60 48 Bernard PoŁednik, Marzenna DudziŃska, Mariusz SkwarczyŃski students present in the auditorium. The bars denote the standard error of the mean particle concentration values. It follows from the graphs that the concentration of all the measured aerosol fractions was about five times higher when the AC system was switched on. Many reasons may be responsible for this fact. However, due to the fact that the same number of students participated in the lectures, their influence on the measurement results may be excluded. The changes of the indoor air thermal parameters could also be of minor importance. The mean temperature and relative humidity amounted to 23.5°C and 48% when the AC system was switched off and respectively 20°C and 40% when the system was switched on. A significant influence of the changes of outdoor aerosol infiltration into the auditorium may also be excluded. The windows during the measurement periods in question were tightly closed. The outdoor air temperature and relative humidity amounted to respectively approximately 15°C and 50% during both measurement periods. The observed higher concentration of aerosol particles in the auditorium when the AC system was switched on may result from the increased indoor air movement and the connected with it increased resuspension of the particles already deposited on the indoor surfaces, which may be confirmed by the findings of Jamriskaet al. [12]. Another possible explana- tion might be that the AC system filters may insufficiently remove aerosols from the air inflowing to the auditorium, as it was stated by Fisket al. [7].

Fig. 2. The mean concentration of aerosol particles during the lectures in the auditorium with 60 students present and with a – switched off AC system (T = 23.5°C, RH = 48%), b – switched on AC system (T = 20°C, RH = 40%) The influence of air-conditioning system and presence of students on... 49

Graphs in Figure 3 present the concentrations of coarse aerosol particles (5–10 µm and > 10 µm) in the air-conditioned auditorium directly before the 2-hour lectures, during the lectures and just after their end. Graph a presents the concentrations of the aforementioned aerosols when the lecture took place from 10:15 a.m. to 12:00 p.m. and there were 45 students in the auditorium. Graph b refers to the situation in which the lecture lasted from 5:15 p.m. to 6:45 p.m. and there were 90 students in the auditorium. While comparing graphs a and b one can notice similar dependencies between the aerosol particle concentration and the duration of the lectures. The difference consists in the fact that aerosol concentrations are almost three times higher when 90 students are present in the auditorium than when 45 students attend the lecture. The coarse aerosol particle concentration changes inside the auditorium may result from the varied activity of the students. Higher aerosol particle concentration was noted both immediately upon the entrance of the students and after they left the auditorium. During the course of the lectures the concentration of these particles decreased, therefore one can assume that a part of the aerosol particles was removed by the AC system or settled on the indoor surfaces [7, 10, 12]. The accumulation of a certain amount of these particles in the students’ respiratory

Fig. 3. The concentration of coarse aerosol particles before, during and after the 2-hour lectures with a switched on AC system, a – lecture from 10:15 a.m. to 12:00 a.m., 45 students, b – lecture from 5:15 p.m. to 6:45 p.m., 90 students 50 Bernard PoŁednik, Marzenna DudziŃska, Mariusz SkwarczyŃski tract cannot be ruled out as well [18–20]. It has to be emphasized that the measured values of the particle concentration at the end of the lectures were lower than at the beginning. The observed differences reached more than 50%. As already mentioned, the auditorium ventilation may be responsible for this fact as it may have caused the removal of a certain amount of coarse aerosol particles and the decrease of their concentration in the indoor air. It is also possible that a certain amount of these particles was deposited on indoor surfaces or accumulated in the students’ respiratory tract. The next step of investigation was to eliminate the influence of the AC system on the aerosol particle concentration. In order to do so the changes of the coarse aerosol particle concentration at the beginning and at the end of the two consecutive 45-minute lectures in the auditorium with a switched off AC system were analyzed. Graphs a and b in Figure 4 show the concentration changes of these particles when, respectively, 84 and 44 students were present in the auditorium. The graphs indicate that the coarse aerosol particle concentration was decisively lower at the end of the lectures. This reduction is mainly caused by the deposition of these particles on indoor surfaces during the lectures. An almost double decrease of the number of students during the second lecture (from 11:15 a.m. to 12:00 a.m.) did not translate into a double reduction of the aerosol particle concentration. The reason for this may be an insufficient amount of time (a 15-minute break) between

Fig. 4. The concentration of coarse aerosol particles during the lectures with a switched off AC system, a – lecture from 10:15 a.m. to 11:00 a.m., 84 students, b – lecture from 11:15 a.m. to 12:00 a.m., 44 students The influence of air-conditioning system and presence of students on... 51 the lectures for an effective particle deposition. A greater activity of the smaller group of students as well as their different seat arrangement cannot also be ruled out [4, 6]. Diagrams a and b in Figure 5 present the changes of the coarse aerosol particle concentration with respect to the number of students present in the auditorium. These dependencies indicate that the mean concentrations of these particles increase together with the increase of the number of students. The bars denote the standard deviation of the measured particle concentrations. The values of the correlation coefficients amount to about 0.42, p = 0.05. The instability of the measurement conditions could be responsible for the considerable scattering of the experimental points around the best fit lines. For example, the indoor air thermal parameters as well as the students’ seating arrangement inside the auditorium varied during the individual measurement periods. A higher increase of the indoor air temperature and relative humidity was reported when more students were present in the room which resulted, among others, in a higher ventilation rate and therefore a more effective aerosol removal from the auditorium [7, 8]. One could also observe that when fewer students were present they usually took seats at the back of the auditorium, closer to the measurement point. In such cases a higher percentage of students was seated near the measurement point comparing to the situation when more students were present and they were more equally spread around the whole auditorium.

Fig. 5. The mean concentration of coarse aerosol particles during the lectures vs. the number of students, a – for particle size fraction 5–10 μm, b – for particle size fraction >10 μm 52 Bernard PoŁednik, Marzenna DudziŃska, Mariusz SkwarczyŃski

Summarizing, the above presented measurement results show the substantial influence of the operating AC system and the presence of students in the auditorium on the indoor aerosol concentrations. The results of a more detailed research could help to improve the indoor environment conditions in the investigated auditorium and other school facilities with AC systems. They could be used for effective control of AC processes connected with e.g. the application of the so-called adaptive demand-controlled ventilation [15–17], which could respond to the actual occupation and aerosol concentration changes. This would ensure constantly low aerosol particle concentrations which would positively influence the indoor air quality in this type of facilities.

Conclusions

The results of the performed measurements allow to conclude the following: 1. There is a high variability of aerosol particle concentrations inside the auditorium which is mainly caused by the AC system and the presence of the students. 2. The aerosol particle concentrations are higher when the AC system is switched on. This may be caused by the increased air movement in the auditorium and consequently the resuspension of the settled particles. 3. The concentrations of coarse aerosol particles increase with the increase of the number of students inside the auditorium irrespectively of the operation of the AC system. 4. The presented results of this preliminary study may be of universal significance in terms of monitoring and control processes carried out in order to improve the indoor air quality in school facilities with AC systems.

Acknowledgements This study has been supported by the scientific grant No. 4955/B/T02/2008/34 from the Ministry of Science and Higher Education, Poland.

References

[1] Abt E., H.H. Suh, P. Catalano, P. Koutrakis: Relative contribution of outdoor and indoor particle sources to indoor concentrations, Environmental Science and Technology, 34, 3579–3587 (2000). [2] Afshari A., U. Matson, L.E. Ekberg: Characterization of indoor sources of fine and ultrafine particles: a study conducted in a full-scale chamber, Indoor Air, 15, 2, 141–150 (2005). [3] Blondeau P., V. Iordache, O. Poupard, D. Genin, F. Allard: Relationship between outdoor and indoor air quality in eight French schools, Indoor Air, 15, 1, 2–12 (2005). [4] Braniš M., P. Řezáčová, M. Domasová: The effect of outdoor air and indoor human activity on mass

concentrations of PM10, PM2.5 and PM1 in a classroom, Environmental Research, 99, 2, 143–149 (2005). [5] Daisey J.M., W.J. Angell, M.G. Apte: Indoor air quality, ventilation and health symptoms in schools: An analysis of existing information, Indoor Air, 13, 53–64 (2003). [6] Ferro A.R., R.J. Kopperud, L.M. Hildemann: Source strengths for indoor human activities that resuspend particulate matter, Environ. Sci. Technol., 38, 1759–1764 (2004). [7] Fisk W.J., D. Faulkner, D. Sullivan, M.J. Mendell: Particle Concentrations and Sizes with Normal and High Efficiency Air Filtration in a Sealed Air-Conditioned Office Building, Aerosol Science & Technol- ogy, 32, 6, 527–544 (2000). [8] Guo H., L. Morawska, C. He, D. Gilbert: Impact of ventilation scenario on air exchange rates and on indoor particle number concentrations in an air-conditioned classroom, Atmospheric Environment, 42, 4, 757–768 (2008). The influence of air-conditioning system and presence of students on... 53

[9] Hacker D.W., E.M. Sparrow: Use of air-cleaning devices to create airborne particle-free spaces intended to alleviate allergic rhinitis and asthma during sleep, Indoor Air, 15, 6, 420–431 (2005). [10] Holmberg S., Q. Chen: Air flow and particle control with different ventilation systems in a classroom, Indoor Air, 13, 2, 200–204 (2003). [11] Hussein T., T. Glytsos, J. Ondráček, P. Dohányosová, V. Ždímal, K. Hämeri: Particle size characterization and emission rates during indoor activities in a house, Atmospheric Environment, 40, 4285–4307 (2006). [12] Jamriska M., L. Morawska, D.S. Ensor: Control strategies for sub-micrometer particles indoors: model study of air filtration andventilation , Indoor Air, 13, 2, 96–105 (2003). [13] Mendell M.J., G.A. Heath: Do indoor pollutants and thermal conditions in schools influence student performance? A critical review of the literature, Indoor Air, 15, 1, 27–52 (2005). [14] Mossolly M., K. Ghali, K. Ghaddar: Optimal control strategy for a multi-zone air conditioning system using a genetic algorithm, Energy, 34, 1, 58–66 (2009).

[15] Połednik B., M. Dudzińska, A. Raczkowski: The influence of occupation on aerosol and CO2 concentration in classroom, [in:] Indoor Air 2008, The 11th International Conference on Indoor Air Quality and Climate, Conference Proceedings, Paper ID: 546, Copenhagen 2008. [16] Report No 22, EUR 19529EN: Risk assessment in relation to indoor air quality, 2000. [17] Sajo E., H. Zhu, J.C. Courtney: Spatial distribution of indoor aerosol deposition under accidental release conditions, Health Phys., 83, 6, 871–883 (2002). [18] Schneider T., J. Sundell, W. Bischof, M. Bohgard, J.W. Cherrie, P.A. Clausen, S. Dreborg, J. Kildesø, S.K. Kjærgaard, M. Løvik, P. Pasanen, K. Skyberg: Airborne particles in the indoor environment. A European interdisciplinary review of scientific evidence on associations between exposure to particles in buildings and health effects, ‘EUROPART’, Indoor Air, 13, 1, 38–48 (2003). [19] Shaughnessy R.J., U. Haverinen-Shaughnessy, A. Nevalainen, D. Moschandreas: A preliminary study on the association between ventilation rates in classrooms and student performance, Indoor Air, 16, 6, 465–468 (2006). [20] Xu X.H, S.W. Wang: An Adaptive Demand-controlled Ventilation Strategy with Zone Temperature Reset for Multi-zone Air-conditioning Systems, Indoor and Built Environment, 16, 5, 426–437 (2007).

Received: April 7, 2009; accepted: August 2, 2009.

WPŁYW KLIMATYZACJI I OBECNOŚCI STUDENTÓW NA KONCENTRACJĘ AEROZOLI W AULI

Aerozole wewnątrz pomieszczeń generowane między innymi przez systemy klimatyzacyjne są szczególnie istotne w szkołach. Pomiary prowadzone w nowym, klimatyzowanym audytorium pokazały, że koncentracja aerozoli w bardzo dużym stopniu zależy od działania klimatyzacji i obecności studentów. Uzyskane wyniki pokazały, że w klimatyzowanej auli koncentracja aerozoli była około pięciokrotnie wyższa w porówna- niu z sytuacją, gdy aula nie była klimatyzowana. Wynikać to może z faktu zwiększonej cyrkulacji powietrza i związanej z tym resuspensji cząstek aerozolowych osiadłych na powierzchniach wewnętrznych. Może to również wskazywać na nieefektywność działania systemu filtrującego powietrze. Obecność studentów w auli powodowała wzrost koncentracji grubych cząstek aerozolowych niezależnie od działania systemu klimatyza- cyjnego. Dla zapewnienia pożądanej jakości powietrza wewnętrznego wyniki monitoringu cząstek aerozolowych powinny być brane pod uwagę przy sterowaniu procesami klimatyzacji w tego typu pomieszczeniach.

54 55

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 55 - 67 2009 PL ISSN 0324-8461

STUDY OF ALUMINIUM SULPHATE COMPLEXES OF SURFACE WATER AND FRACTIONATION OF ALUMINIUM FROM BOTTOM SEDIMENT

MARCIN FRANKOWSKI*, ANETTA ZIOŁA-FRANKOWSKA, JERZY SIEPAK

Adam Mickiewicz University, Department of Water and Soil Analysis ul. Drzymały 24, 60-613 Poznań, Poland * Corresponding author e-mail: [email protected]

Keywords: Aluminium, fractionation, grain size fractions, aluminum-sulphate complexes, Mineql+ program.

Abstract: The paper presents results of aluminium concentration determination in the samples of surface water and bottom sediments of the Mała Wełna River (West Poland). In the surface water the concentration of aluminium varies in the range from 4.14 to 25.9 µg/dm3. With use of the Mineql+ program the concentration of the aluminium sulphate complexes in the water samples studied has been determined in a model way. In the bottom sediments samples of the river aluminium has been determined in the granulometric fractions of the grain sizes > 2.0; 2.0–1.0; 1.0–0.5; 0.5–0.25; 0.25–0.1; 0.1–0.063; < 0.063 mm, using the sequential extraction scheme proposed by Tessier et al. The lowest concentration of aluminium has been found in the granulometric fraction 0.5–0.25 mm, while the highest in the fractions 0.1–0.063 and < 0.063 mm. An elevated concentration of aluminium has been also noted in the fraction > 2.0 mm. Taking into regard the chemical fractions the lowest concentration of aluminium has been found in the exchange fraction and the fraction bounded to carbonates (fractions I and II), whereas the highest concentration of aluminium has been determined in the lithogenic fraction (fraction V). The methods of sample preparation for analysis of aluminium in bottom sediments were compared. It was observed that higher concentration of aluminium was present in grounded samples without its influence on grain size fractions. The concentration of aluminium in surface water samples has been determined by the GF-AAS, while in bottom sediments by F-AAS.

INTRODUCTION

The natural content of aluminium in the Earth’s crust (7.8% of the total mass of the Earth) and susceptibility to external factors and numerous reactions occurring in natural environment is reflected in its forms of occurrence which condition its degree of bioavailability and mobility in aquatic ecosystems [7, 16, 21, 27]. The aluminium concentration in surface waters most frequently is at the range from 60 to 300 μg/dm3, while river waters are characterized by the average aluminium concentration of 64 μg/dm3 [17]. However, it should be emphasized that such low aluminium concentrations occur in the aquatic ecosystems with stable conditions of temperature, pH reaction, redox potential or the amount of inorganic and organic contaminants in waters. The variability of environmental conditions may affect the shift of balance in the sorption – desorption and water – sediment systems, increasing at the same time the occurrence possibility of dissolved, and as a result available, forms of aluminium. The highest solubility of aluminium occurs in 56 MARCIN FRANKOWSKI, ANETTA ZIOŁA-FRANKOWSKA, JERZY SIEPAK the waters of strongly acid environments (for example, in the areas of frequent volcanic activity or the zones of sulfide deposits oxidation) or strongly alkaline environments (for example, in the areas of alkaline lakes, the zones of low-pressure products dissolution or the zones of thermal metamorphism of carbonate rocks). As a result, aluminium may occur at the levels exceeding the acceptable concentrations in drinking water, which is toxic for living organisms. Aluminium in aqueous solutions is characterized by amphoteric properties and may create both cation and anion complexes, organic and inorganic, with the tendency towards polymerization [32]. The factors which determine the type of the complex include pH reaction of water, temperature, concentration of ligands and ionic strength of solution [22]. Depending on the form of complex compounds, the aluminium complexes created are characterized by different toxic influence on living organisms [2, 3, 15, 23]. The inorganic monomeric aluminium with fluoride and sulphate ions complexes is considered the toxic form of aluminium [9, 10, 14]. In the environment with a high level of acidity, sulphate ions make the main anion which occurs together with dissolved inorganic forms of aluminium and creates complex with them [21]. The presence of dominating aluminium-sulphate complex forms depends on the sulphate ions + concentration in the environment. The ions AlSO4 occur with low concentrations, while - 2- the ions Al(SO4)2 are characteristic for higher concentrations of SO4 [22]. The Al-SO4 complexes are dominant only with the high concentrations of sulphate ions and low pH < 4.5 and they are not as stable as the aluminium fluoride complexes [8, 33]. The aim of the research was (1) the determination of aluminium concentration in surface waters, (2) the identification of aluminium forms in bottom sediments by means of the sequential extraction procedure, (3) the assessment of the influence of a granulometric fraction size on aluminium concentration, (4) the assessment of the influence of sample preparation on aluminium concentration at particular stages of the sequential extraction procedure, (5) modeling with the use of Mineql+ program and determination of the concentration of aluminium-sulphate complex forms in the investigated water samples.

MATERIALS AND METHODS

Study area The Mała Wełna River catchment area lies in the centre of the Wielkopolsko-Kujawska Lowland [18]. The river is 83.8 km long and its catchment area is 688 km2. Up to the profile Kiszkowo at the end of the catchment fragment studied, the Mała Wełna River flows through eight lakes with a total water surface area of 392.8 ha and a complex of fish ponds with a surface area of 235.1 ha (Fig. 1). The catchment area of the river is mostly agricultural (arable land 82.7%), forests (8.0%), orchards (0.3%) and idle land (9.0%). The area of the catchment fragment studied is 342 km2, and the length of the river in this fragment is 45.3 km, with a slope of 0.58‰ [17, 18].

Sample collection and preparation Once a month from May to August 2006, the samples of water and bottom sediments were collected at nine sites along the course of the Mała Wełna River (Fig. 1). The water samples were collected with the Toń 2 sampler and placed into polyethylene (PE) bottles. The bottom sediment samples were collected with the Czapla-1 core- STUDY OF ALUMINIUM SULPHATE COMPLEXES OF SURFACE WATER AND... 57

Fig. 1. Sampling points of water and bottom sediment (the Mała Wełna River) sampler (Mera-Błonie, Gdańsk, Poland) and placed into PE containers. The sediment sample was dry sieved into seven-grain size fractions > 2.0 mm, 2.0–1.0 mm, 1.0–0.5 mm, 0.5–0.25 mm, 0.25–0.1 mm, 0.1–0.063 mm, < 0.063 mm through a LAB-11-200/UP mechanical shaker (Brzesko, Poland) with a series of stainless steel sieves. In order to differentiate and conduct quantitative determination of aluminium forms in particular granulometric fractions of bottom sediments samples, the modified sequential extraction scheme suggested by Tessier et al. was used (Tab. 1).

Chemical analysis The determination of total aluminium concentration in water samples was performed by means of the graphite furnace atomic absorption spectrometry (GF-AAS). The atomic absorption spectrometer SpectrAA 20 Plus (Varian, Australia) was used for the determinations. The aluminium determinations in granulometric fractions of bottom sediments were performed with use of the absorption spectrometry with flame atomization (F-AAS) technique on the two-beam Perkin Elmer instrument, model AAnalyst 300 (Perkin Elmer, 58 MARCIN FRANKOWSKI, ANETTA ZIOŁA-FRANKOWSKA, JERZY SIEPAK

Table 1. Operating parameters for determination of aluminium by GF-AAS and F-AAS spectrometers GF-AAS F-AAS Wavelength [nm] 309.3 Slit [nm] 0.5 Lamp current [mA] 6 25 3 Flow of C2H2 [dm /min] – 6 3 Flow of N2O [dm /min] – 8,5 Flame temperature [°C] – 3000 Argon flow [dm3/min] 3.0 – Drying [°C] 120 – Drying time [s] 40 – Ashing [°C] 1000 – Ashing time [s] 2 – Atomization [°C] 2600 – Atomization time [s] 2 – Cleaning [°C] 2700 – Cleaning time [s] 2 – Delay time [s] – 2 Measurement time [s] – 3 Number of replications – 3

Norwalk, Connecticut, USA). The optimized conditions for aluminium determinations have been presented in Table 2. 2- Concentration of SO4 was determined by gravimetric method, pH reaction of the surface water was determined by a multifunctional measuring device, Multi 197, manufactured by WTW (Weilheim, Germany).

Table 2. Optimized conditions of sequential extraction procedure proposed by Tessier et al. [30] with modifications by Sobczyńskiet al. [25]

1 g of sample of bottom sediment Extraction reagents time [h] temperature [°C] steps 3 I 10 cm of 1 M CH3COONH4, pH = 7.00 1 room 20 cm3 of 1 M CH COONa acidify to pH = 5.00 with II 3 2 room CH3COOH 3 III 20 cm of 0.04 M NH2OH×HCl in 25% CH3COOH 5 95 3 3 5 cm of 0.02 M HNO3 + 5 cm of 30% H2O2, pH = 2.00 2 85 3 IV 5 cm of 30% H2O2, pH = 2.00 3 85 3 10 cm of 3.2 M CH3COONH4 in 20% (v/v) HNO3 0.5 room 3 3 cm3 of HNO3 + 2 cm of 30% H2O2 0.5 V 3 cm3 of HF + 2 cm3 30% H O 0.5 2 2 95 3 3 3 cm of HF + 3 cm HNO3 1 STUDY OF ALUMINIUM SULPHATE COMPLEXES OF SURFACE WATER AND... 59

Reagents All the reagents used were of analytical grade, and the water was deionized with a resistance > 18 MΩ in a Milli Q-RG apparatus (Millipore, France). The reference standard solutions were made of commercial standards for AAS analysis by Merck (Merck, Darm- stadt, Germany).

RESULTS AND DISCUSSION

The total aluminium concentration in the all samples of surface waters of the Mała Wełna River in the research period from May to August 2006 was in the range from 4.14 to 25.9 µg/dm3, for pH 7.1–7.5. Concentration of sulphates was in the range of 91.8–197.1 mg/dm3. The lowest concentrations of aluminium were observed at site No. 6, whereas the highest – at the sampling site No. 7 (fish ponds) (Fig. 2). The similar aluminium concentrations as at site No. 6 were observed at sampling sites No. 2 and 4 (Kłeckie Lake and Gorzuchowskie Lake) and in Zakrzewo (site No. 5). During the analysis of variability of aluminium concentration in time, the lowest and highest concentrations were observed in May, at site No. 2 (Kłeckie Lake) and No. 7 (fish ponds) respectively. It should be stressed that the increase of aluminium concentrations was observed in the Mała Wełna River at sites No. 3 and 7 to 9 in comparison with other research points. ] 3 Al [μ/dm

Sampling points

Fig. 2. Concentration of aluminium in water samples of the Mała Wełna River

Based on the obtained results it was observed that, together with the increase of [H+] concentration, the total concentration of aluminium decreased. On the other hand, the decrease of the [H+] was accompanied by the increase of aluminium content, which has been graphically presented in Figure 3. The total aluminium level in the investigated water samples collected from the Mała Wełna River was low in comparison with, for example, the total aluminium content in the Vienne Royere River (from 16.4 to 100.6 µg/dm3, pH 5.8–7.9), or in the Vienne Peyre- levade River (from 22.4 to 130.5 µg/dm3, pH 5.7–6.8) [14]. Definitely higher concentrations of total aluminium were observed in the Vezare River (from 45.2 to 146.4 µg/dm3, 60 MARCIN FRANKOWSKI, ANETTA ZIOŁA-FRANKOWSKA, JERZY SIEPAK

24 ] 3 20

Concentration [mol/dm 8

4 E-8 0 7.1 7.2 7.3 7.4 7.5 7.6 Al tot. ▼ pH

Fig. 3. Concentration of total aluminium in the function of water Ph for all analyzed samples pH 5.6–6.8), the Grande Creuse (from 9.2 do 141.2 µg/dm3, pH 6.5–7.4), or the Gar- tempe (from 8.7 do 274.8 µg/dm3, pH 6.2–7.0) [15]. The rivers were located in the areas of high contamination level, similarly to the surface waters of Adirondack, Maine or Florida, which contained 8.1–756; 8.1–810; 8.1–1350 µg/dm3 of total aluminium respectively [15]. The increased concentrations of aluminium from 27 to 1080 µg/dm3 were determined in the waters exposed to acid rain in the Czech Republic, and from 81 to 1194 µg/dm3 in the waters exposed to air pollution in northern England [20]. In the case of lack of exposure of the river waters to air pollution, the total aluminium concentration amounted to < 1.0 µg/dm3 in Birkenes, and in the case of acid deposition, the aluminium concentration was much higher and it amounted to 110 µg/dm3 [5]. In order to determine the content of aluminium-sulphate complex froms occurring in the waters of the Mała Wełna River, the Statisica 7.1 packet (StatSoft, Poland) and the Mineql+ program 4.5 (USA) were used. Using the Statisica 7.1 packet, the data standardization was done. The data were obtained through calculations with use of the Mineql+ 4.5 program (Tab. 3). The data after standardization are presented in Figure 4. In the case of aluminium-sulphate complexes, it was observed that, together with the + + - increase of [H ] and sulphate ions, the concentration of AlSO4 and Al(SO4)2 complexes increases, with the simultaneous decrease of the total aluminium content. The dominating + complex form in the investigated samples was AlSO4 (Fig. 5). On the other hand, the increased pH level was accompanied by the disintegration of sulphate complexes with the simultaneous aluminium release. It resulted from the fact that complexes of aluminium + with sulphates are characterized by low values of stability constants, log K for AlSO4 and - Al(SO4)2 amounts to 3.89 and 4.92 respectively (Figs 4 and 5). It should be emphasized that, despite determining a low concentration of total aluminium in the investigated waters, only quantitative and qualitative defining of its speciation forms, and especially the inorganic monomeric form which includes the toxic form, will enable the assessment of its actual risk level for the river ecosystem. The forms STUDY OF ALUMINIUM SULPHATE COMPLEXES OF SURFACE WATER AND... 61

2- SO4

+ AlSO4

- Al(SO4)2

[H+]

Altot.

2- + - Fig. 4. Co-occurrence of SO4 , AlSO4 , Al(SO4)2 , total Al and amount of hydrogen ions after standardization (sampling point No. 5)

10 ] 3 8

4 Concentration [mol/dm

2 E-13 0 7.1 7.2 7.3 7.4 7.5 7.6

+ - pH AlSO4 Al(SO4)2

+ - Fig. 5. Concentration of AlSO4 and Al(SO4)2 complexes in the function of water pH which create monomeric aluminium are its complex with fluorides, phosphates and sul- + - phates [4, 31]. Aluminium-sulphate complexes occur in the form of AlSO4 and Al(SO4)2 ions and their presence in river ecosystems depends on sulphate ions concentration and on the pH value. This dependence was used while studying the concentration of aluminium complexes with sulphates based on the actual results of the total aluminium concentration and the sulphates concentration by means of the Mineql+ program. The obtained results 62 MARCIN FRANKOWSKI, ANETTA ZIOŁA-FRANKOWSKA, JERZY SIEPAK

+ demonstrated that the dominating form in the waters under investigation was AlSO4 (Fig. 5), and its highest contents occurred in May (Tab. 3).

Table 3. Concentration of aluminium, sulphate and [H+] in surface water of the Mała Wełna River (sampling

point No. 5) and calculated concentrations of Al-SO4 complexes from Mineql+ program May June July August [mol/dm3] 2- SO4 1.41E-03 1.56E-03 1.61E-03 1.54E-03 + AlSO4 6.75E-14 1.50E-13 6.15E-13 1.48E-13 - Al(SO4)2 1.02E-15 2.51E-15 1.06E-14 2.44E-15 [H+] 3.16E-08 3.98E-08 6.31E-08 3.98E-08

Altot 2.85E-07 2.81E-07 2.30E-07 3.03E-07

- The Al(SO4)2 form occurred at the lower concentration levels, due to the low concentration of sulphates in the investigated samples collected from the Mała Wełna River and the pH reaction of water (Fig. 5). Both isolated forms represent monomeric inorganic aluminium, which has toxic influence on living organisms. Similar trend like for sample No. 5 was observed for other analyzed sampling points (Tab. 4). Table 4 presents mean values of aluminium and sulphates and calculated values of aluminium sulphate complexes [mol/dm3].

Table 4. Concentration of aluminium, sulphate and [H+] in all samples of surface water of the Mała Wełna

River and calculated concentrations of Al-SO4 complexes from Mineql+ program (May – August)

Sampling Al [mol/dm3] SO 2- [mol/dm3] [H+] AlSO + [mol/dm3] Al(SO ) - [mol/dm3] points tot 4 4 4 2 1 4.61E-07 1.74E-03 2.24E-08 7.48E-14 1.39E-15 2 2.35E-07 1.60E-03 1.58E-08 8.86E-15 1.52E-16 3 7.26E-07 1.49E-03 2.24E-08 1.01E-13 1.61E-15 4 2.48E-07 1.56E-03 1.58E-08 9.11E-15 1.52E-16 5 2.68E-07 1.51E-03 4.47E-08 5.84E-13 9.46E-15 6 1.85E-07 1.53E-03 7.08E-08 2.50E-12 4.10E-14 7 7.78E-07 1.42E-03 5.62E-08 3.96E-12 6.02E-14 8 4.61E-07 1.18E-03 5.01E-08 1.24E-12 1.56E-14 9 5.15E-07 1.18E-03 5.01E-08 1.38E-12 1.75E-14

According to Kroglund and Finstad the sum of all forms of monomeric aluminium with the concentration of 1.5 to 3.0×10-7 mol/dm3 is toxic for the Atlantic salmon + -13 3 [19]. However, the obtained concentrations for the AlSO4 (max. 6.15×10 mol/dm ) - -15 3 and Al(SO4)2 (max 2.51×10 mol/dm ) forms do not pose any danger for the living organisms studied in the Mała Wełna River. Contrary to the toxic concentrations of aluminium in the Vienne Royere River (1.1×10-6 mol/dm3), or the Vienne Peyrelevade River (6.0×10-7 mol/dm3) [14], higher values were suggested by Kroglund and Finstad [19]. In comparison to Kroglund and Finstad higher concentrations of the toxic aluminium form were also determined in the Vezer River (from 0.2×10-5 to 0.59×10-3 µmol/dm3), the STUDY OF ALUMINIUM SULPHATE COMPLEXES OF SURFACE WATER AND... 63

Grande Creuse (from 0.27×10-4 to 0.544×10-3 µmol/dm3), the Gartempe (from 0.6×10-5 to 0.112×10-3 µmol/dm3) [15, 19]. The water samples analysis enabled the determination of various forms of aluminium but, in order to find out complete information of the potential cycle of this element in the studied aquatic ecosystem, it was essential to determine its mobile forms in bottom sediments. The obtained results of aluminium fractionation, in particular granulometric fractions, for bottom sediments were presented on the example of the research site No. 5 (Fig. 6) and presented trend of occurring of particular fractionation form of aluminium was observed for all samples from the study area. In the two first most toxic fractions, that is the exchangeable one and the one associated with carbonates, the concentration of aluminium in all the analyzed samples was low and it reached the maximum value of up to 5.65 mg/kg d.m. (for granulometric fraction < 0.063 mm). Higher concentrations of aluminium were determined in the chemical fraction associated with Fe-Mn oxides (fraction III). The highest concentrations of aluminium were determined in the grain size fraction > 2.0 mm which amounted to 1720 mg/kg d.m., while for the fraction 0.25–0.1 mm the aluminium concentration amounted to 356 mg/kg d.m. It is noteworthy that the aluminium occurring in this fraction is less mobile than in the case of fractions I and II, hence its penetration to the water depth is more difficult. In the fraction connected to organic matter (fraction IV), the highest concentration of metal occurred in grain size fraction < 0.063 mm and it amounted to 1710 mg/kg d.m. Sobczyński et al. [25], on the example of bottom sediments of the Oder River and lake sediments, also observed the increase of aluminium concentration in this fraction. Sobczyński et al. related this fact to the increase of organic matter concentration in bottom sediments [25, 26]. Sin et al. while performing mineralization with HCl i HNO3 acids in the samples of river sediments of the Shing Mun River, obtained the aluminium concentration at the levels from 0.249 to 114 mg/g d.m. [24]. When these values are compared with the concentrations obtained for fraction IV in the sediments of the Mała Wełna River, one can observe that they are much lower. On the other hand, Deheyn and Latz using the 45% HNO3 obtained the aluminium concentration at the level of 0.055 to 0.62 mg/g d.m. in the sediments of San Diego Bay, describing this form of aluminium as connected with organic matter [6]. The highest concentration of aluminium in the bottom sediments of the Mała Wełna River was determined in the lithogenic fraction (fraction V), in which aluminium is practically unavailable for living organisms. It results from the fact that aluminium is built in mineral structures, hence, in order to release it, strongly reductive conditions would be necessary. In the bottom sediments of the Mała Wełna River the content of aluminium in fraction V was in the range from 550 to 2330 mg/kg d.m., and the highest concentrations were observed for granulometric fraction < 0.063 mm (Fig. 6). These results are considerably lower than the ones obtained by Baborowska et al. where the total aluminium content in the bottom sediments was determined at the concentration level of 41–73 g/kg d.m. [1]. While analyzing the aluminium concentration in particular granulometric fractions of the investigated bottom sediments samples, the highest concentrations of aluminium were observed in fraction < 0.063 mm for chemical fractions II, IV and V, and for granulometric fraction > 2.0 mm in the case of chemical fraction III (Fig. 6). The similar trend of aluminium was observed in granulometric fraction of tsunami deposit samples determined by Zioła-Frankowska et al. [34]. 64 MARCIN FRANKOWSKI, ANETTA ZIOŁA-FRANKOWSKA, JERZY SIEPAK

grain size fractions Al [mg/kg d.m.]

Fig. 6. Concentration of aluminium in bottom sediment of the Mała Wełna River, in particular chemical fraction and granulometric fractions (sampling point No. 5)

The results of the research by Sutherland et al. [28, 29] in granulometric fractions < 0.063, 0.063–0.125, 0.125–0.25, 0.25–0.5, 0.5–1.0, 1.0–2.0 mm indicate that author obtained a similar dependence of the tendency for one analyzed element (Pb) in comparison to the obtained results presented in this study. Sutherland determined the highest concentration of Pb in bottom sediments in the granulometric fraction 0.500–1.0 mm [28, 29]. Frankowski et al. presented the results of the research on bottom sediments of the

Oder River, where the extraction with use of HNO3 and H2O2 acids in twelve granulometric fractions of river sediments was applied [12]. The results of determination of metals for particular granulometric fractions presented in the study look similar to the results obtained in this study and in the study by Frankowski et al. [11, 13]. Within the scope of the conducted research, the assessment of the influence of the method of bottom sediments sample preparation on the aluminium concentration, in par- Al [mg/kg d.m.]

Grain size fractions * - grounded samples

Fig. 7. Concentration of aluminium in particular chemical fractions for selected grain size fractions in bottom sediments of the Mała Wełna River (sampling point No. 5) STUDY OF ALUMINIUM SULPHATE COMPLEXES OF SURFACE WATER AND... 65 ticular chemical fractions subjected to the procedure of sequential extraction, was conducted. Sample No. 5 with 1.0–0.5 mm, 0.5–0.25 mm, 0.25–0.1 mm grain size fractions was subjected to the sequential extraction procedure for the samples grounded in the agate mortar, and for the samples which were not grounded (Fig. 7). The obtained results indicate a considerably higher concentration of aluminium in chemical fractions III–V for the grounded samples, in comparison with the ones which were not grounded.

CONCLUSIONS

Based on the obtained results of the aluminium research in the samples of surface waters and bottom sediments of the Mała Wełna River in the period from May to August 2006, the following conclusions may be formulated: 1. Low concentrations of total aluminium (from 4.14 to 25.9 µg/dm3) determined in the water of the Mała Wełna River indicate only a small burden of the investigated waters with this element. A slight increase of the aluminium concentration was only observed at the sites located below towns, which may indicate local contamination with this element. 2. It was also observed that, together with the increase of [H+] and sulphate ions + - concentration, the concentration of AlSO4 and Al(SO4)2 complexes increases, with a simultaneous decrease of the total aluminium content. It was assumed that the dominating complex form in the all investigated water samples was + AlSO4 . 3. For particular granulometric fractions of the all investigated samples of bottom sediments the highest concentration of aluminium was determined in fraction < 0.063 mm for chemical fractions II, IV, V and for granulometric fraction > 2.0 mm in the case of chemical fraction III. 4. In the case of bottom sediments, the lowest concentration of aluminium was determined in the exchangeable fraction and the fraction connected with carbonates (fraction I and II – the most mobile), while the highest concentrations were determined in the lithogenic fraction (fraction V), where aluminium is practically unavailable for living organisms. + 5. The concentrations of aluminium speciation forms obtained in water (AlSO4 ; - Al(SO4)2 ) and in bottom sediments (especially for chemical fractions I and II) do not pose any danger for living organisms in the Mała Wełna River. 6. It was found that higher concentration of aluminium in chemical fractions III– V was observed for the grounded samples in comparison with the ones which were not grounded.

Acknowledgements The research was financed from the 2007–2009 research fund as project N 305 101 235 of the Ministry of Science and Higher Education. 66 MARCIN FRANKOWSKI, ANETTA ZIOŁA-FRANKOWSKA, JERZY SIEPAK

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Received: November 12, 2008; accepted: August 5, 2009.

OZNACZANIE I MODELOWANIE GLINU W POŁĄCZENIACH Z SIARCZANAMI W WODACH POWIERZCHNIOWYCH I FRAKCJONOWANIE GLINU W OSADACH DENNYCH

W pracy przedstawiono wyniki oznaczeń glinu w próbach wód powierzchniowych i osadach dennych rzeki Mała Wełna. W wodach powierzchniowych stwierdzono stężenie glinu w przedziale 4,14–25,9 µg/dm3. Przy wyko- rzystaniu programu do modelowania Mineql+ wyliczono stężenie form kompleksów glinowo-siarczanowych w badanych próbkach wody. Frakcjonowanie glinu w osadach dennych przeprowadzono we frakcjach granu- lometrycznych o uziarnieniu: > 2,0; 2,0–1,0; 1,0–0,5; 0,5–0,25; 0,25–0,1; 0,1–0,063; < 0,063 mm, z wyko- rzystaniem zmodyfikowanego schematu ekstrakcji sekwencyjnej zaproponowanego przez Tessiera i współ- pracowników. Najniższe stężenia glinu występowały we frakcji granulometrycznej od 0,25–0,5 mm, natomiast najwyższe stężenia we frakcji 0,1–0,063 mm i < 0,063 mm. Zaobserwowano również wzrost stężenia glinu we frakcji granulometrycznej > 2,0 mm. W przypadku frakcji chemicznych najniższe stężenia glinu oznaczono we frakcji wymienialnej i związanej z węglanami (frakcja I i II), natomiast najwyższe stężenia glinu oznaczono we frakcji litogennej (frakcja V). Porównano metody przygotowania próbki do analizy glinu w osadach dennych. Stwierdzono wyższe stężenia glinu w próbkach poddanych rozcieraniu bez względu na wielkość frakcji granulometrycznej. Glin w wodach powierzchniowych oznaczono techniką absorpcyjnej spektrometrii atomowej z atomizacją w kuwecie grafitowej (GF-AAS), a w osadach dennych techniką absorpcyjnej spektrometrii atomowej z atomizacją w płomieniu (F-AAS). 68 69

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 69 - 77 2009 PL ISSN 0324-8461

OCCURRENCE STUDY OF AGRO-CHEMICAL POLLUTANTS IN WATERS OF SUPRAŚL CATCHMENT

KATARZYNA IGNATOWICZ

Białystok Technical University, Department of Technology in Engineering and Environmental Protection ul. Wiejska 45a, 15-351 Białystok, Poland e-mail: [email protected]

Keywords: Herbicides, pesticides, Supraśl catchment, agropollutants, biogenic, rural catchments.

Abstract: The paper presents the results on the studies on determination of concentrations of four phenoxyacetic herbicides, four triazine herbicides, seven insecticides and other pollutants in the Supraśl catchment. The samples were collected over a period of two years, from May 2003 to April 2005. This work will be a precious source of information about the occurrence of agropollutants in the surface water. The residues of herbicides active ingredients were determined using chromatography methods – GC with ECD and NP detection. The maximum residues of herbicide in surface water were detected in spring and autumn – up to 120 µg/dm3 for phenoxyacetic acid (2,4-D, MCPA, MCPP). The most important fact noted during the research is that in surface water used for drinking significant amounts of crop protection substances were detected, which, in the light of the new law concerning the quality of drinking water, must undoubtedly be removed in the treatment processes.

INTRODUCTION

The river Supraśl basin consists of relatively poorly industrialized areas of typically agricultural character as well as large forests. Wide fragments of river Supraśl valley are characterized by high peat index with great percentage of organic soils. This area is distinguished by high contribution of arable lands (from 61.0 to 63.6) and woodlands (from 30.3 to 33.2) of total area (Fig. 1). The agricultural area in the basin covers about 22 073.7 ha, including 3 937.8 ha of arable lands and 18 135.9 ha of green lands [15]. These areas are potentially threatened by river water pollution due to wastes from agrotechnical operations associated with fertilization and using the plant protection means. The pollutants penetrate into the water not only with surface runoff, but also through melioration ditches and drainage filters, because soils are meliorated in 80. Individual farms with mean area of about 10 ha dominate within the river Supraśl basin. Mineral fertilizers are applied at amounts much lower than in the rest of the country. In total, about 62 kg of pure NPK/ha were used in the river Supraśl basin in 2004 [6]. N : P : K ratio is 1.3 : 1.0 : 0.8, which gives: N – 62/3.1 × 1.3 = 26 kg/ha,

P2O5 – 62/3.1 × 1.0 = 20 kg/ha,

K2O – 62/3.1 × 0.8 = 16 kg/ha. According to Sapek [11], nitrogen, phosphorus and potassium losses due to washing out are: nitrogen – 6, phosphorus – 0.4–0.5, and potassium – 21–25. About 573.9 70 KATARZYNA IGNATOWICZ

- built-up area

- coniferous forest

Jałówka Sokołda - mixed forest

Kamionka - green crops

- arable land Nereśl

Jaskranka Czaplinówka Kulikówka

Czarna Słoja

Supraśl Radulinka Pilnica Starzynka Narew Choroszczanka Biała Płoska Czaplinianka

Supraśl Ciek Tartaczny

Fig. 1. The map of sampling points in the Supraśl catchment

Mg of pure nitrogen (26 kg N/ha × 22 073.7 ha), 441.5 Mg of phosphorus P2O5 (20 kg/ha × 22 073.7 ha) and 353.2 Mg of potassium K2O (16 kg/ha × 22 073.7 ha) are applied in fertilizers annually. Theoretically, 34.4 Mg of nitrogen (573.9 Mg × 6%), 11.0 Mg of phosphorus (22 073.7 ha × 0.0005 Mg/ha) and 88.3 Mg of potassium (353.2 Mg × 0.25) may be washed out every year. The amount of pesticides applied was estimated on the base of screening studies upon selected plants in 2004 in Białystok community, including the river Supraśl valley. The studies were carried out by the Department for Plant Protection and Sowing at Re- gional Inspectorate in Białystok. It reached 2 716.54 kg of biologically active substance of pesticides that may be partially washed out into the river. Pesticides are applied ex- clusively on arable lands. In general, 10 times less pesticides are used in Poland than in former EU countries. Performance of the river Supraśl valley also includes the utilization of river water for drinking purposes for Białystok city [5, 6]. EU regulations and those currently binding in Poland precisely define the quality of surface water for drinking as well as they characterize sampling frequency and measurement methods along with permissible limits of pesticide residues in water. Directives [3, 4], Ordinance of November 7, 2002 [9] and Ordinance of August 20, 2008 [10] lists maximum chosen pesticide levels. Because north-eastern region of Poland is typically agricultural and phenoxoacetic and triazine herbicide utilization is high, there is a serious threat of an excessive penetration of these substances into the surface water. The available literature data does not present their current concentrations in Podlasie region waters. Only the measurements of DDT content (that has not been applied for tens of years) and its metabolites have been OCCURRENCE STUDY OF AGRO-CHEMICAL POLLUTANTS IN WATERS OF SUPRAŚL... 71 conducted for several years. Therefore, undertaking the study upon the agrochemical pollution occurrence within the river Supraśl basin seemed to be advisable, because of the fact that the river is a source of drinking water.

MATERIAL AND METHODS

The river Supraśl basin is apparently asymmetric. The river has 18 tributaries, including 11 right and 7 left ones. The right tributaries irrigate 70% and left only 30% of the area. The major right-side tributaries are rivers: the Słoja, the Sokołda and the Czarna, and left-side: the Płoska, the Biała and the Pilnica [6]. The characteristic flow of chosen rivers in the Supraśl catchment is presented in Table 1, and the morphology parameters of the Supraśl tributaries are presented in Table 2. The study area (Fig. 1) besides the river Supraśl (19 points for water sampling), also consisted of its tributaries (14 points): the Słoja, the Pilnica, the Czarna, the Biała, the Radlinka, the Dzierniakówka, the Starzynka, the Płoska, and the Sokołda.

Table 1. The characteristic flow of chosen rivers located in the Knyszyn Primeval Forest Landscape Park during 1976–1995

River Płoska Sokołda Supraśl Sampling point Królowy Most Sokołda Załuki Catchment surface (km2) 190 464 344 Woodiness (%) 68.1 47.3 53.5 Gauging period 1981–1991 1976–1995 1976–1995 Average flow [m3/s] 0.92 2.61 1.81 Variability [%]. 49.5 54.9 60.6 Low-water flow NNQ [m3/s] 0.18 0.38 0.34 Variability [%] 39.7 44.2 42.2 Largest flow WWQ [m3/s] 10.9 40.1 31.2 Variability [%] 97.9 107.9 105.8 WWQ/NNQ 60.6 105.5 91.8 Mean specific runoff [l/(s×km2)] 4.84 5.62 5.26 [%] underground runoff 75.6 58.2 55.8

Table 2. The morphology parameters of Supraśl tributaries

Mean basin Mean river Basin River length Area Circular Lengthen River gradient gradient order [km] [km2] index index [%] [%] Słoja IV 19.6 220.6 0.38 1.94 0.66 1.22 Pilnica IV 10.1 35.0 1.07 3.17 0.49 1.41 Czarna IV 24.5 199.1 0.73 1.3 0.65 1.23 Biała IV 29.9 115.4 1.07 2.1 – –

The study was performed to evaluate the oscillations of agrochemical pollution concentration – biogenic (nitrite, nitrate and ammonium nitrogen, phosphate) and pesticides: 72 KATARZYNA IGNATOWICZ

− phenoxyacetic herbicides – 2,4-D (2,4-dichlorophenoxyacetic acid), MCPA (2-methyl-4-chlorophenoxyacetic acid), MCPP (methylchlorophenoxypropi- onic acid), dichloroprop (2-(2,4-Dichlorophenoxy)propionic acid); − triazine herbicides – atrazine, metribuzon, prometryn, simazine; − insecticide – chloropyrifos, endosulfan, parathion. The data presented here are the result of over 1500 measurements and analytical determinations. The study was conducted between April 2003 and October 2005. Samples were taken once a month. Minimum water sampling frequency during pesticide pollution screening to evaluate the current concentrations and seasonal changes is four times a year with additional measurements during their application and heavy rainfalls [4]. Thus, the assumed sampling rate (once a month) was sufficient. Gas chromatography (GC) is a preferred method for pesticide determination in surface water ensuring about 25% precision level [9, 10]. Pesticide residue in water samples were analyzed using GC techniques in certified Laboratory of Plant Protection Institute in Poznań. The list of analyzed pesticides is presented in Table 3. Statistical evaluation of GC-EC method is presented in Table 4. Active substances were identified using gas chromatography with specific detectors: electron capture (EC), nitrogen-phosphorus (NP), and mass spectrometer (MS). The content of examined substances was calculated on the basis of water matrix calibration. The main problems of pesticides in water analysis, besides small concentrations, are diversification of their properties and the complex- ity of the matrix. The analysis of nitro- and phosphoroorganic insecticides was carried out by means of gas chromatography with thermoionic detector (GC-NPD), analysis of chloroorganic insecticides – gas chromatography with electron capture (GC-ECD), and more polar pesticides (phenoxyacids) – after previous esterification, i.e. transforming into volatile derivatives, by means of gas chromatography with electron capture (GC-ECD). Agrochemical pollutants in water from the river Supraśl basin (nitrogen and phosphorus compounds) were determined in the Institute of Engineering and Environment Protection at Technical University in Białystok.

Table 3. List of substances marked by gas chromatography in water (determination and precision level min 25%) LD LD Method of Method of Active substance Water Active substance Water detection detection [mg/kg] [mg/kg] Atrazine GC-NP 0.0001 Chloropyrifos GC 0.00008 Metrybuzyna GC-EC 0.00003 Endosulfan GC-NP 0.0002 Prometryna GC 0.0002 Parathion GC-NP 0.00035 MCPA GC-EC 0.0010 Azynofos GC 0.0001 Dichloroprop GC-EC 0.003 Fenitrition GC 0.0001 H Mecoprop GC-EC 0.0010 I Fipronil GC 0.0001 Simazine GC-NP 0.0001 Pirymifos GC 0.00005 2.4-D GC-EC 0.0010

H – herbicides, I – insecticides, LD – limit of detection OCCURRENCE STUDY OF AGRO-CHEMICAL POLLUTANTS IN WATERS OF SUPRAŚL... 73

Table 4. Statistical evaluation of GC-EC method

Level of Active Recovery Detectability Limit detection fortification N substances [%] [µg/dm3] [µg/dm3] [µg/dm3] 2.4-D 1 4 87.1 1 1 2.4-D 14 4 94.9 0.5 1 MCPA 1 4 89.9 1 1 MCPA 12 4 95.4 0.5 1 MCPP 1 4 68.5 1 1 MCPP 14 4 94.6 0.5 1

DISCUSSION OF RESULTS

Results confirmed the presence of agrochemical pollutants in water of the river Supraśl basin, namely most common plant protection means – phenoxoacetic herbicides (Tabs 5 and 6). Chemical analyses revealed that those herbicides concentrations oscillated within wide range from 10 up to 120 μg/dm3 (Tab. 5). These levels were higher than those found by Żelechowska and Makowski [18] in waters of the rivers Redunia and Reda, as well as by Siepak et al. in ground water of the Poznań region [12, 13], but they ranged at similar level as in water of the rivers: Narew, Biebrza and Supraśl in previous years [7]. The De- partment of Agriculture in Washington [1] discovered that the amount of phenoxyacetic

Table 5. Herbicides analyzed in the Supraśl catchment

Percent of samples with detections Minimum Maximum Heath value Pesticide season spring summer autumn [µg/dm3] [µg/dm3] [µg/dm3] Phenoxyacetic herbicide 2.4-D 37.65 34.1 20 33.3 10 60 30 MCPA 47.05 38 25 44.4 10 50 – MCPP 64.71 42.5 22.5 55.5 20 120 Dichloroprop ND ND ND ND ND ND Triazine herbicide Atrazine ND ND ND ND ND ND 40.0 Metribuzin ND ND ND ND ND ND 100 Prometryn ND ND ND ND ND ND – Simazine ND ND ND ND ND ND 20.0 Insecticide Chloropyrifos ND ND ND ND ND ND Endosulfan ND ND ND ND ND ND Parathion ND ND ND ND ND ND Azynofos ND ND ND ND ND ND Fenitrition ND ND ND ND ND ND Fipronil ND ND ND ND ND ND Pirymifos ND ND ND ND ND ND

ND – not detected 74 KATARZYNA IGNATOWICZ acid herbicide in surface waters in Salmonid-Bearing Streams ranged 0.022–19 2,4-D μg/dm3, 0.012–15 MCPP μg/dm3 and 0.022–76 MCPA μg/dm3. Stramer [14] estimated the top value of concentrations 2,4-D in the surface waters in England at 100 μg/dm3. Thurman [16] estimated the mean value of concentrations of herbicides in Midwestern Reservoir Outflows at 13.6 μg atrazine, 2.1 μg simazine, 0.25 μg metribuzine, and 0.1 μg propazine per dm3. Table 6. The concentration of agropollutants in the Supraśl catchment

Residue Agropollutants Mean Median Standard deviation Min Max Spring 2.4-D [µg/dm3] 25.9 20 11.37 10 50 MCPA [µg/dm3] 27.6 25 9.71 10 50 MCPP [µg/dm3] 52 50 16.12 20 100 3 P-PO4 [mg/dm ] 0.56 0.53 0.24 0.25 1.42 3 N-NH4 [mg/dm ] 0.48 0.38 0.40 0.12 1.82 3 N-NO2 [mg/dm ] 0.021 0.014 0.0244 0.005 0.157 3 N-NO3 [mg/dm ] 1.51 1.35 0.79 0.60 5.10 Conductivity [µS/cm] 468 427 130 388 953 Summer 2.4-D [µg/dm3] 27.9 30 10.14 10 50 MCPA [µg/dm3] 29.1 30 8.12 10 50 MCPP [µg/dm3] 56.3 50 20.49 20 120 3 P-PO4 [mg/dm ] 0.50 0.47 0.14 0.20 0.78 3 N-NH4 [mg/dm ] 0.47 0.34 0.39 0.24 1.8 3 N-NO2 [mg/dm ] 0.039 0.013 0.078 0.007 0.375 3 N-NO3 [mg/dm ] 2.18 2.00 1.09 0.60 5.70 Conductivity [µS/cm] 472 426 142 382 1057 Autumn 2.4-D [µg/dm3] 27.9 25 13.19 10 60 MCPA [µg/dm3] 30.3 30 10.00 15 50 MCPP [µg/dm3] 61.8 60 18.78 30 100 3 P-PO4 [mg/dm ] 0.76 0.69 0.43 0.08 2.06 3 N-NH4 [mg/dm ] 0.37 0.28 0.35 0.16 2.18 3 N-NO2 [mg/dm ] 0.032 0.011 0.063 0.006 0.310 3 N-NO3 [mg/dm ] 2.35 2.15 0.97 1.10 5.20 Conductivity [µS/cm] 483 439 140 259 954 Research season 2.4-D [µg/dm3] 27 25 11.5 10 60 MCPA [µg/dm3] 29 30 9.3 10 50 MCPP [µg/dm3] 58 60 19.0 20 120 3 P-PO4 [mg/dm ] 0.63 0.55 0.33 0.08 2.06 3 N-NH4 [mg/dm ] 0.41 0.32 0.34 0.12 2.18 3 N-NO2 [mg/dm ] 0.032 0.013 0.063 0.005 0.375 3 N-NO3 [mg/dm ] 2.06 1.90 0.99 0.60 5.70 Conductivity [µS/cm] 478 436 140 259 1057 OCCURRENCE STUDY OF AGRO-CHEMICAL POLLUTANTS IN WATERS OF SUPRAŚL... 75

The highest amounts of these compounds were observed in summer and in autumn. It is associated with spring agrotechnical operations and washing out of the compounds with thawing snow cover as well as further rainfalls. Strong snow thaws and heavy surface runoffs caused the increase of field pollution losses, which has recently occurred, because winters lasted till the beginning of April in the Podlasie region. Maximum phenoxoacetic acids concentrations were present in June – August and September. Their average con- 3 3 3 centration in autumn was 61.8 μg/dm MCPP (at cmax = 120 μg/dm ), 30.3 μg/dm MCPA 3 3 (at cmax = 50 μg/dm ). In summer, herbicide contents were: 56.3 μg/dm MCPP, 29.1 μg/dm3 MCPA, and 27.9 μg/dm3 2,4-D (Tab. 6). The temperature drop delays the activity of microorganisms taking part in plant protection means degradation in the soil and water, and thus the rate of compounds in question [2]. 3 3 Larger amounts of herbicide MCPP (cśr = 58 μg/dm at cmax = 120 μg/dm ) than MCPA or 2,4-D were found in samples (Tab. 6, Fig. 2). This fact may be elucidated not only by massive application of the compound, but also its highest durability in an environment, as well as by a long half-life in water (to 20 days) and in soil (up to 180 days). The highest concentrations of the studied compounds were recorded at the sampling point on the rivers Czarna and Supraśl (the most distant from river springs). It is probably associated of a constant supply with pollution load from the basin area. ] 3 Pesticide concentration [μg/dm

Fig. 2. Mean phenoxyacetic herbicide concentration in the Supraśl River catchment In studied river, the content of ammonia nitrogen ranged from 0.012 to 2.18 mg/dm3. A typical dependence – low ammonia nitrogen concentration at higher temperatures when it is taken by plants and nitrified, and higher in winter when nitrification process is inhibited – was observed. Because of the fact that winter has been recently delayed even to April in Podlasie region, the lowest mean ammonia nitrogen concentration occurred in spring (0.48 mg/dm3). “Classical” summer is shifted to the end of August and beginning of September, thus the lowest mean ammonia nitrogen contents were recorded in autumn (0.37 mg/dm3). Under aerobic conditions, nitrites are transient and unstable products that are quickly converted into nitrates, which was confirmed by significant correlation 76 KATARZYNA IGNATOWICZ dependences. In the examined surface water, the concentration of nitrite nitrogen was 3 from 0.005 to 0.375 mg/dm . Its highest contents were recorded in summer (cśr = 0.032 mg/dm3). Nitrate nitrogen is the biogenic substance that is necessary for aqueous plant’s living. Changes of nitrate concentrations occurred analogously to those for phosphates (Tab. 6). Vervier’s opinion on seasonal dependence of biogenic substances occurrence, including pesticides, in rivers of agricultural basins, was here confirmed [17]. The obtained results revealed that there was similar time dependence for nitrogen and phosphorus concentrations in the studied water (Tab. 6). Almost 600 values were analyzed, thus significant dependencies were present just at correlation coefficient 0.25. Calculated correlations led to conclusions about the inter-relation between phenoxoacetic acids and biogenic compounds amounts, namely phosphates. During the study, correlation coefficient between concentrations of various chemical forms of phenoxoacetic herbicides was high ranging from 0.32 to 0.87. Similar dependence may be found between nitrate and nitrite contents (R = 0.68).

CONCLUSIONS

1. The largest amount of pesticide remains was found in surface water in summer; it amounted to 120 µg/dm3 (2,4-D, MCPA, MCPP). 2. Biogenic concentrations varied through seasons and their largest contents were present in summer and autumn. 3. It was found that the sum of pesticides remains exceeded 5 µg/dm3, thus a systematic screening of the river Supraśl and its tributaries for these agents should be conducted. 4. Great amounts of plant protection means were found in surface waters often used for drinking. They must be removed during water treatment processes in accordance to a new Decree on the quality of water meant for drinking.

Acknowledgments Financial support for this research was provided by Ministry of Science and Higher Edu- cation within the project W/IIŚ/23/07 and G/IIS/22/07 (N305 070 32/2535).

REFERENCES

[1] Anderson P., R. Jack, Ch. Burke, J. Cowles, B. Moran: Surface Water Monitoring Program for Pesticides in Salmonid-Bearing Streams April to December 2003, WSDA, Washington State, Department of Agri- culture, Ecology Publication 04-03-048, 2004. [2] Dojlido J.R.: Chemia wód powierzchniowych, Wydawnictwo Ekonomia i Środowisko, Białystok 1995. [3] Dyrektywa 75/440/EWG z 16 czerwca 1975 r. dotycząca wymaganej jakości wód powierzchniowych przeznaczonych do pobierania wody pitnej. [4] Dyrektywa 79/869/EWG z 9 października 1979 r. dotycząca metod poboru i częstotliwości pobierania próbek oraz analizy wód powierzchniowych przeznaczonych do pobierania wody pitnej. [5] Górniak A.: Klimat Województwa Podlaskiego, IMiGW, Białystok 2000. [6] Górniak A.: Wody Parku Krajobrazowego Puszczy Knyszyńskiej, IMiGW, Supraśl 1999. [7] Ignatowicz K.: Ocena stanu czystości rzeki Białej ze szczególnym uwzględnieniem zanieczyszczeń pesty- cydowych i biogennych, Archives of Environmental Protection, 30, 2, 51–60 (2004). [8] Ignatowicz K., I. Skoczko: Occurrence study of Agro-chemical pollutions in chosen waters on marshland and flooding of Biebrza, Polish Journal of Environmental Studies, 15, 5, 431–434 (2006). OCCURRENCE STUDY OF AGRO-CHEMICAL POLLUTANTS IN WATERS OF SUPRAŚL... 77

[9] Rozporządzenie Ministra Środowiska z dnia 27 listopada 2002 r. w sprawie wymagań, jakim powinny odpowiadać wody powierzchniowe wykorzystywane do zaopatrzenia ludności w wodę przeznaczoną do spożycia, Dz. U. nr 204, poz. 1728 z 2002 r. [10] Rozporządzenie Ministra Środowiska z dnia 20 sierpnia 2008 r. w sprawie sposobu klasyfikacji stanu jednolitych części wód powierzchniowych, Dz. U. nr 162 z 2008 r. [11] Sapek B.: Rolnictwo polskie i ochrona jakości wody, Instytut Melioracji i Użytków Zielonych Falenty, Zeszyt edukacyjny, nr 2/97 (1997). [12] Siepak J., J. Zerbe, M. Kabacinski: Wstępna ocena degradacji studni na obszarach wiejskich wojewódz- twa poznańskiego, Przyroda i Człowiek, 4, 117–123 (1993). [13] Siepak J., J. Zerbe, M. Kabacinski, T. Sobczyński: Wpływ antropopresji na wody gruntowe na obszarze województwa poznańskiego i miasta Poznania, Wydawnictwo Sorus, Poznań 1997. [14] Stamer J.K., W.A. Battaglin, D.A. Goolsby: Herbicides in Midwestern Reservoir Outflows, 1992–93, U.S. Geological Survey Open-File Report 134–98, 1998. [15] Stuczyński T. (red.): Wdrożenie systemu informacji o rolniczej przestrzeni produkcyjnej w województwie podlaskim, Instytut Uprawy Nawożenia i Gleboznawstwa, Puławy 2003. [16] Thurman E.M., D.A. Goolsby, M.T. Meyer, D.W. Kolpin: Herbicides in surface waters of the Midwest- ern United States – the effect of spring flush, Environmental Science & Technology, 25, 10, 1794–1796 (1991). [17] Vervier P., A. Pinheiro, A. Fabre: Spatial changes in the modalities of N and P inputs in a rural river network, Wat. Res., 33, 1, 95–104 (1999). [18] Żelechowska A., Z. Makowski: Pestycydy w wodach rzek o zlewniach rolniczych zasilających Zatokę Gdańską, Gaz, Woda i Technika Sanitarna, 2-3, 35–42 (1990).

Received: February 12, 2009; accepted: August 18, 2009.

WYSTĘPOWANIE ZANIECZYSZCZEŃ AGROCHEMICZNYCH W WODACH ZLEWNI SUPRAŚLI

W pracy zaprezentowano wyniki badań dotyczących określenia aktualnych stężeń pozostałości agrochemicznych: herbicydów fenoksyoctowych (4), herbicydów triazynowych (4) i insektycydów (7) oraz innych zanieczyszczeń w wodach zlewni rzeki Supraśli. Okres badawczy trwał dwa lata, od maja 2003 do kwietnia 2005 roku. Pozostałości pestycydów określano metodą chromatografii gazowej GC z detektorem ECD. Największe stężenia pestycydów fenoksyoctowych wykryto w okresie wiosenno-jesiennym (120 µg/dm3). Najważniejszym jednak spostrzeżeniem jest fakt występowania w wodach powierzchniowych, często ujmowanych do picia, znacznych ilości środków ochrony roślin, które w świetle nowej ustawy o jakości wody przeznaczonej do picia, należy usuwać w procesach uzdatniania. 78 79

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 79 - 90 2009 PL ISSN 0324-8461

CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN WATER OF A SUBMOUNTAIN DAM RESERVOIR – EFFECT OF LATE SUMMER STORMFLOW

EWA SZAREK-GWIAZDA*, GRAŻYNA MAZURKIEWICZ-BOROŃ, ELŻBIETA WILK-WOŹNIAK

Institute of Nature Conservation, Polish Academy of Sciences al. Mickiewicza 33, 31-016 Kraków, Poland * Corresponding author e-mail: [email protected]

Keywords: Dam reservoir, summer stormflow, water chemistry, phytoplankton.

Abstract: Physicochemical parameters of water and phytoplankton composition were studied in the dimictic, submountain Dobczyce Reservoir (southern Poland) affected by summer stormflow, which took place in Sep- tember 2007. During summer (except September) temperature, pH, dissolved oxygen, and carbonates showed vertical differentiation. Stormwater flow through the system had a destabilizing effect on summer stratification. It diluted the concentrations of salts (sulphate and chloride) and slightly increased the concentration of nutrients in the reservoir. In phytoplankton some changes in the dominant species among the Cyanobacteria group were noted.

INTRODUCTION

It is well known that hydrological conditions influence various processes in dam reservoirs. Seasonal hydrological fluctuations effect both the physical, chemical and biological features of reservoirs [4, 5, 14, 17, 20, 21]. According to Bonell [2], flow pathways that dominate during storm or snowmelt events determine the surface water chemistry both during and after the event. It is also the most important feature affecting the diversity and dynamics of phytoplankton [18]. Changes in retention time might be crucial for changes in the phytoplankton community composition and density both in shallow [8] and in deep water bodies [6]. Floods are natural, periodically occurring events. However, in recent years/decades, increased frequencies of heavy rainfall and flood events in southern Poland have been observed. Because heavy precipitation and maximum flow in rivers in southern Poland usually occur in summer, summer stormflow strongly disturbs the typical summer stratification that occurs in submountain reservoirs. Literature focusing on the effects of periodic flood events on reservoir physicochemical and biological features is scarce [6]. In fact, only a few studies examine the effect of floods on phytoplankton in dam reservoirs, especially the deep ones [16, 25, 26]. This issue is an important one since it is predicted that global warming will result in heavier precipitation and more frequent and violent floods. 80 EWA SZAREK-GWIAZDA, GRAŻYNA MAZURKIEWICZ-BOROŃ, ELŻBIETA WILK-WOŹNIAK

The aim of the current study was to present the effects of stormwater on the distur- bance of late summer stratification and changes in the water chemistry, phytoplankton composition and biomass (chlorophyll a) in a dimictic, submountain Polish reservoir.

STUDY AREA

The Dobczyce Reservoir (49°52’N, 20°02’E, alt. 270 m) is a deep, submountain dam reservoir located in southern Poland (Fig. 1). It was built on the Raba River (Wisła basin) in 1986. It is a drinking water reservoir for the city of Krakow. It has a length 10 km, an area of c. 1000 ha, a mean depth of 11 m (max. c. 30 m), and a capacity of 99.2 mln m3. The Raba River supplies 88.6% of the total inflow. The average water exchange is 3.6 times a year [12]. The reservoir is eutrophic and dimictic in its lower, deeper part where the circulation of the water during the spring and autumn takes place. In summer thermal and oxygen stratification occurs. The metalimnion occurs usually at the depths of between 6–8 m [14]. According to Materek [11], the ‘flood wave’ is characterized as flows greater than 300 m3·s-1. Flood waves were observed several times in the Raba River: in 1987 (max water flow 451 3m ·s-1), in 1996 (529 m3·s-1), in 1997 (884 m3·s-1), in 2001 (484 m3·s-1) [6]. The data concerning years 2005 and 2007 was obtained from Regional Water Management Board in Krakow and present as follows 348 m3·s-1, 430 m3·s-1 respectively.

Fig. 1. Location of the sampling stations

MATERIAL AND METHODS

Samples for physicochemical parameters and phytoplankton were collected monthly from January to December 2007 from the deepest part of the Dobczyce Reservoir (depth ca. 26 m; Fig. 1). Samples to examine the effects of the flood were taken 3 days after CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN ... 81 the flood event (September 19, 2007). At the same time, samples for physicochemical analyses were collected from the Raba River close to the inlet to the reservoir (Fig. 1). Samples for physicochemical parameters and chlorophyll a measurements were taken using a bathometer at depths of 0, 2.5, 5, 7.5, 10, 12.5, 15, 20 and 1 m above the bottom (108 samples in total). Samples for qualitative and quantitative analyses of phytoplankton were taken using a 5 dm3 sampler from the epilimnion. The following parameters were measured: water temperature, conductivity, pH, dis- - solved oxygen, anions (chloride, sulphate, hydrocarbanate) and nutrients (P-tot, NO3 , + N-NH4 ). Water temperature, conductivity, and pH were measured in situ. Analyses of anions: chloride, sulphate, hydrocarbonate, and nitrate were conducted using ion chromatography (DIONEX, IC25 Ion Chromatograph). Dissolved oxygen was determined according to the Winkler method. Ammonia was analyzed with the nesslerization method, while P-tot (after mineralization) was measured using the molybdenum blue method [1]. Chlorophyll a was extracted in hot 90% ethanol and measured spectrophotometrically at 665 nm and at 750 nm [15]. Samples of phytoplankton were fixed with Lugol’s solution and concentrated by sedimentation from a 1 dm3 sample [19]. Algae were counted according to Lund et al. [9]. Daily discharge data for the Raba River were recorded from Regional Water Man- agement Board in Krakow. To calculate the relationship between discharge of the Raba River and physicochemical parameters in the Dobczyce Reservoir, monthly water discharge in the Raba River was calculated. Statistica 8.0 was used for statistical analysis.

RESULTS

Discharge and physicochemical parameters in the Raba River Mean annual water discharge in the Raba River near the inlet to the Dobczyce Reservoir was 12.7 m3·s-1 in 2007. The lowest mean water discharge was recorded from April to July (2.8–4.5 m3·s-1), while discharge was the highest in September (mean 42.6 m3·s-1). Between 6–11 September, stormflow discharge ranged from 85 to 430 3m ·s-1 (maximum on 8 September; Fig. 2). In total, 90 mln m3 of water reached the reservoir in that period. It constituted 81% of the reservoir capacity. Physicochemical parameters of water during

Fig. 2. Daily water discharge in the Raba River in 2007 82 EWA SZAREK-GWIAZDA, GRAŻYNA MAZURKIEWICZ-BOROŃ, ELŻBIETA WILK-WOŹNIAK that time (11 September) were as follows: temperature 12°C, conductivity 251 µS·cm-1, pH 7.9, oxygen dissolved 9.9 mg·dm-3, chlorides 5.9 mg·dm-3, hydrocarbonates 167.8 -3 -3 - -3 + -3 mg·dm , sulphates 19.2 mg·dm , NO3 4.6 mg·dm , N-NH4 0.39 mg·dm , and P-tot 0.046 mg×dm-3.

Physicochemical and biological parameters of the reservoir water Water transparency (Secchi-depth measurements) ranged from 0.55 to 5.7 m from Janu- ary to December 2007. The lowest transparency was found in September (the flood event; 0.55 m) and in November (0.8 m), whereas the highest occurred in summer from June to August (3.1–5.7 m). Temperature, pH, and dissolved oxygen showed seasonal variations (Fig. 3). Ac- cording to those parameters variations, spring and autumn overturn in 2007 occurred in April and November, while summer stratification occurred from May to October (except September). During stratification, three distinct layers were distinguishable: the epilimnion (0–5 m), metalimnion (7.5–12.5 m), and hypolimnion (from 15 to the bottom). Water temperature was the highest in the epilimnion and decreased to the bottom from May to

Fig. 3. Mean values, standard deviations (SD) and standard error (SE) of temperature, dissolved oxygen, oxygen saturation, conductivity, pH, and chlorides in the water of the Dobczyce Reservoir in 2007 CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN ... 83

August (Fig. 4). In August, the temperature of the surface water was 22°C, while near the bottom it was 12.8°C. Summer stormflow (September) affected the water temperature. It decreased from the surface to a depth of 15 m (the range of decrease was 4.5 to 6.1°C), while close to the bottom (at a depth of 25 m) it slightly increased (by ca. 1°C, Fig. 4). In October more homogenous temperature in the water column occurred.

Fig. 4. Temperature, dissolved oxygen, oxygen saturation, conductivity, pH, and chlorides in the water column of the Dobczyce Reservoir in August, September, and November 2007

pH of the water was always nearly neutral or alkaline (pH 7.3–8.5) (Fig. 3). In the winter months, spring and autumn overturn, pH ranged from 7.9–8.3 and was characterized by low variability in the water column (CV = 0.06–1.1). During summer stratification (except September) great pH variability in the water column was found (Fig. 4). It was higher in the epilimnion (pH 8.1–8.6) and lower in the hypolimnion (pH 7.3–7.8). In September similar pH (7.8–7.9) in the water column was found. The water was well oxygenated during winter as well as spring and autumn overturn (8.0–12.8 mg·dm-3, Fig. 3). In summer (except September) the concentration of dissolved oxygen was higher in the epilimnion (oxygen saturation reached ca. 103% in June and August) compared to the meta- and hypolimnion (Fig. 4). Hypolimnion was poorly oxygenated (0.4– 3.8 mg·dm-3 from June to August). In September (the flood event) the whole water mass was moderately well oxygenated (6.7–8.3 mg·dm-3, oxygen saturation 69–83%, Fig. 4). Subsequently, in October, typical summer oxygen stratification was again present (4.4–9.4 mg·dm-3, oxygen saturation 45–97%). 84 EWA SZAREK-GWIAZDA, GRAŻYNA MAZURKIEWICZ-BOROŃ, ELŻBIETA WILK-WOŹNIAK

Conductivity (reflecting salt concentration) ranged from 200 to 332 µS·cm-1 (Fig. 3). Higher salt concentrations (expressed by conductivities of 281–306 µS·cm-1) occurred in the periods January- June, November, and December, with low variability in the water column (CV = 0.2–0.7). The lowest salt concentrations were found in September (the flood event, 200–270 µS·cm-1) and October (260–270 µS·cm-1). In summer (August, Sep- tember) great variability in salt concentrations throughout the water column occurred (Fig. 4). In August salt concentrations increased from the surface to the bottom (277–322 µS·cm-1) except at a depth of 15 m, while conversely levels decreased in September. In October salt concentrations were homogenous in the water column. Concentrations of chlorides (5–10.7 mg·dm-3) and sulphates (15.7–24.3 mg·dm-3) showed characteristically low variability in the water column during the year (except in September; Figs. 3 and 5). Higher levels were found from January to August, while the lowest concentration occurred in September during the flood event (chloride 5–10.3 mg·dm-3; sulphate 15.7–22.9 mg·dm-3). In September, their variability in the water column was considerable. Their amounts decreased from the epilimnion to the hypolimnion (Figs 4 and 6). Increased chloride and sulphate concentrations were observed from Oc- tober to December.

- Fig. 5. Mean values, standard deviations (SD) and standard error (SE) of sulphates, hydrocarbonates, NO3 , + N-NH4 , and P-tot concentrations in the water of the Dobczyce Reservoir in 2007 CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN ... 85

- + Fig. 6. The concentrations of sulphate, hydrocarbonate, NO3 , N-NH4 , and P-tot in the water column of the Dobczyce Reservoir in August, September, and November 2007

Hydrocarbonates ranged from 86.1 to 192.0 mg·dm-3 (Fig. 5) and were characterized by higher vertical variability compared to chlorides and sulphates. Higher hydrocarbonate concentrations (mean 150–180.5 mg·dm-3) occurred in the whole water mass in winter, spring and autumn overturn, as well as in the metalimnion and hypolimnion in summer (except in September; peak 191 mg·dm-3 in June at the depth of 10–12.5 m). The lowest concentrations of hydrocarbonates were found in the epilimnion in summer (in August 86 mg·dm-3; Fig. 6). In August and October, hydrocarbonate concentrations increased from the surface to the bottom (Fig. 6). During the September flood event, the concentrations of hydrocarbonates were low (128–148 mg·dm-3) and more homogenous in the whole water mass. - The highest nitrate (NO3 ) concentrations in the water mass occurred in the winter months, and during the spring and autumn overturn (4.0–5.9 mg·dm-3), while concentrations were the lowest in August (2.3–3.8 mg·dm-3, except the concentrations at 25 m, Fig. 5). During summer stratification vertical variability in nitrate concentrations was observed (Fig. 6). Concentrations were lower in the epilimnion than in the hypolimnion (Fig. 6). In September, during the flood event, nitrate concentrations (3.0–3.7 mg·dm-3) in the water (especially in the epilimnion) were higher compared to August. 86 EWA SZAREK-GWIAZDA, GRAŻYNA MAZURKIEWICZ-BOROŃ, ELŻBIETA WILK-WOŹNIAK

+ -3 Ammonia nitrogen (N-NH4 ) ranged from 0.20 to 0.93 mg·dm in the reservoir + (Fig. 5). Low N-NH4 concentrations occurred in January, February, April, September, and from October to December (mean 0.23–0.27 mg·dm-3), while the highest concentrations occurred in the hypolimnion in August (0.25–0.93 mg·dm-3). In September during + -3 the flood event, N-NH4 concentrations were low (0.34–0.51 mg·dm ) and rather ho- + mogenous in the water column. A decrease in N-NH4 concentration in the hypolimnion compared to August was observed (Fig. 6). Concentrations of P-tot were low (mean 0.022–0.025 mg·dm-3) in the winter months (January-March), during spring mixing (May), and in summer (June, August; Figs 5 and 6). The highest P-tot concentrations were found during the flood event in September (0.055–0.075 mg·dm-3 at the depths of 7.5–12.5 m) and in the hypolimnion in October (0.12 mg·dm-3 at the depth of 25 m). A statistical analysis showed the relationships between the Raba River discharge and selected parameters in the water of the Dobczyce Reservoir, i.e.: a significant negative correlation with water transparency (r = -0.6, p < 0.05), conductivity (r = -0.71, p < 0.02), chloride (r = -0.61, p < 0.05), and sulphates (r = -0.66, p < 0.02), and a significant positive relationship with P-tot (r = 0.62, p < 0.05). The highest chlorophyll a concentration and variability in the water column was noted in January, whereas the lowest occurred in July. Diatoms constituted the dominant group in January. Almost 80% of total density and 90% of total biomass of phytoplankton was composed of Stephanodiscus neoastrea “complex” Hakansson & Hickel. Subsequent months were characterized by generally low concentrations of chlorophyll a. In August, the dominant group was the blue-green algae (mostly Merismopedia tenuissima Lemm. and Microcystis spp.) and cryptophytes (Cryptomonas spp.). The concentrations of chlorophyll a in September were insignificantly higher compared to August. The dominant groups were again the blue-green algae and cryptophytes. However, changes were observed in the dominant species among blue-green algae (Woronichinia naegeliana (Un- ger) Elenkin. was dominant) but not among the cryptophytes. The highest concentration of chlorophyll a was noted in the upper part of epilimnion (0–5 m). In September, chlorophyll a concentrations reached 9.5 µg·dm-3 (the highest concentration at 2.5 m). In August and October, there were insignificantly lower maxima – 7.1 µg·dm-3 (both months’ max. concentration at 2.5 m). We observed decreases in chlorophyll a concentrations at the deepest water level (from 7.5 m to the bottom) in October.

DISCUSSION

Mean annual water discharge in the Raba River in 2007 was higher compared to those found during 1986–1999 (10.65 m3·s-1) [14], but lower than those found in 1997 (14.86 m3·s-1) [13] when the greatest flood event in the 20th century was noted. Maximum water discharge in the Raba River in September 2007 was twice as low as that recorded during a flood in July 1997 (884 m3·s-1) [13]. Between 6–11 September 2007, about 90 mln m3 of water entered the reservoir, making up about 81% of the total reservoir capacity. Such high water inflow affects summer stratification in the deeper part of the reservoir. Our results indicated that the most significant variation in water transparency of the Dobczyce Reservoir was inversely related to the water discharge of the Raba River. CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN ... 87

In general, water transparency in the deep dam reservoirs in southern Poland is more strongly related to the riverine water discharge rather than with primary production [14]. The lowest water transparency was found in the Dobczyce Reservoir at the time of the enhanced Raba River water discharge (September). Similar phenomenon was found in the Dobczyce Reservoir during the flood in 1997 [6, 13], and in other reservoirs [4, 10]. During the flood events, high loads of suspended matter leached from the catchment basins by stormwater are transported through the reservoir, causing reduced water transparency [4, 6]. Temperature, pH and dissolved oxygen in the Dobczyce Reservoir showed seasonal patterns typical of dimictic submountain dam reservoirs in Poland [14]. pH ranged from slightly neutral to alkaline, related to the geochemical background of the catchment basin. Temperature, pH, and oxygen dissolved showed summer stratification. Summer stormflow (September) caused destabilizing effects on the water mass and disturbed stratification. At that time, the above mentioned parameters showed little variability in the water column. The reservoir became riverine in nature. An inflow of colder Raba River stormwater (12°C) in September affected a decrease of water temperature from the surface to the depth of 15 m. This effect of stormwater on the thermal gradient (increase or decrease) in dam reservoirs was also stated by Tüzün and İnce [20] and Godlewska et al. [6]. The summer stormflow affected also a decrease of pH in the epi- and metalimnion, and an increase in the hypolimnion of the Dobczyce Reservoir (compared to August). A similar decrease in pH during a flood was observed by Faithful and Griffiths [4]. However, it was only observed in the mid-column, the area of water flow through the Lake Dalrymple (dam reservoir in north Queensland, Australia). The water of the Dobczyce Reservoir was well oxygenated in the majority of the year. The depletion of oxygen occurred in the hypolimnion only in summer as a result of the decomposition of organic matter and the oxidation of ammonium. Such summer oxygen depletion is typical for the Dobczyce Res- ervoir [14]. Well oxygenated stormwater (9.92 mg·dm-3) flowing through the reservoir in September improved oxygen conditions in the hypolimnion. Similar re-oxygenation of hypolimnetic water was observed earlier in the Dobczyce Reservoir during the flood in 1997 [6]. Conversely, the lack or only slight re-oxygenation of anoxic hypolimnetic water was observed in Lake Dalrymple [4]. The authors explained that water flow through the reservoir affected only the mid-column section but not the hypolimnetic water. Thus the extent of re-oxygenation of the hypolimnion depends on the vertical range of water flow through the dam reservoir during a flood event. The concentration of salts (expressed as conductivity) in the water of the Dob- czyce Reservoir was the lowest in September during the flood event, which reflected the conductivity of the Raba River stormwater. Low conductivity of reservoir waters during flood events was also observed by Mazurkiewicz and Żurek [13] as well as by Faithful and Griffiths [4]. The latter authors found out that stormwater flowing through the reservoir (Lake Dalrymple, Australia) resulted in characteristically low conductivity and high turbidity. The lowest conductivity occurred with the most highly turbid water. Sulphate and chloride concentrations showed similar patterns of occurrence in the water of the Dobczyce Reservoir. Their concentrations showed little seasonal and vertical variability and were inversely related to the Raba River discharge. Summer stormwater caused dilu- 2- - - tion of SO4 , Cl , and HCO3 in the water column of the Dobczyce Reservoir. Similarly - 2- reduced concentrations of Cl and SO4 in streamflow in response to rain events were 88 EWA SZAREK-GWIAZDA, GRAŻYNA MAZURKIEWICZ-BOROŃ, ELŻBIETA WILK-WOŹNIAK found by Brown et al. [3] and Żelazny [27]. Considerable dissolution of Cl- concentrations (from 275 to 36 mg·dm-3) in the Vistula River (Poland) during summer stormflow in 1997 was found by Mazurkiewicz and Żurek [13]. According to Brown et al. [3], dilution of stormflow is more closely related to the timing of the contribution of the event-water component to stormflow than by the volume of discharge in the stream channel. In most catchments, the maximum stormwater contributions occurred immediately after the hy- drograph peak. The seasonal patterns of nitrates and P-tot concentrations in the water of the Dob- czyce Reservoir were typical of submountain dam reservoirs [14]. They are usually related to the biological activity of primary producers. In September, slight increases in - NO3 and P-tot concentrations in the water of the Dobczyce Reservoir indicated higher leaching from the catchment during heavy rainfalls. Concentration of P-tot in the water of the Dobczyce Reservoir was positively related to the Raba River discharge. The relationship between P-tot concentration in dam reservoir and water inflow was also found by Tüzün and İnce [20]. Elevated amounts of N-tot and P-tot in the water of the Vistula River during the flood of 1997 was found by Mazurkiewicz and Żurek [13]. Accord- - ing to Żelazny [27], the leaching of macroelements and NO3 from soils is higher when stormwater easily infiltrates deeper soil layers than when the infiltration is limited (frozen soils). According to Faithful and Griffiths [4], a great part of P-tot (almost all) and N-tot (more than 50%) is transported with suspended particulate matter in stormwater (Lake Dalrymple, Australia). However, other parameters like water temperature and dissolved oxygen concentration may also influence P-tot concentration in the water. In summer, ammonium concentrations in the hypolimnion of the Dobczyce Reservoir were high. This results from digenesis processes occurring at the bottom. In September the water inflow through the system caused considerable dilution of ammonium in the hypolimnion. High water influxes to dam reservoirs are responsible for the development of fast growing algal species [7]. Similar observations were made shortly after the passage of a flood wave into a deep dam reservoir [6, 16, 26]. According to Faithful and Griffiths [4], an influx of highly turbid water may affect processes within the water column; for instance diminishing light penetration and reducing primary production and phytoplankton biomass. In 2007, high concentrations of chlorophyll a were observed in the winter (January) in the Dobczyce Reservoir but not at any other time of the year. After the flood wave an insignificant increase of chlorophyll a concentration was observed in the upper epilimnion and there was a change in the dominant species among the blue-green algae. However, the development of fast growing species was not observed. It appears that Woronichinia naegeliana is a species which may tolerate water mixing. It frequently develops in masses during the autumn overturn and has been causing water blooms in the Dobczyce dam reservoir since 1995 [22], but not every year. It usually forms water blooms in October [23] and sometimes long lasting blooms persist until December [24]. The late summer stormwater in 2007 did not change autumn algal dynamics in the Dob- czyce dam reservoir, while the floods in July 1997 changed completely this ecosystem and altered summer algal dynamics [6]. The only similarity of 2007 to other floods (stormwater years) in the Dobczyce dam reservoir was that chlorophyll a concentrations after the flood wave passage were higher compared to the previous month. It appears that because this flood wave was close to the regular autumn overturn, it did not cause any significant changes in phytoplankton dynamics or composition. CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN ... 89

CONCLUSION

Most of hydrochemical parameters of the Dobczyce Reservoir showed seasonal patterns that are typical of Polish dimictic submountain dam reservoirs. Temperature, pH, and dissolved oxygen were higher in the epilimnion and lower in the hypolimnion, while hydrocarbonate concentrations showed a reverse trend during summer stagnation (except September). The substantial flow through the system in September had a considerable destabilizing effect on the water mass. The reservoir became riverine in nature. Its water chemistry mirrored those of the Raba River. Thus, summer stratification was disturbed and parameters showed no variability (pH) or small variability (temperature, O2, % O2) within the water column. In October, there was a return to pH and oxygen stratification in the water column. Stormwater had a diluting effect on the concentrations of salts (sulphate and chloride) in the reservoir water. Conversely, higher concentrations of nutrients were transported through the reservoir. The results obtained indicate that water discharge in the Raba River affects the water transparency, conductivity, chloride, sulphates (negative correlation) concentrations, and P-tot (positive correlation) in the Dobczyce Reservoir. In terms of phytoplankton composition there were notable differences in the dominant species before and after the flood event. While a slight increase of chlorophyll a was observed after the flood, chlorophylla was not significantly correlated with water discharge.

Acknowledgements The authors thank Rafał Słonka M.S. (Regional Water Management Board in Krakow) for available discharge data for the Raba River. We are grateful to Tara Higgins for revision of the text.

REFERENCES

[1] APHA: Standard Methods for the Examination Water and Wastewater, 18th ed., American Public Health Association, Washington D.C., 1992. [2] Bonell M.: Progress in the understanding of runoff generation dynamics in forests, Journal of Hydrology, 150, 217–275 (1993). [3] Brown V.A., J.J. McDonnell, D.A. Burns, C. Kendall: The role of event water, a rapid shallow flow component, and catchment size in summer stormflow, Journal of Hydrology, 217, 171–190 (1999). [4] Faithful J.W., D.J. Griffiths: Turbid flow through a tropical reservoir (Lake Dalrymple, Queensland, Austra- lia): Responses to a summer storm event, Lakes & Reservoirs: Research and Management, 5, 231–247 (2000). [5] Geraldes A.M., M-J. Boavida: Seasonal water level fluctuations: Implications for reservoir limnology and management, Lakes & Reservoirs: Research and Management, 10, 59–69 (2005). [6] Godlewska M., G. Mazurkiewicz-Boroń, A. Pociecha, E. Wilk-Woźniak, M. Jelonek: Effects of flood on the functioning of the Dobczyce reservoir ecosystem, Hydrobiologia, 504, 305–313 (2003). [7] Huszar V.L.M., C. Reynolds: Phytoplankton periodicity in sequences of dominance in an Amazonian flood-plain lake (Lago Batata, Para, Brazil): responses to gradual environmental change, Hydrobiolgia, 346, 169–181 (1997). [8] Jones I.D., J.A Elliott: Modelling the effects of changing retention time on abundance and composition of phytoplankton species in a small lake, Freshwater Biology, 52, 988–997 (2007). [9] Lund J.W.G., G. Kipling, E.D. Le Cren: The inverted microscope method of estimating algae numbers and the statistical basis of estimation by counting, Hydrobiologia, 11, 143–170 (1958). [10] Mac Donagh M.E., M.A. Casco, M.C. Claps: Plankton relationships under small water level fluctuations in a subtropical reservoir, Aquatic Ecology, 43, 371–381 (2009). [11] Materek E.: Hydrology of tributaries and reservoir, [in:] J. Starmach, G. Mazurkiewicz-Boroń (eds), Dob- czyce Reservoir ecology – eutrophication –conservation, Institute of Freshwater Biology PAS, Kraków 2000, pp. 15–31 (in Polish). 90 EWA SZAREK-GWIAZDA, GRAŻYNA MAZURKIEWICZ-BOROŃ, ELŻBIETA WILK-WOŹNIAK

[12] Mazurkiewicz G.: Environmental characteristics of affluents of the Dobczyce Reservoir (Southern Po- land) in the preimpoundment period (1983–1985). 1. Some physico-chemical indices, Acta Hydrobio- logia, 30, 287–296 (1988). [13] Mazurkiewicz G., R. Żurek: Bezpośrednie ekologiczne skutki powodzi w lipcu 1997 roku na przykładzie rzeki i zbiornika zaporowego, [in:] Konferencja Naukowa Powódź w dorzeczu górnej Wisły w lipcu 1997 roku, Kraków, 7–9 maja 1998 r., Wydawnictwo PAN oddział w Krakowie, pp. 195–203 (1998). [14] Mazurkiewicz-Boroń G.: Factors of eutrophication processes in submontain dam reservoirs, (in Polish), Supplementa ad Acta Hydrobiologica, 2, pp. 68 (2002). [15] Nusch E.A.: Comparison of different methods for chlorophyll and phaeopigment determination, Archiv für Hydrobiologie, 14, 14–36 (1980). [16] Pociecha A., E. Wilk-Woźniak: Effect of the summer flood on the ecosystem of the Dobczyce Reservoir, Poland, Acta Hydrobiologica, 42, 59–67 (2000). [17] Pociecha A., E. Wilk-Woźniak: The life strategy and dynamics of selected species of phyto- and zooplank- ton in a dam reservoir during “wet” and “dry” years, Journal of Polish Ecology, 54, 29–38 (2006). [18] Soares M.C., M.M. Marinho, V.L.M. Huszar, C.W.C. Branco, S.M.F.O. Azevedo: The effects of water retention time and watershed features on the limnology of two tropical reservoirs in Brazil, Lakes and Reservoirs: Research and Management, 13, 257–269 (2008). [19] Starmach K.: Methods for plankton analysis, PWRiL, Warszawa 1955 (in Polish). [20] Tüzün İ., O. İnce: Relationship between water flow volume and in-lake total phosphorus concentrations and temperature in w warm temperate reservoir: Implication by path analysis, Lakes & Reservoirs: Re- search and Management, 11, 83–96 (2006). [21] Wetzel R.G.: Limnology, lake and reservoir ecosystem, 3rd ed., Elsevier Science Imprint, San Diego, San Francisco, New York, Boston, London, Sydney, Tokyo 2001. [22] Wilk-Woźniak E.: Late autumn mass development of Woronichinia naegeliana (Cyanophyceae) in a dam reservoir in Southern Poland, Biologia (Bratislava), 53, 1–5 (1998). [23] Wilk-Woźniak E., H. Bucka, T. Mrozińska: Contribution to a broadening of taxonomical and ecological knowledge on Woronichinia naegeliana (Unger) Elenkin., Archiv Für Hydrobiologie/Algological Stud- ies, 109, 499–508 (2003). [24] Wilk-Woźniak E., G. Mazurkiewicz-Boroń: The autumn dominance of cyanoprokaryotes in a deep meso- eutrophic submontane reservoir, Biologia (Bratislava), 58, 17–24 (2003). [25] Zeng H., L. Song, Z. Yu, H. Chen: Distribution of phytoplankton in the Three-Gorge Reservoir during rainy and dry seasons, Science and Total Environment, 367, 999–1009 (2006). [26] Znachor P., E. Zapomelova, K. Rehakova, J. Nedoma, K. Simek: The effect of extreme rainfall on summer succession and vertical distribution of phytoplankton in a lacustrine part of a eutrophic reservoir, Aquatic Sciences, 70, 77–86 (2008). [27] Żelazny M.: Biogenic compounds in precipitation water, streamwater and groundwater in catchments with different land uses in the Wiśnickie Foothills, southern Poland, Jagiellonian University Institute of Geography and Spatial Management, Kraków 2005, pp. 216 (in Polish).

Received: March 25, 2009; accepted: September 2, 2009.

ZMIANY PARAMETRÓW FIZYKOCHEMICZNYCH I FITOPLANKTONU W WODZIE PODGÓRSKIEGO ZBIORNIKA ZAPOROWEGO – WPŁYW LETNIEJ FALI POWODZIOWEJ

Badano zmiany parametrów fizykochemicznych oraz strukturę fitoplanktonu w wodzie dimiktycznego, podgór- skiego zbiornika zaporowego (Zbiornik Dobczycki, południowa Polska), przez który we wrześniu przeszła fala powodziowa. Temperatura wody, pH oraz zawartości tlenu rozpuszczonego i wodorowęglanów wykazywały znaczne zróżnicowanie w słupie wody w okresie lata. Fala wezbraniowa płynąca przez zbiornik we wrześniu zaburzyła letnią stratyfikację wykształconą w pelagialu. Spowodowała ona rozcieńczenie stężeń soli (chlor- ków i siarczanów) oraz niewielki wzrost zawartości azotanów i fosforu ogólnego. Porównując okres przed wezbraniem i krótko po przejściu fali powodziowej, w składzie fitoplanktonu stwierdzono zmiany w obrębie dominujących gatunków należących do sinic (Cyanobacteria). 91

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 91 - 103 2009 PL ISSN 0324-8461

THE STRUCTURE OF MACROZOOBENTHOS ASSEMBLAGES IN THE AREA OF SEWAGE-TREATMENT PLANT IN JURATA – JASTARNIA (THE PUCK BAY COASTAL ZONE)

KRYSTIAN OBOLEWSKI*, ANNA JAROSIEWICZ

Pomeranian Academy in Słupsk, Department of Water Ecology ul. Arciszewskiego 22B, 76-200 Słupsk, Poland * Corresponding author e-mail: [email protected]

Keywords: Macrozoobenthos, sandy bottom, the Puck Bay, sewage treatment plant.

Abstract: Single study on horizontal distribution of macrozoobenthos in the sandy bottom of Jastarnia and Jura- ta coastal zone was conducted in summer 2004. 15 sampling sites in Jurata were divided into 4 radii every 100 m and 4 sampling sites were located near the harbor in Jastarnia. 18 species and 3 groups represented benthic invertebrates in the studied area. They reached the density of x = 1840 indiv.·m-2 and wet mass of x = 121.8 -2 x -2 x -2 gww·m near Jurata and near Jastarnia = 638 indiv.·m and = 376.6 gww·m , respectively. The most abundant species were Hediste diversicolor, Cerastoderma glaucum and Hydrobia ulvae. As for the biodiversity calculated with the Shannon index, it reached the highest values at sampling sites the most distant from the shore in Jurata. Species composition as well as qualitative and quantitative structure of benthic fauna in the studied area indicated unsatisfactory environmental conditions and low value of the area as a feeding ground for fish.

INTRODUCTION

The Puck Bay is a specific part of the Baltic Sea, which peculiarity results from its geo- graphical location and hydrological conditions [16]. The Bay is divided by a sandy, sub- merged bank, ranging from the headland near village Rewa towards Kuźnica on the Hel Peninsula and is called Rybitwia Mielizna [9]. The western, separated fragment of the Puck Bay (120 km2) is a shallow-water lagoon known as the internal Puck Bay [8] or the Puck Lagoon [4]. Its biological, physical and chemical conditions are influenced by the rivers (Reda, Gizdepka and Płutnica) rather than by marine waters [9, 10]. In turn, the eastern part of the Bay, called the external Puck Bay, is deeper and directly connected to the Gulf of Gdańsk [1]. As a result, a higher resistance to anthropogenic influence is observed in this part of the Puck Bay. Therefore, a sewage-treatment plant has been located on the Hel Peninsula, at the border between the internal and external Puck Bay. Its role is to collect sewage from the peninsula the amount of which is considerably high during summer. As a result, deterioration in water quality has particularly influenced benthic organisms – a widely studied fauna of the southern Baltic Sea – mostly due to their scare migration [3, 12, 13, 21, 25]. Structural changes of zoobenthos and decrease in the number of stenotopic species indicate the acceleration process of the Puck Bay eutrophi- 92 KRYSTIAN OBOLEWSKI, ANNA JAROSIEWICZ cation [22]. The most disturbing changes have taken place in the shallow zone around the Hel Peninsula (up to 10 m depth), where molluscs and polychaetes – resistant to contamination – have substituted crustaceans. One of the factors, resulting in an increase of water fertility, can be the post-treatment waters discharged from the sewage-treatment plant directly to the bay. Recently, in order to minimize negative effects, a 1630 m long pipeline has been built, which pipes the waters away to the deeper zones of the reservoir. However, the ecological changes caused by the former practice have not been thoroughly studied so far [19]. Long-term investigations of the sewage-treatment plant influence on benthos in Swarzewo (the Puck Lagoon) [6, 23] suggest, that in the case of the Hel Penin- sula negative effects can also be considerable. The aim of this study was to determine the qualitative and quantitative structure of macrozoobenthos in the shallow zone of the Puck Bay near the Jurata – Jastarnia sewage- treatment plant within the EU Water Framework directive, particularly its part concerning estuary research.

MATERIALS AND METHODS

The sampling material for this study was collected in summer 2004 in the coastal zone near Jurata (15 sampling sites) and near the water lane at the entrance to the harbor in Jastarnia (Fig. 1). The sampling sites near the sewage-treatment plant were located in 4 radii every 100 m. Samples were taken using the Petersen scoop bottom sampling device (area of 0.225 m2) 2–3 times at each site. The collected material was next sifted through a benthos sieve of 1 mm mesh size and then preserved in the 4% formalin solution. In each sample the following parameters were determined: species composition; abundance of the consecutive taxa; formalin mass (wet mass) after removal of water on a filter paper, measured on a laboratory scales (WPT 60) exact to 0.01 g. Molluscs were weighted jointly with shells. The results were related to the area of 1 m2. Biocenotic indexes of structural relations in benthic macrofauna (domination – D, frequency – Fr) were used in the successive analysis. Domination index was calculated both in case of density (D) and biomass (Dm). The most abundant of the species with the highest biomass in a given assemblage were divided according to the common classification [5]. In order to determine biodiversity, the Shannon index (H’) was used. Statistically the agglomeration analysis with Euclidian distances was performed using Statistica 5.1 G software [17]. In order to assess significance of the differences between average values, the Cochran and Cox test was used (for α = 0.05), because of a small size of the data set and non-homogeneity of variances. The lack of differences between the compared objects (C < Ca) indicated that the samples originated from the same general population and any differences observed were random. The Cochran and Cox test: E = error of standard deviation

α = 0.05 (from t-student distribution) THE STRUCTURE OF MACROZOOBENTHOS ASSEMBLAGES IN THE AREA OF... 93 Fig. 1. Localization of sampling sites 94 KRYSTIAN OBOLEWSKI, ANNA JAROSIEWICZ

RESULTS

Performed sampling revealed presence of 18 species and representatives of 4 groups, which were not divided into species (Tab. 1). Those groups included Prostoma, Jaera and also partly Gammarus representatives. Their species classification was found impossible due to their small size.

Table 1. Qualitative composition and domination structure of macrozoobenthos density (D) and biomass (Dm) in the studied area of the Puck Bay

Jurata Jastarnia radius [m] distance [m] Species I II III IV 100 200 300 400 100 300

D Dm D Dm D Dm D Dm D Dm D Dm NEMERTINEA Prostota sp. ------POLYCHAETA Hediste diversicolor (Müller) ++ + ++ - + ------Pygospio elegans Claparĕde -- -- CRUSTACEA Cyathura carinata (Kröyer) ------Idotea chelipes (Pallas) ------Idotea balthica (Pallas) -- -- Jaera sp. -- -- Gammarus tigrinus Reid ------Gammarus salinus Spooner -- -- Gammarus zaddachi Sexton -- -- Gammarus sp. -- -- + ------+ -- + -- Leptocheirus pilosus Zaddach -- -- Corophium volutator (Pallas) ------GASTROPODA Theodoxus fluviatilis(L.) -- -- Hydrobia ulvae Pendant + ------++ -- Hydrobia ventrosa Montagu ------+ -- BIVALVIA Mytilus edulis trossulus Gould ------Cerastoderma glaucum -- + -- ++ -- ++ -- ++ - ++ -- + (Poiret) Macoma balthica (L.) ------+ -- ++ Macoma calcarea Chemnitz -- -- Mya arenaria L. ------+

+++ – eudominant, ++ – dominant, + – subdominant, - – recedent, -- – subrecedent

At the sampling sites located close to Jurata (radius I) only 5–7 macrozoobenthos species were observed, with predominant Hediste diversicolor (Fr = 100%). The remaining species were recedent or subrecedent (Tab. 1). In turn, 5 taxa with predominant Hy- THE STRUCTURE OF MACROZOOBENTHOS ASSEMBLAGES IN THE AREA OF... 95 drobia ventrosa (Fr = 75%) were distinguished in the vicinity of harbor in Jastarnia. The calculated biodiversity index ranged from 1.04 to 1.91 in Jurata while in Jastarnia it reached 2.04 (Tab. 2). An average macrozoobenthos density in the zone 100 m off the shore in the sewage-treatment plant was measured at 1328 indiv.·m-2, which was 2.3 times higher than near the harbor in Jastarnia (Tab. 3). The highest fraction in macrozoobenthos density structure fell to Polychaeta near the shore in Jurata and to Gastropoda in Jastarnia (Fig. 2). As for the wet mass, Bivalvia predominated at the sampling sites close to the sewage-treatment plant, reaching ¾ of the total macrozoobenthos mass in that zone (Fig. 3). Near the harbor in Jastarnia clearly prevailed Gastropoda (95% of the total benthofau- -2 na mass). On average, wet mass values in the first radius were measured at 80.26 wwg ·m -2 in Jurata, while in Jastarnia –58.50 gww·m (Tab. 3). Higher density and wet mass values were observed at one sampling site, west of the sewage-treatment plant.

Table 2. Species and biocenotic biodiversity (Shannon index, H’) in the studied area of the Puck Bay

Jurata Jastarnia West off the sewage- East off the sewage- Radius [m] Mean no. treatment plant treatment plant Mean no. H’ H’ of taxa Number of of taxa No. of taxa H’ H’ taxa I – 100 6 1.48 7 1.91 5 1.04 5 2.04 II – 200 7 1.60 5 1.28 9 2.26 – – III – 300 7 2.06 6 1.54 8 2.30 7 2.00 IV – 400 5 1.30 4 1.05 5 1.68 – –

Fig. 2. Density (D) domination structure of macrozoobenthos near the sewage-treatment plant in Jurata and the harbor in Jastarnia 96 KRYSTIAN OBOLEWSKI, ANNA JAROSIEWICZ B 0.01 2.90 0.10 0.02 0.70 0.04 0.15 0.15 0.01 3.70 332.00 355.00 694.78 300 A 11 11 11 45 22 45 22 56 34 45 22 289 653 Jastarnia B distance [m] 0.3 1.1 0.90 58.5 36.90 19.30 100 A 67 89 44 222 122 564 + B 6.68 0.07 0.10 4.44 0.02 56.12 101.20 168.63 400 ) in the studied area of Puck Bay 4 4 A 18 40 22 58 -2 382 1404 2291 ·m ww + B 9.50 0.40 1.48 1.18 0.90 0.01 0.42 0.02 4.92 90.04 108.87 300 4 4 A 98 44 33 13 27 462 689 125 169 191 1889 ) and biomass (B – g -2 Jurata radius [m] B 0.01 1.42 0.01 0.40 3.27 2.37 1.47 22.13 98.30 129.38 200 7 A 61 15 96 59 15 430 178 1133 2014 -2 ·m ww B 0.06 0.01 0.04 11.45 11.90 19.25 37.55 80.26 100 A 11 11 96 56 111 911 122 1328 Table 3. Macrozoobenthos density (A – indiv.·m 3. Macrozoobenthos density (A Table and biomass < 0.01 g -2

sp. NEMERTINEA sp. Prostota POLYCHAETA Hediste diversicolor CRUSTACEA Cyathura carinata Pygospio elegans Gammarus GASTROPODA Theodoxus fluviatilis Hydrobia ulvae Hydrobia Idotea chelipes Idotea balthica Jaera sp. Gammarus salinus Gammarus zaddachi Leptocheirus pilosus volutator Corophium Gammarus tigrinus ventrosa Hydrobia BIVALVIA Mytilus edulis trossulus Cerastoderma glaucum Macoma balthica Macoma calcarea Mya arenaria ∑ + abundance < 1 indiv.·m THE STRUCTURE OF MACROZOOBENTHOS ASSEMBLAGES IN THE AREA OF... 97

Fig. 3. Biomass (Dm) domination structure of macrozoobenthos near the sewage-treatment plant in Jurata and the harbor in Jastarnia

At the sampling sites in Jurata, 200 m off the sewage-treatment plant, the abundance of macrofauna ranged from 5 to 9. As regards density, Polychaeta (mainly H. diversicolor, Fr = 100%) was predominant while Gastropoda (mainly Hydrobia ulvae, Fr = 75%) subdominant (Tab. 1). The average biodiversity index (H’) amounted to 1.603 and was slightly higher in comparison to the first radius. Macrozoobenthos density at the sites 200 m off the Jurata shore varied between 22 and 1133 indiv.·m-2 ( x = 2014 indiv.·m-2) and was 4-fold higher west of the sewage- -2 treatment plant (Tab. 3). In turn, biomass in the second radius reached 62.2–260.1 gww·m (Tab. 4). The wet mass value was mostly influenced by bivalves (82% of the total biomass) and polychaetes (17%), (Fig. 3). The highest mass among Bivalves reached lagoon cockles while among Polychaeta – H. diversicolor (Tab. 1). At the sampling sites of the third radius (300 m off the sewage-treatment plant) in Jurata, the collected benthofauna was represented by 5–9 taxa, the most in front of the sewage-treatment plant. Mean biodiversity index (H’) was definitely the highest of the studied coastal zone near Jurata (Tab. 2). In turn, in Jastarnia macrozoobenthos was represented by 9–10 taxa, with the highest number observed at the harbour exit. The obtained mean H’ values were similar to those in Jurata (Tab. 2). Macrozoobenthos density at the third radius in Jurata varied between 22 and 1911 indiv.·m-2. Gammaridae (Fr = 80%) representative predominated but H. diversicolor (Fr = 60%) and Cerastoderma glaucum (Fr = 100%) also significantly contributed to the total density (Tab. 1). In Jastarnia, the observed benthofauna density ranged from 510 to 711 indiv.·m-2 and was 1.4-fold higher east of the sewage-treatment plant than at the western sampling sites (Tab. 4). Biomass of benthic invertebrates at the third radius near the sewage-treatment plant varied between -2 -2 59.94 and 171.70 gww·m while in Jastarnia it reached 50.90–1339.05 gww·m . The species that mostly contributed to the total biomass where C. glaucum in Jurata ( x = 90 -2 -2 gww·m ) and Macoma balthica ( x = 355 gww·m ) in Jastarnia (Tab. 3). The last radius (400 m off the sewage-treatment plant) was inhabited by a lower number of taxa than sampling sites closer to the coast. Biodiversity index varied between 98 KRYSTIAN OBOLEWSKI, ANNA JAROSIEWICZ

0.70 and 2.47, with the highest values west of the sewage-treatment plant. Benthofauna density at the studied sites of the last radius ranged from 22 to 4667 indiv.·m-2 (Tab. 4) with the highest contribution of common Hydrobia ulvae (Fr = 60%, x = 1404 indiv.·m-2) and then euconstants – C. glaucum and H. diversicolor. As for biomass, it varied in a -2 wide range (32.10–467.83 gww·m ). The observed wet mass was based on Bivalvia which constituted 90% of the total macrozoobenthos biomass (Fig. 3). Lagoon cockles were predominant (Tab. 1). The agglomeration analysis of macrozoobenthos density indicated the tendency for group sampling sites of the same distance from the shore and located east and west (Fig. 4A). The most similar sites were the furthest ones off the coast (400 m) while one site to the west near Jurata was considerably different. As for biomass, agglomeration was formed by sampling sites near the shore of Jurata while the most different were the sites at the water lane to the harbor entrance in Jastarnia (Fig. 4B). It should be also noticed, that similarly as for macrozoobenthos density, biomass was grouped into western and eastern agglomerations. The Cochran and Cox test (a = 0.05) revealed that there were no significant differences in mean densities between the consecutive radii near the sewage-treatment plant and the harbor in Jastarnia, except for the sampling sites 300 m off the shore in both of the studied zones (Tab. 4).

DISCUSSION

Macrozoobenthos in the shallow-water zone of the Polish Baltic coast is the main food for fry and also serves as a bioindicator of water quality. Therefore, its qualitative and quantitative structure has been widely studied [3, 6, 21]. Performed investigations have indicated negative influence of contamination on benthic macrofauna development and unfavorable changes in species composition. The analysis of benthofauna structure also allows for assessment of estuary ecological conditions according to the guidelines of EU Water Framework Directive. Sewage-treatment plants in Swarzewo and Jurata were supposed to organize water- sewage management in the drainage basin of the Puck Bay and improve ecological conditions of that ecosystem [24]. However, sewage-treatment plants are also sources of contamination and the discharge point of waters rich with nutrients negatively influences biocenosis of that reservoir. The data obtained from the Jurata – Jastarnia sewage-treatment plant reveal a high 3 -1 amount of sewage discharged in 2004 (Q24h = 2344 m ·d ) but with reduced content of most of the pollutants (Tab. 5). However, concentration of phosphorus compounds in the bay waters is still considerable. In general, post-treatments waters are classified as II class of water quality and only the amount of suspended matter corresponds with class I. Pip- ing post-treatment waters off with 1630 m long and 300 mm diameter pipe to the deeper zone (> 6 m) of the Bay seems to be rational. However, due to the currents, post-treatment waters may still influence hydrobionts in the Bay. The density of benthic fauna near the sewage-treatment plant in Jurata was mostly contributed by Hediste diversicolor – species resistant to organic contamination. Its high abundance was typical for contaminated waters and indicated bad ecological conditions in the studied zone of the Puck Bay. The discussed species is an important food for ben- THE STRUCTURE OF MACROZOOBENTHOS ASSEMBLAGES IN THE AREA OF... 99 7 2.00 55.7 62.4 55.5 n = 2 610.5 0–578 300 m 694.97 22–578 Distance ), standard deviation = 1.711 < 2.748 = 1.711 x Jastarnia α(0.05) 5 Jastarnia – 2.04 69.7 56.8 n = 2 133.2 666.0 58.50 0–244 100 m 44–244 Distance C < 5–9 1.82 69.5 n = 7 948.2 93.39 1199.0 1364.4 0–1911 sewage- 22–1911 East off the East off treatment plant = 2.282 > 2.200 = 1.438 < 2.376 α(0.05) α(0.05) Profiles West – East Profiles 4–7 1.44 78.5 n = 8 1766.5 1910.8 2433.3 148.47 0–4667 West off off West 22–4667 C < C > the sewage- treatment plant Radius III Jurata – Jastarnia 300 m 5 1.30 n = 5 311.9 172.0 355.5 = 0.971 < 2.375 400 m 2226.2 168.61 0–4667 22–4667 Radius IV α(0.05) = 0.7 < 2.341 Jurata C < α(0.05) Radius I Jurata – Jastarnia 100 m 7 489 2.06 n = 5 139.7 175.8 = 0.784 < 2.352 300 m Radius III – IV 1840.0 108.89 0–1911 C < 22–1911 Radius III α(0.05) Radius II – IV = 1.200 < 2.360 = 0.192 < 2.263 C < α(0.05) α(0.05) 7 244 1.60 Radius I – IV n = 3 Radius II – III 163.3 257.7 200 m 2014.7 128.97 0–1133 22–1133 Radius II C < C < = 0.791 < 2.323 α(0.05) (SD), different of variability (CV) and biodiversity Shannon index Cochran Cox test for ring (SD), different 6 155 Radius I – II 1.48 n = 2 175.3 198.4 80.25 0–911 100 m 1321.0 22–911 Radius I C < ] ] ] -2 -2 -2 ] -2 ·m – average density – average biomass average – ww x x Cochran & Cox test (C) Shannon index CV [%] CV Density range [indiv.·m SD Median (Me) Average no. of taxa Average [indiv.·m [g Density min.–max. [indiv.·m Table 4. Comparison of density bentofaunal in the vicinity sewage treatment plant Jurata city and harbor Jastarnia: range, arithmetic average ( Table 100 KRYSTIAN OBOLEWSKI, ANNA JAROSIEWICZ

Fig. 4. Agglomeration analysis of the sampling sites with reference to macrozoobenthos density (A) and biomass (B) in the studied area of the Puck Bay THE STRUCTURE OF MACROZOOBENTHOS ASSEMBLAGES IN THE AREA OF... 101

thivorous fish, for example sand lances (Ammodytes tobianus L., total P 96.2 Hyperoplus lanceolatus Sauvage), sticklebacks (Gasterosteus ac- uleatus L., Pungitius pungitius (L.), Spinachia spinachia L.) and

total gobies (Gobius niger L., Phe omatoschistus minutus (Pall.), Poma- 97.1 N toschistus microps (Kröyer), Coryphopterus flavescens (Fabricius), Neogobius melanostomus Pall.). Water discharged from sewage-treatment plants is rich in nu- 99.6

matter trients and may induce phytoplankton blooms as well as increase in Suspended macrozoobenthos abundance, mostly bivalves. Particularly Maco- 5

Reduction of pollutants [%] pollutants of Reduction ma balthica is resistant to eutrophication [14], opposite to benthic 96.5

BOD crustaceans. In the investigated zone near Jurata, Macoma had the highest density at the sampling site the closest to the sewage-treat- ] -3

4 ment plant, where the constant inflow of organic contaminants used to take place. Macoma was accompanied by Mya arenaria, which 0.32 P-PO is commonly treated as an indicator of contaminated sediments [7, [mg P·dm 13]. That species occurred at the closest and the furthest sites with

] relation to the sewage-treatment plant, where its direct influence -3 and post-treatment water discharge were observed, respectively. total P 0.60 Mya arenaria is often eaten by Neogobius melanostomus, which

[mg P·dm compete for food with viviparous blenny and flounder fry [15]. Among filter feeders, lagoon cockles predominated in the ]

-3 studied zone. That confirms the thesis that it is the most common 4 bivalve in the Baltic Sea, highly resistant to anthropogenic pres- 0.18

N-NH sure [11, 20]. Mean density of that species in the Polish costal zone -2 [mg N·dm amounts to 180 indiv.·m and is similar to the density observed in Jurata and Jastarnia (191 indiv.·m-2) [20]. However, frequency of ] -3 lagoon cockles in the studied zone was higher (Fr = 100%) than

total given for the Polish coastal zone (Fr = 58%) while biomass was 6.5 N 12-fold higher. Due to considerable size and thick shells, fish reluc-

[mg N·dm tantly eat lagoon cockles. The clear water indicator, Pygospio elegans, avoided the zone

] adjacent to the sewage-treatment plant in Jurata. It occurred at the -3 entrance to the harbor in Jastarnia with low density. This contra-

9.4 dicts the investigation performed 10 years before at the same place

[mg·dm [19], which reported high abundance of Pygospio elegans and sug-

Suspended matter gested the improvement in habitat conditions. Post-treatment waters discharged to the Puck Bay the Puck to discharged waters Post-treatment

] The littoral zone (0–2 m depth) of the southern Baltic coast -3

5 is inhabited by the assemblage with predominant Corophiumvolu- ·dm 2 tator, Hydrobiidae [20]. It is adapted to a sandy, moving bottom, 1.7 BOD which in the studied zone occurred only in the strip directly in con-

[mg O tact with the land. That strip was narrow; therefore the observed

] density and biomass were low for Crustacea representatives. -3 The obtained bivalve biomass was mostly influenced by ·dm 2 Cerastoderma glaucum. Its average wet mass for the Polish coast 29.1 COD amounts to 9.25 g ·m-2, which is 9-fold higher than the wet mass

Table 5. Quality of post-treatment waters from the Jurata – Jastarnia sewage treatment plant piped off to the Puck Bay in summer 2004 (sewage treatment plant data) 5. Quality of post-treatment waters from the Jurata – Jastarnia sewage treatment plant piped off Table ww [mg O obtained near Jurata and almost 25-fold higher in the case of Jas- 102 KRYSTIAN OBOLEWSKI, ANNA JAROSIEWICZ tarnia region [11]. Considerable contribution to the benthic invertebrate biomass in Jurata was observed for Hediste diversicolor, which was accompanied by molluscs and to some extent by the Mya arenaria – Macoma balthica assemblage, typical for sandy bottom in the deeper zone of the Baltic Sea (10–25 m). Among the Crustacea representatives, Gam- maridae reached the highest biomass. They avoided the closest and the furthest zones in relation to the shore and gained the highest biomass 300 m off the coast, at sampling sites with sandy, sludge bottom. In Jastarnia, the highest biomass was observed near the water lane, at the exit from the harbor, where crustaceans appeared. They were mainly represented by Gammaridea (G. tigrinus, G. salinus, G. zaddachi) and Corophium volutator. That made the discussed zone a valuable feeding ground for benthivorous fish. The only problem could be posed by the noise caused by ships near the harbor, petroleum contaminants and regular deepening of the water lane. High abundance of Crustacea in that zone must have been the result of sludge removement that had revealed sandy bottom, which is favored by crustaceans [25]. The structure of benthic fauna in the shallow-water zone of the Puck Bay may be formed not only by ichtyofauna but also by water fowls. Avifauna of the whole Puck Bay varies considerably and each year over 50 000 individuals are recorded [18]. They can reduce the molluscs population. Moreover, some species (for example Clangule hymealis L., Samaterie mallissima, Fulica atra L.) feed even on Gammaridae. In winter, common golden eye can reach a high number – on average 1144 indiv. This species feed only on crustaceans [2, 18]. As a result, all these factors influence macrozoobenthos density and biomass and also ecological conditions of the shallow-watered zone near Jurata and Jastarnia.

CONCLUSIONS

1. Macrozoobenthos near the sewage-treatment plant in Jurata was characterized by a low biodiversity, which is typical for simplified ecological systems. 2. As regards macrozoobenthos density, Hediste diversicolor predominated, as a species abundant in degraded aquatic ecosystems, while biomass was influenced by Cerastoderma glaucum. 3. Macrozoobenthos density and biomass were the highest at sites the most distant from contamination sources. 4. The performed analysis of benthic fauna structure in the studied area indicates bad ecological conditions according to the classification proposed in the EU Water Framework Directive.

REFERENCES

[1] Bolałek J.: Krążenie materii między wodą naddenną a osadem na przykładzie Zatoki Puckiej, Uniwer- sytet Gdański, Rozprawy i monografie, nr 186, Gdańsk 1993. [2] Brodecki Z., L. Żmudziński: Morskie obszary chronione w Polsce, CBM PAN, Uniwersytet Gdański, nr 138, Gdańsk 1997. [3] Demel K., Z. Mulicki: Studia ilościowe nad wydajnością biologiczną dna południowego Bałtyku, Prace Morsk. Inst. Ryb., 7, 75–126 (1954). [4] Jackowski E.: Stan tarlisk w Zatoce Puckiej, Morsk. Inst. Ryb., Studia i Materiały, Seria B, nr 71, Gdynia 1998. [5] Kasprzak K., W. Niedbała: Wskaźniki biocenotyczne stosowane przy porządkowaniu i analizie danych w badaniach ilościowych, [w:] Metody stosowane w zoologii gleb, M. Górny, L. Grüm (red.), PWN, Warszawa 1981, pp. 397–402. THE STRUCTURE OF MACROZOOBENTHOS ASSEMBLAGES IN THE AREA OF... 103

[6] Kotwicki S., M. Miłosek, M. Szymelfenig, A. Witkowski, M. Wołowicz: Struktura i dynamika zespołów bentosu w strefie brzegowej Zatoki Puckiej w rejonie oczyszczalni ścieków w Swarzewie, Archiwum Ochrony Środowiska, 3-4, 133–154 (1993). [7] Kruk-Dowgiałło L.: Przyrodnicza waloryzacja morskich części obszarów chronionych HELCOM BSPA województwa pomorskiego, Nadmorski Park Krajobrazowy, Crangon 7 CMB PAN, Gdynia 2000[8] Majewski W.: Morfometria i hydrografia, [w:] Zatoka Gdańska, A. Majewski (red.), Wyd. Geolog., 1990, pp. 10–19. [9] Nowacki J.: Ogólna charakterystyka warunków termiczno-zasoleniowych w Zatoce Puckiej, Zesz. Nauk. Wydz. BiNOZ UG, Oceanografia, 10, 67–93 (1984). [10] Obolewski K., M. Konkel: Zagęszczenie makrofauny bezkręgowej w strefie płytkowodnej Zatoki Puckiej porośniętej trzciną, Słup. Prace Biol., 4, 79–92 (2007) [11] Obolewski K., M. Konkel, A. Strzelczak, Z. Piesik: Distribution and the role of Cerastoderma glaucum (Poiret, 1789) in the Polish Baltic Sea coast, Balt. Coast. Zone, 11, 13–24 (2007) [12] Okołotowicz G.: Biomasa makrozoobentosu polskiej strefy Bałtyku wskaźnikiem jej zanieczyszczenia, Biul. Mor. Inst. Ryb., 5-6, 27–39 (1985). [13] Ostrowski J.: Wpływ zanieczyszczenia na zoobentos Zatoki Gdańskiej ze szczególnym uwzględnieniem określenia gatunków wskaźnikowych, Stud. i Mater. Morsk. Inst. Ryb., 26A, 5–20 (1985). [14] Piesik Z.: Macrozoobenthos of the coastal zone in the region of Słowiński National Park, Balt. Coast. Zone, 2, 47–60 (1998). [15] Skóra K.: Ryby dla Zatoki, Założenia do koncepcji odtworzenia zasobów ryb Zatoki Puckiej, Stacja Mor- ska UG, Hel 1997. [16] Słomianko P.: Zatoka Pucka, Oceanologia, PAN – KBN, 5-2, 271 (1974). [17] StatSoft Inc.: STATISTICA for Windows (Computer program manual), Tulsa, http://www.statsoft.com (1997). [18] Stepniewicz L., W. Meissner: Assessment of the zoobenthos biomass consumed yearly by diving ducks wintering in the Gulf of Gdańsk (southern Baltic Sea), Ornis Svecica, 9, 143–154 (1999). [19] Szcześniak E.: Makrofauna denna przybrzeżnej okolicy oczyszczalni ścieków w Juracie w latach 1992– 1993, maszynopis, Uniwersytet Gdański 1994. [20] Warzocha J.: Classification and structure of macrofaunal communities in the southern Baltic, Arch. Fish. Mar. Res., 42, 3, 225–237 (1995). [21] Wenne R., K. Wiktor: Fauna denna wód przybrzeżnych. Biocenoza wód przybrzeżnych Zatoki Gdańskiej w warunkach wzrostu eutrofizacji, Biologia Morza, (6), 39, KBM PAN, 137–172 (1982). [22] Wiktor K.: Makrozoobentos, [w:] Zatoka Pucka, K. Korzeniewski (red.), Inst. Oceanogr. Uniw. Gdańskiego, 442–454 (1993). [23] Wołowicz M.: Zmiany biocenozy strefy płytkowodnej Zatoki Puckiej w rejonie ujścia oczyszczalni ścieków w Swarzewie, [w:] Materiały Konferencji Ekologia rejonów lądowych, przybrzeżnych i morskich Bałtyku – ochrona i kształtowanie, Cz. 1 – Środowisko morskie, Sopot 1993, 97–114. [24] Wołowicz M., S. Kotwicki, M. Geringer d’Odenberg: Wieloletnie zmiany biocenoz Zatoki Puckiej w rejonie ujścia oczyszczalni ścieków w Swarzewie, [w:] Zatoka Pucka, K. Korzeniewski (red.), Inst. Oceanogr. Uniw. Gdańskiego, 510–519 (1993). [25] Żmudziński L.: Zoobentos płytkowodnej strefy Bałtyku, WSP, Słupsk 1982.

Received: April 4, 2008; accepted: August 10, 2009.

STRUKTURA ZESPOŁU MAKROZOOBENTOSU W STREFIE BRZEGOWEJ ZATOKI PUCKIEJ W OKOLICACH OCZYSZCZALNI ŚCIEKÓW JURATA – JASTARNIA

Badania nad poziomym rozmieszczeniem makrozoobentosu piaszczystego dna w okolicach Jastarni i Juraty prowadzone były jednorazowo latem 2004 roku. Wyznaczono 15 stanowisk w okolicach Juraty dzieląc stanowiska na cztery promienie oddalone od siebie o 100 m oraz 4 stanowiska w pobliżu portu w Jastarni. Bezkręgo- wce denne na tym obszarze reprezentowane były przez 18 gatunków i 3 grupy ponadgatunkowe, które w x -2 x -2 pobliżu Juraty osiągały zagęszczenie = 1840 osobn.·m i masę mokrą = 121,8 gmm·m , a w okolicach Jas- x -2 x -2 tarni = 638 osobn.·m i = 376,6 gmm·m . Najczęściej spotykanymi gatunkami były Hediste diversicolor, Cerastoderma glaucum i Hydrobia ulvae. Większą bioróżnorodnością wyznaczoną wskaźnikiem Shannona- Wienera charakteryzowały się stanowiska najbardziej oddalone od brzegu w Juracie. Skład gatunkowy oraz struktura jakościowo-ilościowa fauny dennej w tej części Zatoki Puckiej świadczy o niezadowalającym stanie środowiska oraz niskiej wartości tych obszarów jako miejsca żerowania ryb. 104 105

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 105 - 117 2009 PL ISSN 0324-8461

SEWAGE SLUDGE AND FOAM MANAGEMENT IN ENHANCED BIOLOGICAL NUTRIENTS REMOVAL PLANT (EBNRP)

JAN SUSCHKA, ELIGIUSZ KOWALSKI

Institute of Environmental Engineering of the Polish Academy of Sciences ul. M. Skłodowskiej-Curie 34, 41-819 Zabrze, Poland Corresponding author e-mail: [email protected]

Keywords: Activated sludge, anaerobic digestion, biomass lyses, foam disintegration.

Abstract: Most often sewage treatment and sludge disposal are handled as two separate technological parts of treatment plants. Attempts are made to change the practice. Keeping the standards of treated sewage is the primary objective, and sewage sludge is a by-product which has to be get rid of. The environmental consequences of various procedures of sludge disposal are rarely considered. On the other hand, incorporation of sludge handling procedures in the processes of sewage treatment can result in cost savings and be environmentally friendly. In the presented paper, suggestions are given on possibilities of closer integration of sewage and sludge treatment, based on experiments. Research aimed at sewage sludge quantity minimization and quality upgrading, recovery of phosphorous and efficient nitrogen removal. Appearing occasionally scum floating over biological sewage treatment units was shown to be considered as an integrated part of sewage treatment and sludge handling at EBNRP’s.

INTRODUCTION

Activated sludge is the most widely used biological waste water treatment process. In- dependently of the type of the activated sludge process applied, there is always a certain amount of excess sludge produced to be wasted. Even at very low organic substrate load there is a yield coefficient of about 0.4. For conventionally activated sludge with a load of about 0.5 g BOD/(g·d), the yield coefficient can be as high as 0.8. With the introduction of biological sewage treatment aiming at nutrients removal (nitrogen and phosphorous) in addition to organic substrates removal (expressed as BOD or COD), denominated as EBNRP’s the first mechanical stage of sewage treatment is most often omitted. The main reason is supplying sufficient organic substrate (organic carbon) for efficient denitrification (nitrogen removal). That approach resulted in production of distinctly larger amounts of surplus activated sludge to be disposed, which is difficult to dewater. Also phosphorous removal can contribute distinctively to the amount of surplus activated sludge to be wasted. Although newly constructed wastewater treatment plants are designed for biological phosphorous removal, the prevailing practice is phosphorus precipitation with ferrous or aluminum salts. As a result additional sludge to be wasted is produced. If supporting the advanced biological nutrients removal process with chemical 106 JAN SUSCHKA, ELIGIUSZ KOWALSKI precipitation of phosphorous, an increase of waste activated sludge by about 6 kg TS/kg

Premoved is possible. The additional amount of sludge to be disposed will be about 15%. Treatment and disposal of excess sludge from waste water treatment plants is costly and simple land fill or direct agriculture application methods can no longer be used in Eu- rope. Therefore, sludge minimization is at present of paramount importance. An overview of possible to be applied methods of sludge minimization was given by Wei et al. [23]. Anaerobic sewage sludge digestion if composed mainly of preliminary sludge (re- tained in primary settling tanks) with a part of surplus activated sludge is recognized as an effective process, resulting in an “acceptable”, almost odorless sludge, readily dewatering and drying. After eventual additional conditioning, agricultural use was widely practiced. The advantage of anaerobic sludge digestion is biogas production of high energetic value. Anaerobic digestion of surplus activated sludge as a solely substrate is less effective, both in quality of digested sludge and the amount of produced energy (biogas). Also in addition to higher content of phosphorous in activated sludge microorganisms’ precipitation of intregit and struvit become a serious problem of pipe and peripheral equipment clogging. At EBNRP scum is often formed at bioreactors surfaces and entering anaerobic digesters cause foaming, minimizing the operational (effective) volume and affecting negatively mixing efficiency of the digesters’ content.

ANAEROBIC SLUDGE DIGESTION – UPGRADING THE HYDROLYSIS STEP

The microbiology of anaerobic digestion is complex, involving several bacterial groups. Four major steps can be distinguished. The first step is solubilisation of insoluble particulate matter and biological decomposition of organic polymers to monomers or dimmers. This step is denominated as the hydrolysis step. The second and the third steps, acidoge- nesis and acetogenesis, allow production of methane in the following fourth step. The first stage of anaerobic digestion, the hydrolysis step, is regarded as the rate limiting step in the degradation of complex organic compounds, such as waste activated sludge. Therefore, several techniques have been investigated to upgrade the effects of organics decomposition by introduction of pretreatment hydrolysis. Much attention is given to thermal hydrolysis as an alternative pretreatment process. In fact, thermal pretreatment increases the rate of hydrolysis, thus leading to a greater extent of solubilisation of the available chemical oxygen demand. This allows for enhanced rates of degradation in the process of anaerobic sludge digestion. The developed and commercialized CAMBI process [11] can be an example of thermal treatment which precedes sludge digestion. It is considered to be a thermal disintegration procedure which substantially hydrolyses the sludge. Saturated steam is used for sludge hydrolysis at a temperature of 165°C at 6 bar pressure for 30 minutes without addition of chemicals. The thermal pretreatment results in a substantial biogas production increase. Also a 60% VS reduction with the digester loading of 5–6 kg VS/m3 per day is possible. The final product is fully pasteurized – free of all known pathogens. Typically, thermal pretreatment allows for reduction of the digesters volume in comparison to conventional process. However, it has been documented that thermal pretreatment of sludge is responsible for the formation of refractory dissolve organic compounds [3, 5]. Among other refractory compounds, melanoidin has been hypothesized to be produced, resulting in dark brown liquor [17]. After commissioning of the CAMBI process at the treatment plant SEWAGE SLUDGE AND FOAM MANAGEMENT IN ENHANCED BIOLOGICAL NUTRIENTS ...107

Oxley Creek – Australia [4], a distinctive increase of color and dissolved nitrogen in the liquor has been experienced. Color produced during the thermal hydrolysis of waste activated sludge was found [4] to be highly dependent on the operating temperature of the process. By decreasing the thermal hydrolysis process operating temperature from 165 to 140°C, for a reaction period of 30 min, a reduction of 70% of the color was obtained. Thermal pretreatment, as documented [1], at a temperature of 121°C effectively reduces foam formation in anaerobic digesters. This indirectly contributes to higher biogas production. Refractory compounds are also produced in the process during the synergetic pretreatment in a microwave-enhanced advanced hydrogen peroxide oxidation process

(MW/H2O2-AOP) [6]. Activated sludge treatment with H2O2 resulted in an 11–34% loss of total solids, COD and total biopolymers (humic acids, proteins and sugar), further enhanced by microwave irradiation resulting in solubilisation of particulate COD. However, the generated soluble organics were slower to biodegrade. Probable elevated microwave temperature could contribute to the production of refractory products. Another approach of sewage sludge pretreatment prior to anaerobic digestion is based on oxidation processes using ozone [2, 8] and hydrogen peroxide, or hydrolysis with alkaline or enzyme. Alkaline disintegration is simple in terms of necessary equipment and operation. Alkaline sludge treatment can disrupt flocks and cells, release inner organic matters and accelerate hydrolysis. If applied as sludge pretreatment before anaerobic digestion better effects of digestion can be expected [10]. Besides this, alkaline sludge treatment can also release the water held inside flocks and cell structure, which can not be removed by conventional dewatering processes. Therefore, alkaline treatment can improve sludge dewatering ability [16]. Hydrolysis as an effect of NaOH addition depends on the added amount and reaction time. An initial period of 30 minutes is given to allow chemical reactions and penetration of the liquid of higher pH to activate sludge flocks. An example of the increase of soluble chemical oxygen demand (SCOD) is presented in Figure 1. The released SCOD is substantially higher for the initial pH of 10.

Fig. 1. Release of SCOD as an effect of alkaline addition 108 JAN SUSCHKA, ELIGIUSZ KOWALSKI

The effects of alkalinization are more pronounced when samples are maintained for some time under anaerobic conditions as shown in Figure 2.

Fig. 2. Solubilization effects in anaerobic conditions for various initial pH values

The time to achieve the constant level of SCOD concentration depended on the desired alkalinization, i.e. the intended pH. The quasi constant level could be interpreted as the maximum possible to achieve degree of chemical hydrolysis. The intensity of that process depended on the initial pH. For the initial pH of 7, 8, 9 and 10, the respective solubilization time was approximately 55, 50, 30 and 15 hours (Fig. 3).

Fig. 3. Time elapsed before reaching a quasi constant solubilization effect in anaerobic conditions for different initial pH values

The effects of organic matter release SCOD can be further upgraded if combined with hydrodynamic disintegration [19, 21]. The effects of hydrodynamic disintegration SEWAGE SLUDGE AND FOAM MANAGEMENT IN ENHANCED BIOLOGICAL NUTRIENTS ...109 of waste activated sludge, with an initial pH of 8, 9 and 10 – measured after 30 minutes of NaOH addition are given in Figure 4. ] 3 /dm 2 ChZT [mg O ChZT

Sludge without pH=8 + hydrodynamic pH=9 + hydrodynamic pH=10 + hydrodynamic disintegration disintegration disintegration disintegration Fig. 4. Release of organic matter SCOD in the process of waste activated sludge hydrodynamic disintegration, previously spiked with NaOH

The examples discussed above show that simple activated sludge flocks dissolution techniques exist at low cost and simple additional equipment. Probable the most promising technique of sludge disintegration prior to anaerobic digestion will be alkalinisation followed by hydrodynamic disintegration. Nevertheless, all of the aforementioned chemical, mechanical or thermal pretreatment processes have found practical full technical application; however, all have some faults either technical, or operational, or are not sufficiently cost effective.

TWO-PHASE ANAEROBIC DIGESTION

While the first phase of the process of anaerobic sludge digestion is complex organic matter hydrolysis, which, as said before, is regarded as the rate limiting step, it seems natural to exercise that step under thermophilic conditions. Obviously, the organic matter hydrolysis at higher temperature of 55°C, typical for thermophilic digestion, is more effective in comparison to the temperature of 33°C of mesophilic digestion. Unfortunately, thermophilic conditions as the first stage of anaerobic digestion result in a final product more difficult to dewater and dark brown color of the supernatant. There are no unanimous statements about the effectiveness, in terms of gas production and volatile substances reduction, of the application of thermophilic digestion as the first step or the single-stage. The other configuration, the use of mesophilic digestion as the first step and thermophilic digestion as the second step is very seldom considered. In order to overcome the conventional approach, a co-phase consisting of mesophilic and thermophilic processes was suggested [18]. The comparison with single stage mesophilic or thermophilic digestion has shown a much higher effect of volatile solid reduction and a sludge and supernatant quality comparable to a single stage mesophilic digestion. A 58.4% volatile solids reduction in the two stage process, that is much higher than 43.5% and 46.8% reduction respectively in the mesophilic and thermophilic single 110 JAN SUSCHKA, ELIGIUSZ KOWALSKI stage processes was achieved [18]. Also the soluble chemical oxygen demand (SCOD) was only about 2180 mg/dm3 in comparison to 5240 mg/dm3 for thermophilic digestion.

THE QUESTION OF FOAM

Filamentous bacteria such as Microthrix parvicella, Nocardia amarae or Gordonia amarae are responsible for activated sludge bulking and foam (scum) formation at wastewater treatment plants aiming at nutrients removal. From the very beginning of enhanced nutrients removal processes introduced in the last century, scum floating over the surface of bioreactors and secondary settling tanks raised a lot of attention. The reasons of the scum appearance and possible techniques of destruction or avoidance have been intensively investigated. The filamentous bacteria themselves do not cause foaming. They do produce biosurfactants at concentrations sufficient to generate persistent foams by reducing the rate of drainage from the foam lamellae [7]. Surprisingly, the capacity of filamentous bacteria to accumulate phosphorus has attracted very little attention. It is well documented that specific micro-organisms have the ability of excess phosphorus assimilation, which enters into composition of several macro- molecules in the cell. Some bacteria including Acinetobacter have the ability to store phosphorus as polyphosphates in special granules (volutin granules). It has been demonstrated that the mentioned before filamentous bacteria (but not only) also accumulate phosphorus as polyphosphates in volutin granules [14]. The amount of stored phosphates is at least similar, or even higher, to that of specialized phosphorus accumulating bacteria like Acinetobacter. The most often present in scum filamentous bacteria Microthrix parvicella and Nocardia amarae can accumulate about 20% more phosphorus than Aci- netobacter calcoaceticus [13]. Actinomycetes synthesize polyphosphates and poli-β-hydroxybutyrate as reserve material [13], and are able to use many nitrogen compounds, and thus have the potential to tolerate both nitrogen and phosphorus deficiencies. Phosphorus and nitrogen were found to be present in filamentous organisms in excess [12, 13] which showed that nutrients can accumulate at interfaces, thus providing a relatively nutrient reach environment (haven). The principle of phosphorus accumulation by filamentous bacteria follows the principle of the micro-organisms present in the activated sludge flocks. Under anaerobic condition phosphates are released, and accumulated in aerobic conditions. The foam or scum floating over the surface of bioreactors, very often over all of the three sectors – anaerobic, anoxic and aerobic – does not only cause a visual negative effect but also, as it is claimed, causes serious operational troubles. There are however, properties of positive aspects in connection to the overall process of waste water treatment. The content of phosphorus in the scum biomass expressed as g P/kg MLSS most often is found to be somewhat higher (exceptionally much higher) than that in the activated sludge. The average amount of accumulated phosphorus in the activated sludge biomass (from several large EBNR plants) that was measured in the our experiments was 26 g P/kg MLSS (2.6%), while in the scum biomass floating over the surface the accumulated phosphorus could be as high as 32 g P/kg MLSS (3.2%). Actually the possible amounts of phosphorus to be accumulated by e.g. Acineto- bacter calcoaceticus, or filamentous organisms such as Nocardia amarae, or Microthrix SEWAGE SLUDGE AND FOAM MANAGEMENT IN ENHANCED BIOLOGICAL NUTRIENTS ...111 parvicella are very similar [13]. The higher content of phosphorus in the scum biomass in comparison to activated sludge flocks is the result of higher content of filamentous micro-organisms in the scum. Microscopic observations show clearly the polyphosphorus volutins in the filamentous organisms, as given e.g. in Figure 5.

Fig. 5. Micrograph of scum showing phosphorus volutins in filamentous organisms (black or yellow dots) Sludge or scum disintegration results in micro-organisms and associated polymeric matter dissolution, as well as release of phosphates. The photo below (Fig. 6) shows clearly partially destructed filaments and phosphorus granules thrown out. Disintegra- tion of scum in comparison to waste activated sludge, achievement of a similar degree of organic matter and phosphates release, requires at least 50% less time and consequently the power consumption. It becomes therefore evident that the scum promises to be an effective medium for phosphorus recovery. To show the effects of disintegration (hydrodynamic disintegration) two examples are given in Figure 7.

Fig. 6. Microphotos of partially disintegrated scum showing the shot out phosphorus volutins (black dots) 112 JAN SUSCHKA, ELIGIUSZ KOWALSKI ] 3 /dm ] 4 3 /dm 4 Phopshates [mg PO Phopshates [mg PO

Fig. 7. Example of phosphates concentration in the liquid associated to activate sludge and scum, before (A) and after (B) disintegration

The amounts of phosphates released from waste activated sludge in the process of disintegration, were similar at all investigated EBNRP’s. Seldom the amount of phos- 3 phates released, reached a level of 100 mg PO4/dm . However, the amount of phosphates 3 dissolved in the process of scum disintegration can surpass the value of 400 mg PO4/dm (approximately 130 mg P/dm3). Definitively the release of phosphorus is accompanied with the release of organic matter. Expressing the organic matter as dissolved (soluble) SCOD, a correlation between the released organic matter and phosphates was found. Obviously, the correlation between released SCOD and phosphates differs for different WWTP’s. In our experiments the SCOD/P ratio for WAS (Waste Activated Sludge) most often was about 18.6 g/g, while the respective ratio for scum was about 14.6 g/g. As mentioned before, the ratios can differ from case to case and the given values do not have a universal meaning. Determined here, the SCOD/P ratios correspond well to results given, e.g. by Kampas et al. [15]. They gave an approximate value for RAS ~ 13 g/g. What is most interesting is the reverse ratio P/SCOD (g P/g SCOD). With the concentration increase of disintegrated biomass, there is an increase of P/SCOD ratio. Ap- proximate values of P/SCOD are as follows: activated sludge 0.0325 or 3.25%, RAS 0.0538 or 5.35%, foam 0.0685 or 6.85%. The message from the results is that the amount of phosphorus released form the scum could be twice as high as from activated sludge taken from a bioreactor in relation to the amount of released organic matter (SCOD). That phenomenon could be explained by more effective destruction of filamentous micro-organisms. Besides the mechanical destruction of micro-organisms also the polyphosphates volutins are more easily “shot” out from the filaments. SEWAGE SLUDGE AND FOAM MANAGEMENT IN ENHANCED BIOLOGICAL NUTRIENTS ...113

Substantial release of phosphates by filamentous microorganisms occurs if the foam is left for some time under anaerobic conditions. Under prolonged anaerobic conditions and higher temperature of 33°C, for 15 days the determined concentration of released 3 phosphates varied in the range from 210 up to 290 mg PO4/dm . That effect is the result of biological hydrolysis. In combination with disintegration the effects of phosphates release can drastically increase. The liquor associated to the scum contains relatively low concentrations of ammo- 3 nia – up to 18 mg NH4/dm . However, if left under anaerobic conditions the amount of 3 ammonia can increase to as much as to 110 mg N-NH4/dm . This means that in order to fulfill the struvit formula, (MAP – magnesium ammonia phosphate – MgNH4PO4) only magnesium which is in deficit has to be added [22]. It applies also to the classical process of anaerobic sludge digestion, eventually with the addition of disintegrated scum. Recovery of phosphorus in the form of struvit is already a well established process; therefore it seems to be the most appropriate technique.

PERSPECTIVES OF SUSTAINABLE SLUDGE MANAGEMENT – AN ALTERNATIVE

Based on an extensive review of the investigated and implemented in practice sludge management options, as well as on performed investigations, an alternative approach is proposed, mainly for WAS at EBNRP’s. It has been proved that preliminary waste activated sludge disintegration has a distinctive positive effect on the effects of mesophilic anaerobic sludge digestion. On average, the effects of biogas production can increase by a factor of 1.4 (Fig. 8) /g dry solids] 3 Biogas production [cm

Fig. 8. Mesophilic anaerobic activated sludge digestion – biogas yield A – only waste activated sludge, B – plus 35% of waste activated sludge preliminarily disintegrated

Disintegration of activated sludge in combination with anaerobic sludge digestion is also advantageous in terms of filamentous micro-organisms eradication being a hazard at EBNRP’s. Disintegration of filamentous microorganisms in advance to anaerobic sludge

12 114 JAN SUSCHKA, ELIGIUSZ KOWALSKI digestion effectively reduces foaming in digesters, increases the biogas production, and as said before, increases the amount of phosphates released and recovered. Having in mind a two stage anaerobic digestion process, in which the first stage would be performed at mesophilic temperatures (about 33°C), followed by thermophilic digestion, the crucial step would be volatile acids production in the first stage. Separa- tion of the process of anaerobic digestion into two stages is widely admitted. The aim is production of higher amounts of VFA in the first stage. The optimal concentrations of VFA are obtained within a period of 3–5 days, thus the first mesophilic stage can be relatively small. Sludge lyses in advance of anaerobic digestion are advantage. As already mentioned, alkalinisation and disintegration were found to be promising alternatives [9]. The second stage of anaerobic sludge digestion, in thermophilic (55°C) conditions allows further, by up to 30%, to increase produced biogas. Simultaneously, volatile solids reduction in the order of 65% and above can be achieved. Although it is widely admitted that recycling sewage sludge to farmland is the best practical environmental option, the threat of spreading pathogens within the environment resulted in its limited use. However, the significant benefit gained from adding organic matter and essential plant nutrients to soil for crop production and soil structural improve- ments has to be stressed. Much more attention is required to develop sufficiently safe sludge handling procedures, reduce the risk, and assure wider recycling of sewage sludge to the land. Pathogen inactivation in mesophilic anaerobic digestion processes occurs however; the effects differ from case to case, and are considered to be insufficient. The inactivation process is not directly influenced by temperature (about 33°C) but is attributed to other complex factors such as microbial competition and inhibition. Additionally, thermophilic anaerobic digestion (about 55°C), as the second sludge treatment stage, decreases distinctively the risk of pathogens distribution to the farmland. Heating further the sludge to the pasteurization level of 70°C degree, a microbial safe product can be obtained. The recommended minimum time of pasteurization is usually 30 minutes. Based on existing knowledge and carried out experiments (except for pasteurization) the below presented layout is suggested as an alterative of sludge handling (Fig. 9).

W Hydrolysis Mesophilic Termophilic Pasterisation C 55°C 70–90°C A S MAP fertilizer

Scum Agriculture – farmland

Fig. 9. Suggested alternative stream-line of complex sewage sludge handling

There are many measurable benefits, which comprise – logical stepwise temperature increase and avoiding intermittent cooling procedures. Produced sludge after thermophilic anaerobic digestion is odorless and has reasonable good dewatering conditions. SEWAGE SLUDGE AND FOAM MANAGEMENT IN ENHANCED BIOLOGICAL NUTRIENTS ...115

The proposed layout can be supplemented by phosphorous recovery e.g. as struvit [20] being a fertilizer. ] The problem3 1800of scum (foam) has to be mentioned again, while addition of disintegrated scum to the 1600anaerobic digester results in pronounced biogas yield (Fig. 10).

] 1800

3 1400 1600 1200 1400 1000 1200 800 1000 Gas production [cm 600

Gas production [cm 800 400 600 200 400 0 200 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 0 Time [d] 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 activatedactivated sludge s ludge ++20% 20% of disintegratedof dis integrated sludge added s ludge added

++20% 20% of disintegratedof dis integrated foam added foam addedTime [d] Fig. 10. Effects of disintegrated sludge or disintegrated scum addition on biogas production

The suggested above stream line of sludge management could be enriched by addition of the return stream of supernatant from sludge dewatering step of digested sludge after struvit precipitation to the sewage treatment units. Also a small part of hydrolyzed waste activated sludge can be returned to the denitrification step as a readily degradable organic substrate, including volatile fatty acids.

CONCLUSIONS

Sustainability of the environment should be based on organic matter recovery to the land. Recycling of organic matter of sewage sludge should be a priority to maintain the fertility of farm land for future food and industrial plants production. The goal of the presented alterative stream-line of processes is to demonstrate that simple, power saving or even power production and cost effective sludge handling is feasible. Anaerobic sewage sludge digestion is an almost universally used process at medium and large waste water treatment plants for sludge handling before disposal or use as a substrate in the agriculture. New, more stringent environmental regulations as well as the introduction of nutrients removal techniques from sewage have imposed refurbishment of the anaerobic digestion process. At EBNRP’s in general the only sewage sludge to be treated is waste activated sludge (WAS). Microorganisms present in WAS do not hydro- lyze easily, and make the anaerobic digestion process less effective, both in terms of biogas production as well as in terms of pathogens absence in treated sludge. To overcome the obstacles an effective pre-hydrolyzes (prior to anaerobic digestion), and an effective pathogen removal process have to been introduced. 116 JAN SUSCHKA, ELIGIUSZ KOWALSKI

Based on carried out experiments it was proven that sludge alkalization to pH 9 with subsequent mechanical disintegration allows for a drastic reduction of the digestion time, and a distinct increase of biogas production. A two phase anaerobic sludge digestion process is advocated, in the order, first phase methanogenic conditions (about 33°C), the second step thermophilic conditions (about 55°C). Both steps (phases), each with a hydraulic retention of 5 days, permit a good digestion sludge quality. If there is such a requirement, to the two steps of anaerobic sludge digestion, pasteurization can be added. Supernatant (liquor) of digested sludge thickening and/or drying, rich in phosphates should serve for magnesium ammonium phosphates (struvit) precipitation. Appearing occasionally over bioreactors the foam formed by filamentous microorganisms which have a high ability of phosphorus accumulation, could actively participate in nutrients removal process. Foam, if disintegrated before being supplied to anaerobic digesters, contributes to higher biogas production.

REFERENCES

[1] Barjenbruch M., H. Hoffman, J. Träncker, O. Kopplow: Verminderung des Schäumens in Faulbehäl- tern durch Vorbehandlung des Überschussschlames, KA – Wasserwirtschaft, Abwasser, Abfall, 47, 3, 366–372 (2000). [2] Bohler M., H. Siegrist: Partial ozonation of activated sludge to reduce excess sludge, improve denitrification and control scumming and bulking, Wat. Sci. Technol., 49, 10, 41–49 (2004). [3] Climent M., I. Ferrer, M.D. Baeza, A. Artola, F. Vazquez, X. Font: Effects of thermal and mechanical pretreatment of secondary sludge on biogas production under thermophilic conditions, Chem. Eng. J., 133, 1-3, 325–342 (2007). [4] Dwyer J., D. Starrenburg, S. Tait, K. Barr, D. Batstone, P. Lant: Decreasing activated sludge thermal hydrolysis temperature reduces product color, without decreasing degradability, Wat. Res., 42, 20, 4699– 4709 (2008). [5] Eskicioglu C., K.J. Kennedy, R.L. Droste: Characterisation of soluble organic matter of waste activated sludge before and after thermal pretreatment, Wat. Res., 40, 20, 3725–3736 (2006). [6] Eskicioglu C., A. Prorot, J. Marin, R.L. Droste, K.J. Kennedy: Synergetic pretreatment of sewage by micro-

wave irradiation in presence of H2O2 for enhanced anaerobic digestion, Wat. Res., 42, 18, 4674–4582 (2008). [7] Heard J., E. Harvey, B.B. Johnson., J. Wells, M.J. Angove: The effect of filamentous bacteria on foam production and stability, Colloids and Surfaces B; Biointerfaces, 63, 21–26 (2008). [8] Huysmans A., M. Weemaes, P.A. Finseca, W. Verstraete: Ozonation of activated sludge in the recycle stream, J. Chem. Technol. a. Biotechnol., 76, 3, 321–324 (2001). [9] Kampas P., S.A. Parsons, P. Pearce, S. Ledoux, P. Vale. J. Churchley. E. Cartmell: Mechanical sludge disintegration for the production of carbon source for biological nutrient removal, Wat. Res., 41, 1734–1742 (2007). [10] Kim T-H., T-H. Kim, S. Yu, Y.K. Nam, D-K. Choi, S.R. Lee, M-J. Lee: Solubilization of waste activated sludge with alkaline treatment and gamma ray irradiation, J. Ind. Eng. Chem., 13, 7, 1149–1153 (2007). [11] Kopp J., W. Ewert: New processes for improvement of sludge digestion and sludge dewatering, European Biosolids and Organic Resources Conference, Wakefield, UK 2006. [12] Lemmer H., R.M. Kroppenstedt: Chemotaxonomy and physiology of some actinomycetes isolated from summing activated sludge, Systematic and Applied Microbiology, 5, 124–135 (1984). [13] Machnicka A.: Assimilation and release of phosphorus by filamentous micro-organisms in process of wastewater treatment, PhD dissertation, (in polish) Silesian University, Gliwice 2007. [14] Machnicka A., J. Suschka. K. Grübel: Phosphorous uptake by filamentous bacteria, World Water Con- gress and Exhibition, Maroko, Marrakech, 19–24 September 2004. [15] Marshall K.C.: Growth at interfaces, [in:] Strategies of Microbial Life in Extreme Environments, ed. M. Shilo, 281–290, Berlin 1979, Dahelm Konferenzen. SEWAGE SLUDGE AND FOAM MANAGEMENT IN ENHANCED BIOLOGICAL NUTRIENTS ...117

[16] Neyens E., J. Baeyens, C. Creemers: Alkaline thermal sludge hydrolysis, J. Hazard. Mater., 106, 83–92 (2003). [17] Penaud V., J.P. Delgenes, R. Moletta: Characterisation of soluble molecules from thermochemically pre- treated sludge, Journal of Environmental Engineering ASCE, 126, 5, 397–402 (2000). [18] Song Y-Ch., S-J. Kwon, J-H. Woo: Mesophilic and thermophilic temperature co-phase anaerobic digestion compared with single-stage mesophilic and thermophilic digestion of sewage sludge, Wat. Res., 38, 1653–1662 (2004). [19] Suschka J., K. Grűbel A. Machnicka:;. Możliwość intensyfikacji procesu fermentacji beztlenowej osadów ściekowych poprzez dezintegrację osadu czynnego w procesie kawitacji mechanicznej, Gaz, Woda i Tech- nika Sanitarna, 3, 26–28 (2007). [20] Suschka J., E. Kowalski. J. Mazierski, K. Grübel: Alkaline solubilisation of waste activated sludge (WAS) for soluble organic substrate (SCOD) production, International Conference – Nutrient Recovery from Wastewater Streams, Vancouver, Canada, 2009. [21] Suschka J., A. Machnicka, K. Grűbel: Surplus activated sludge disintegration for additional nutrients removal, Archives of Environmental Protection, 33, 2, 55–65 (2007). [22] Suschka J., A. Machnicka. S. Popławski: Specific Problems of Phosphorous removal and recovery from waste waters, Conference Ecology and Eco-Technology, Vienna, 24–28 February 2002. [23] Wei Y., R. van Houten, A. Borger, D. Eikelboom, Y. Fan: Minimization of excess sludge production for biological wastewater treatment, Wat. Res., 37, 4453–4467 (2003).

Received: May 20, 2009; accepted: October 5, 2009.

POSTĘPOWANIE Z OSADAMI I PIANĄ W ZAAWANSOWANYCH PROCESACH BIOLOGICZNEGO OCZYSZCZANIA ŚCIEKÓW WRAZ Z USUWANIEM POŻYWEK

Procesy oczyszczania ścieków i przeróbki osadów są bardzo często prowadzone jako dwa oddzielne procesy technologiczne. Podejmując wysiłki zmierzające do zmiany tej praktyki trzeba pamiętać, że dotrzymanie stan- dardów oczyszczania ścieków jest celem nadrzędnym a osady ściekowe są produktem ubocznym, który należy usunąć z oczyszczalni. Konsekwencje środowiskowe różnych sposobów postępowania z osadami ściekowymi są rzadko rozważane, z drugiej strony włączenie procesów przeróbki osadów w ciąg technologiczny oczyszczania ścieków może przynieść oszczędności i być przyjazne środowisku naturalnemu. W pracy, w oparciu o eksperymenty, sugeruje się możliwość ściślejszej integracji procesów oczyszczania ścieków i przeróbki osadów. Celem badań było zminimalizowanie ilości osadów, poprawienie ich jakości oraz odzysk fosforu i poprawa efektów usuwania azotu. Pojawiająca się na powierzchni bioreaktorów piana może być eliminowana w procesach przeróbki osadów. 118 119

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 119 - 128 2009 PL ISSN 0324-8461

THE EFFECT OF MICROWAVE RADIATION ON WASTE TREATMENT IN A REACTOR WITH A BIOFILM

MARCIN ZIELIŃSKI*, MIROSŁAW KRZEMIENIEWSKI

University of Warmia and Mazury in Olsztyn, Department of Environmental Protection Engineering ul. Prawocheńskiego 1, 10-957 Olsztyn, Poland * Corresponding author e-mail: [email protected]

Keywords: Microwave, organic compounds, nitrification, denitrification, athermal properties of microwaves.

Abstract: This paper presents the results of research into the effect of microwave radiation on waste treatment in a reactor with a biofilm. 2.45 GHz microwave radiation was supplied to the reactors placed inside a microwave chamber. The radiation was generated by magnetron and the amount of radiation was controlled by varying the times of alternating phases of radiation and treatment. The study was conducted in three arrangements of alternating phases: 7 s radiation and 10 min treatment; 7 s radiation and 5 min treatment; 25 s radiation and 10 min treatment. The results obtained in the study show that microwave radiation affects the process of biological waste treatment not only through heating but also through its athermal properties. An increase in the effectiveness of the treatment was particularly visible in the microwave action in nitrogen removal.

INTRODUCTION

The rate of waste treatment processes which take place in a biofilm reactor depends on a number of parameters: the amount and activity of the biofilm, the size of the contact surface between the waste and biofilm and the mass exchange rate between the biofilm and waste. Additionally, the final purification effect is connected with the effectiveness of internal diffusion, external diffusion and biochemical transformations of organic compounds in cell metabolism. The size of diffusion (the amount of transferred substance), is the result of concentration gradient, the surface and the factor of proportionality – also called the diffusion coefficient. The value of the coefficient is affected by physical conditions, with the temperature being the predominant factor. By affecting the diffusion, the temperature influences the kinetics of a number of unit processes of waste treatment, e.g. gas exchange, substrate solubility, liquid mixing. The rate of biochemical decomposition of waste depends on the activity of microorganisms (precisely – on the enzymatic reaction rate). The ambient conditions, i.e. the substrate concentrations, temperature, redox potential, osmotic pressure and the presence of enzymes activating and inhibiting substances have an influence on the activity of enzymes. The relationship between the reaction rate and temperature is expressed by the van ’t Hoff-Arrhenius equation. A transformed form of the equation which compares the reaction rates at different temperatures is commonly used. 120 MARCIN ZIELIŃSKI, MIROSŁAW KRZEMIENIEWSKI

(1) where: kT1 – reaction rate constant at the temperature T1 in variable units, depending on the reaction order, kT2 – reaction rate constant at the temperature T2 in variable units, depending on the reaction order, E – activation energy [J·mol], R – universal gas constant [8.314 J·mol.K],

T1,2 – temperature [K]. A transformed form of the equation is more commonly applied in modeling the processes of waste treatment:

(2)

where: k20 – reaction rate constant at the temperature 293K (20°C) in variable units, depending on the reaction order, θ – temperature coefficient,

T20 – referenced temperature 293K (20°C). The effect of temperature on the enzyme-catalyzed reaction rate is decided by two processes. An increase in temperature is accompanied by an enzyme-catalyzed reaction, which is consistent with the van ’t Hoff-Arrhenius equation. However, because of the protein character of enzymes, the relationship is only valid below a certain temperature value. An increase in temperature above the optimum value for a given enzyme brings about its denaturation. Assuming that optimizing the thermal conditions can improve the effectiveness of waste treatment processes, research was initiated into applying microwave radiation to this end. Microwave heating is selective. Its direct action causes an increase in the temperature of only those bodies whose dielectric properties allow them to absorb it [12]. These relationships are useful in trickling filters. Microwave radiation makes it possible to deliver energy directly to the biofilm (a radiation absorbing body). When the packing material for the reactor is made of plastic, which is transparent to radiation, the loss of radiation caused by radiation absorption is prevented. Applying a trickling filter makes it possible to heat up only biomass, with limited energy absorption by the treated waste.

EXPERIMENTAL PROTOCOLS

The experiment was conducted with use of a dripping reactor with a biofilm, placed inside a chamber where it was exposed to microwave radiation. The casing and packing material for the reactor were made of material transparent to microwaves. The reactor’s sensitive volume was V = 145 cm³, the packing specific surface s = 202 m2·m-3 and the theoretical active surface of the reactor was F = 0.029 m2. The radiation was generated in a magnetron from where it was sent to the reactor chamber through a waveguide. The generator’s total power was 800 W, its efficiency was 52% and it produced radiation at a frequency of 2.45 GHz. The magnetron emitted THE EFFECT OF MICROWAVE RADIATION ON WASTE TREATMENT IN A REACTOR... 121 radiation with a constant efficiency and the amount of energy supplied to the reactor was controlled by changing the times within the operation-break cycles. The operation of the microwave generator was synchronized by feeding the waste to the reactor. Before starting the generator, the feeding of waste to the reactor was cut off. Thanks to this, the microwave energy was absorbed primarily by the biofilm and not by the waste being treated. After the radiation phase ended, the waste dispensing pump restarted and the system returned to the purification phase (Tab. 1).

Table 1. The temperature inside the bioreactor in relation to the radiation input

The temperature The temperature Radiation phase/Tre- The amount of micro- following the radiation following the treatment atment phase wave energy* [W·s] phase [°C] phase [°C]

7 s/10 min 1.2 22.5 21.3 7 s/5 min 2.5 20.9 20.1 25 s/10 min 4.3 36.3 32.6 * the amount of energy input stands for the total supplied power divided by the total work time of the one reactor.

The microwave radiation caused the temperature inside the biological reactor to rise. The temperature of the biofilm was the highest just after the work phase of the microwave generator ended and depended on the amount of supplied radiation. It then dropped as the purification phase continued (Tab. 1). The temperature of the control reactor and the environment was kept at a constant level of 20°C. The study was conducted with use of municipal waste. It was taken directly from the municipal collector at the same hour once daily. After being collected, the waste was left for 0.5 hour for sedimentation and chemical analyses were conducted (Tab. 2).

Table 2. The values of pollution indexes in raw sewage

Index Unit Mean value Standard deviation 3 COD [mg O2·dm ] 220 21.1 3 BOD5 [mg O2·dm ] 175 14.4 3 Total nitrogen [mg Nog·dm ] 45 5.6 3 Ammonium nitrogen [mg N-NH4·dm ] 25 5.3 3 Total phosphorus [mg Pog·dm ] 18 3.8 3 Phosphates [mg P-PO4·dm ] 12 3.7 Total suspended matter [mg·dm3] 240 81.5

The experiment was conducted periodically. Every 24 hours, the entire volume of waste in the impounding reservoir was replaced. The waste from the impounding reservoir was fed to the biological reactor and then returned to it (Fig. 1). The hydraulic load q = 0.15 m3·m-2·h-1 was applied, as a result of which the whole amount of waste in the reactor flowed through the biological reactor 21 times in 24 hours. The organic pollution load on the surface of the reactor with the pollution, expressed as COD, was close to A’ – 8.6 2 -1 g O2·m ·d . The experiment was conducted for 30 days for each series which differed by the amount of radiation supplied to the reactors (Tab. 1). 122 MARCIN ZIELIŃSKI, MIROSŁAW KRZEMIENIEWSKI

A B

2) radiation phase 7 s; 25 s

1) 5)

treatment phase 6) 5 min; 10 min

3) 6)

Fig. 1. A – diagram of the experiment layout: 1) biological reactor, 2) microwave chamber, 3) retention reservoir, 4) sewage supply to the reactor, 5) microwave generator, 6) sewage replacement in the retention reservoir; B – diagram of the operation of the experiment arrangement

In the purified waste taken each day, the organic substance, expressed as COD, was determined as well as the nitrogen compound concentration: nitrogen in ammonium

N-NH4, nitrogen in nitrates N-NO3, nitrogen in nitrites N-NO2, Kjeldahl’s nitrogen (ammonium nitrogen + organic nitrogen). Additionally, the biomass yield was calculated. The quantity of biomass was analyzed inside the reactor at the beginning and at the end of the measuring period, including the amount of excess biofilm in the effluent. Based on the analyses, the effect of the applied microwave radiation on the effectiveness of organic compound and nitrogen compound removal was measured. The results were analyzed statistically with use of a single-factor analysis of variance, at the assumed level of significance of p < 0.05. The normality of distribution was confirmed by the W Szapiro-Wilk test, while the hypothesis of the variance uniformity was verified with Leveney’s test. The differences between the average values of various groups were examined with Tukey’s HSD test. The reaction rate constants were determined by the method of regression and based on the experimental data. As in the control, tests were conducted with a reactor which was not exposed to microwave radiation and which worked in identical hydraulic conditions, with the same load of pollution. Inside the control reactor, the temperature was 20°C and hot air was used for heating.

THE EFFECT OF MICROWAVE RADIATION ON WASTE TREATMENT IN A REACTOR... 123

RESULTS

The experiment provided data for determining the effect of the applied microwave radiation on the effectiveness of waste treatment. This paper presents the basic parameters which determine the efficiency of biological waste treatment. The efficiency of the process can be described by the efficiency of organic compound removal, nitrogen compound removal and biomass increase. Nitrogen compounds were removed as a result of a biochemical reaction cascade. Normally, three consecutive phases are mentioned: ammo- nification, nitrification and denitrification. Nitrogen transformations were described by determination of nitrification efficiency and nitrogen loss when the denitrification process and biomass increase were taken into account. The effectiveness of organic compound removal was expressed as a decrease of COD in the waste being treated. The contribution of oxidation and biomass synthesis to the process of organic substance removal was also determined. Microwave radiation had a considerable effect on the efficiency of organic substance removal from waste only in one of the three doses used in the experiment. When 2.4 W·s was supplied to the reactor in the system in which the reactor worked for 7 seconds every 5 minutes, the reactor’s efficiency increased by 7.3% as compared to that of the control reactor. When the amount of radiation was smaller – 1.2 W·s – a low efficiency increase of 2.3% was observed. However, when the radiation was supplied to the reactor for 25 seconds every 10 minutes (4.3 W·s), this resulted in a slight drop in the efficiency of organic substance removal by 3.5% (Fig. 2). Statistically significant differences were not found among the series, using a level of significance of p < 0.05. Although the effect of microwaves on the final efficiency of organic substance removal was slight, it was significant in the unit processes. Microwaves caused an increase in the contribution of oxidation in organic substance removal, while the significance of biomass synthesis decreased. As a result of supplying as little as 1.2 W·s of radiation to the system, more than 10% more organic substance was removed due to oxidation. When twice as much energy (2.4 W·s) was supplied, oxidation was responsible for removing 78.4% of organic matter, while in the control reactor the value was merely 54% (Fig. 2).

100 [%] 80

0 1.2 W·s 2.4 W·s 4.3 W·s con.

respiration synthesis efficiency of COD removal

Fig. 2. Dependence of efficiency of COD removal and participation respiration and synthesis in this process on microwave amount 124 MARCIN ZIELIŃSKI, MIROSŁAW KRZEMIENIEWSKI

The most significant effect was observed when microwave radiation affected the efficiency of the nitrification process. As a result of supplying a mere 1.2 W·s of microwave energy, the efficiency of nitrification increased by 32% as compared to the control reactor. A larger amount of energy (2.4 W·s) caused a similar effect – an increase by 30.4%. There were no statistically significant differences between the series. Supplying radiation for 25 seconds every 10 minutes caused the efficiency to drop by 19.5% in relation to the control reactor, although the amount of supplied microwaves was the largest (4.3 W·s) (Fig 3). Nitrification efficiency in this series was statistically lower than in the other series.

100 [%]

0 1.2 W·s 2.4 W·s 4.3 W·s con.

reduction synthesis efficiency of nitrogen removal

Fig. 3. Dependence of efficiency of nitrogen removal and participation reduction and synthesis in this process on microwave amount

An analysis of the effect of microwaves on the efficiency of nitrogen removal revealed a 23% increase compared to the control reactor when 1.2 W·s of microwave energy was supplied to it. However, an increase in the amount of radiation supplied to the reactor to 2.4 W·s caused the removal of 45.4% of the total nitrogen from the raw waste, while in the control reactor it did not exceed 8.6%. These differences were statistically significant at the assumed level of significance of p < 0.05 with the use of Tukey’s test. In the third arrangement of power and time of radiation (4.3 W·s), the nitrogen removal was similar to that in the control reactor. It is even more interesting to analyze the effect of microwaves on the contribution of various processes to nitrogen removal. Reduction of nitrates to gaseous forms dominated in those series where 1.2 W·s and 2.4 W·s of radiation was supplied to the system, accounting for as much as 83.1% of the transformations, while in the other cases almost all the nitrogen was removed by incorporating it in the newly created biomass (Fig. 4). In the control reactor, 90.1% of the removed nitrogen was incorporated in the new biomass, with 9.9% denitrified. Among the key factors in the analysis of the process of biological waste treatment there are the thermal conditions in the reactor during the consecutive parts of the experiment. The study was conducted with three various amounts and time arrangements of radiation supply to the system. In the series when the radiation was supplied for 7 seconds every 10 minutes, the temperature rose to 21.2°C and then dropped to 20.0°C. The THE EFFECT OF MICROWAVE RADIATION ON WASTE TREATMENT IN A REACTOR... 125 average temperature was about 20.5°C, which was higher by 0.5°C than in the control reactor. In another series, when the generator worked for 7 seconds every 5 minutes, the maximum temperature in the reactor was 22.5°C. At the end of the purification phase, after 5 minutes, it dropped to 21.7°C, the average value being 22.0°C. The highest temperature differences were observed when the radiation was supplied for 25 seconds every 10 minutes. At the end of the radiation phase, the temperature inside the reactor rose to 36.3°C and after the 10-minute purification phase it dropped to 32.6°C, with the average value equal to 33.7°C (Fig. 5).

100 [%] 80

0 1.2 W·s 2.4 W·s 4.3 W·s con.

Fig. 4. Dependence of nitrification efficiency on microwave amount

38 36 34

] 32 25 s/10 min 4.3 W·s C

o [

e 30 tur a

r 28 e 26

Temp 24

22 7 s/5 min 2.4 W·s 7 s/10 min 1.2 W·s 20 control 18 0 600 1200 1800 2400 3000 3600 Time [s] Fig. 5. Changes of temperature inside reactors during experiment

DISCUSSION

The effect of microwave radiation on the efficiency of waste treatment, observed in the experiment, depended on the amount of supplied radiation and on the time arrangement in which it was supplied. The efficiency of pollution removal changed very little as a

126 MARCIN ZIELIŃSKI, MIROSŁAW KRZEMIENIEWSKI result of radiation. The maximum increase observed in the efficiency of the process was by about 7.3% in the series when 2.4 W·s of microwave energy was supplied, and the average temperature inside the reactor was higher by 2°C than inside the control reactor. Such results were consistent with the expectations. The literature contains numerous comments on the relatively small effect of change in the temperature on the activity of heterotrophic bacteria in the mesophilic temperature range. Kadlec and Reddy [5] point out that the reactions of microorganisms depend on temperature to a greater extent at its lowest values (below 15°C) than in the optimum range between 20 and 35°C, and a change in temperature in this range does not have a significant effect on BOD5 removal. A study into the colony forming abilities of heterotrophic bacteria conducted by Mayo and Noike [6] showed that the process rate is the same at 20°C and at 35°C. The authors emphasized that under stable conditions, heterotrophic bacteria did not react to temperature changes within the range from 10 to 20°C. The number of heterotrophic bacteria at 10 and 20°C was similar. Pabello et al. [7] found that a 21% increase in carbon compound removal took place between 10 and 20°C, while a further increase to 30°C brought about only an increase by 13%. In the current study, a temperature increase to the mean value of 33.7°C by radiating the waste for 25 seconds every 10 minutes reduced the amount of removed organic matter. This effect can probably be attributed to large temperature differences. During the 25 second radiation phase, the temperature inside the reactor rose by 3.7°C, to drop subsequently during the purification phase. According to numerous authors, an adverse effect of unstable temperature on the efficiency of the removal of organic matter expressed as COD is observed mainly in the processes which take place at higher temperatures. Tripathi and Allen [13] found that in order to avoid the adverse effect of temperature shock, an adaptation period of at least one week must be applied when the temperature is increased by 5°C. Microwave radiation of the biofilm significantly affected nitrogen removal from the waste. Thanks to the action of 1.2 W·s and 2.4 W·s of radiation, the nitrogen was removed, not only by biomass synthesis, but primarily as a result of the reduction of oxidized forms. Denitrification was possible mainly thanks to creating anoxic areas deep inside the biofilm, which was primarily due to microwave heating. Microwave energy causes a body to heat up in its whole volume. Considering the low thickness of a biofilm in relation to the depth of radiation penetration, it can be supposed that the biofilm was heated up uniformly. The relationship between creating the anoxic zones and the temperature of the biofilm was corroborated by a study conducted by Hao et al. [3], who found the oxygen penetration depth increased with a decrease in temperature. However, it must be noted that in the part of the experiment in which 4.3 W·s of radiation was supplied to the system, only a limited denitrification was observed, despite favorable temperature conditions and the possibility of creating anoxic zones. In this case, the nitrogen removal may have been limited by a low efficiency of nitrification. The possibility of simultaneous nitrification and denitrification in a settled biomass has been widely discussed in literature [2, 4, 11, 14]. The effect of microwave radiation on the process of waste treatment in the biofilm reactor can be explained by the presence of a thermal effect. A small increase in the degree of organic compound removal can be explained by the relatively low sensitivity of heterotrophic bacteria to temperature changes, while an increase in nitrogen was caused by the fact that temperature changes affected the creation of anoxic zones. However, THE EFFECT OF MICROWAVE RADIATION ON WASTE TREATMENT IN A REACTOR... 127 numerous phenomena were observed during the study which cannot be explained by the temperature effects which accompanied the radiation. The lowest of the applied amounts of radiation (1.2 W·s) caused the efficiency of nitrification to increase by as much as 32%, with the average temperature inside the reactor higher than that inside the control system by only 0.5°C. Surprisingly, such a small temperature increase was accompanied by a considerable increase in the amount of oxidized organic compounds and in the efficiency of nitrification. A temperature rise may have influenced the process of nitrification, but the efficiency of nitrogen removal in the control reactor, with a temperature lower by mere 0.5°C, was equal to one third of the former and denitrification was hardly observable. These unexpected effects were probably caused by the athermal properties of microwaves. Electromagnetic radiation can stimulate enzyme activity. Banik et al. [1] provide numerous examples to show the possibility of an athermal positive effect of microwaves on microorganisms. Parker et al. [10] examined the effect of microwaves on hydrated lipase. It was found that when the reaction environment was heated with microwaves, the enzymatic reaction rate increased 2- or 3-fold in relation to conventional heating. In discussing the effect of microwave radiation on biological matter, Ponne and Bartels [9] referred to a number of studies in which both positive and negative effects on microorganisms were found. On the other hand, some authors have questioned the very existence of non-thermal microwave effects [10].

CONCLUSIONS

− The effect of microwave radiation on the efficiency of organic matter removal was low and not statistically significant. − A significant (over 30%) increase in the nitrification effectiveness with a slight temperature increase could suggest the athermal properties of microwave radiation. − A large increase in denitrification efficiency in a radiation reactor with only a slightly higher temperature could also demonstrate the positive athermal effect of microwaves.

Acknowledgements This study was financed by the State Committee for Scientific Research within grant No. 3 P04G 038 22.

REFERENCES

[1] Banik S., S. Bandyopadhyay, S. Ganguly: Bioeffects of microwaves, a brief review, Biores. Technol., 87, 155–162 (2003). [2] Chui P.C., Y. Terashima, J.H. Tay, H. Ozaki: Performance of a partly aerated biofilter in the removal of nitrogen, Wat. Sci. Tech., 34, 187–194 (1996). [3] Hao X., J.J. Heijnen, M.C.M. van Loosdrecht: Model-based evaluation of temperature and inflow variations on a partial nitrification-anammox biofilm process, Wat. Res., 36, 4839–4849 (2002). [4] Helmer C., S. Kunst: Simultaneous nitrification/denitrification in aerobic biofilm system, Wat. Sci. Tech., 37, 183–187 (1998). [5] Kadlec, R.H., K.R. Reddy: Temperature effects in treatment wetlands, Wat. Environ. Res., 73, 543 (2001). [6] Mayo A.W., T. Noike: Effects of temperature and pH on the growth of heterotrophic bacteria in waste stabilization ponds, Wat. Res., 30, 447–455 (1996). [7] Pabello L.V., A. Alardo-Lubel, C. Durana-De-Bazua: Temperature effects on ciliates diversity and abundance in rotating biological reactor, Biores. Tech., 39, 55–60 (1992). 128 MARCIN ZIELIŃSKI, MIROSŁAW KRZEMIENIEWSKI

[8] Parker M.C., T. Besson, S. Lamare, M.D. Legoy: Microwave radiation can increase the rate of enzyme catalysed reaction in organic media, Tetrahedron Letters, 37, 8383–8386 (1996). [9] Ponne C.T., P. Bartels: Interaction of electromagnetic energy with biological material – relation to food processing, Radiat. Phys. Chem., 45, 591–607 (1995). [10] Porcelli M., G. Cacciapuoti, S. Fusco, R. Massa, G. D’ambrosio, C. Bertoldo, V. de Rosa Zappia: Non- thermal effects of microwaves on proteins: thermophilic enzymes as model system, FEBS Letters, 402, 102–106 (1997). [11] Siegirst H., S. Reithaar, G. Koch, P. Lais: Nitrogen loss in a nitryfing rotating contactor treating ammonium-rich wastewater without organic carbon, Wat. Sci. Tech., 38, 241–248 (1998). [12] Thostenson E.T., T.-W. Chou: Microwave processing: fundamentals and applications, Composites, A, 30, 1055–1071 (1999) [13] Tripathi C.S., D.G. Allen: Comparison of mesophilic and thermophilic aerobic biological treatment in sequencing batch reactors treating bleached kraft pulp mill effluent, Wat. Res., 33, 836–846 (1999). [14] Watanabe Y., S., Masuda, M. Ishiguro: Simultaneous nitrification and denitrification in micro-aerobic biofilms, Wat. Sci. Tech., 26, 511–522 (1992).

Received: July 16, 2008; accepted: August 5, 2009.

WPŁYW PROMIENIOWANIA MIKROFALOWEGO NA OCZYSZCZANIE ŚCIEKÓW W REAKTORZE Z BŁONĄ BIOLOGICZNĄ

W pracy przedstawiono wyniki badań nad wpływem promieniowania mikrofalowego na proces oczyszczania ścieków w reaktorze z błoną biologiczną. Do reaktorów umieszczonych we wnętrzu komory mikrofalowej dostarczano promieniowanie mikrofalowe o częstotliwości 2,45 GHz. Jako źródło mikrofal wykorzystano pracujący ze stałą moc magnetron, natomiast sterowania ilością dostarczanego promieniowania odbywało się poprzez zmienne czasy trwania następujących kolejno faz napromieniowania i oczyszczania. Badania przeprowadzono w trzech układach następujących cyklicznie faz: 7 s napromieniowanie 10 min oczyszczanie, 7 s napromieniowanie 5 min oczyszczanie oraz 25 s napromieniowanie 10 min. oczyszczanie. W ten sposób dostarczanego do reaktora promieniowania, odpowiednio w ilości 1,2 W·s, 2,5 W·s oraz 4,3 W·s. Uzyskane wyniki badań wskazują, że promieniowanie mikrofalowe wpływa na proces biologicznego oczyszczania ście- ków nie tylko w wyniku klasycznego ogrzewania, ale i poprzez swoje właściwości atermiczne. Szczególnie w przypadku przemian prowadzących do usunięcia azotu obserwowane było istotne zwiększenie ich sprawności w wyniku oddziaływania mikrofal. 129

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 129 - 144 2009 PL ISSN 0324-8461

HYDROCHEMICAL CONDITIONS FOR LOCALIZATION OF SMALL WATER RESERVOIRS ON THE EXAMPLE OF KLUCZBORK RESERVOIR

MIROSŁAW WIATKOWSKI

University of Opole, Department of Land Protection ul. Oleska 22, 45-052 Opole, Poland e-mail: [email protected]

Keywords: Water reservoir, water quality, water protection, pre-dam.

Abstract: The paper presents an analysis of hydrochemical conditions of the Stobrawa River – the right tributary of the Odra River. The aim of the analysis was to assess the possibility of storing the Stobrawa water in Kluczbork storage reservoir. A preliminary assessment of the reservoir water quality and its usability was made. The quality of water in the reservoir is particularly important as the main functions of the reservoir are flood protection, agricultural irrigation and recreation. The following physicochemical parameters of the Stobrawa - - + 3- River were analyzed: NO3 , NO2 , NH4 , PO4 , BOD5, COD, dissolved oxygen (DO), water temperature, pH, electrolytic conductivity and total suspended solids (TSS). Main descriptive statistical data were presented for the analyzed water quality indicators and loads. A statistical analysis of the correlations among all investigated water quality indicators and water flow was performed. The analysis showed that some of the indicators were mutually correlated with water flow at a significance level of p < 0.05. The carried out research showed significant contamination of the Stobrawa River in the cross-section of the planned reservoir, which indicates that the Stobrawa water could deteriorate the quality of water in the reservoir. Some reparatory actions to improve water quality in the reservoir were presented. One of them is rearrangement of water and wastewater management in the reservoir catchment. This must precede the construction of the reservoir. Another solution is construction of a pre-dam which will contribute to the improvement of water quality in the reservoir and extend its lifetime.

INTRODUCTION

Small water reservoirs, such as Kluczbork reservoir, constitute the basic elements of the so-called “small retention” and improve water balance. They are built mainly for storing water in the period of its overflow and for providing it in the low-flow periods. They have also some economic functions (agricultural irrigation, watering place, water supply for villages) and can be used for energy, natural and recreational purposes [20, 24, 26, 29, 31, 37]. They can also contribute to flood protection [27]. Moreover, quite significant is their impact on the adjacent areas [25]. Since in the upper and middle Odra River basin the possibilities for constructing big retention reservoirs are rather limited due to location and costs, the construction of small retention reservoirs seems to be justified. When building a water reservoir one should take into consideration not only the quantitative aspect but also the quality of water to be stored in the reservoir. There are various opinions on water quality and the impact of water storage in the reservoir on wa- 130 MIROSŁAW WIATKOWSKI ter quality changes. According to the prevailing opinion this contributes to intensification of a self-purification process [21, 43, 48–50]. However, in small reservoirs the quality of heavily contaminated water deteriorates [49, 51, 53]. Changes caused by damming up water in dams in water environment are rather complicated and may vary in time, depending on the use and age of the reservoir. Very often contaminants flowing to the reservoir with water and bed load can jeopardize the use and existence of the reservoir [1, 19, 23, 28]. What is important here is providing monitoring in river basins, in which small water reservoirs are to be built. These basins are usually not controlled hydrological. No water quality analyses are carried out. Therefore, contamination of planned and constructed reservoirs is one of the key issues [6, 16, 33, 34, 48, 52–54]. As far as water quality in the reservoir is concerned a significant role is played by the quality of water feeding the reservoir, which usually results from water and wastewater management in the basin [9, 52]. Phosphorus and nitrogen compounds are the key factors having an impact on the quality of water in the reservoir. The effect of nutrition of surface water is excessive growth of plant communities, mainly plankton. This can be easily noticed in summer in the form of “water blooms” covering small water reservoirs [11, 15, 51]. This eutrophication process should be taken into account already in studies and at the stage of designing of water reservoirs so that after their construction no unfavorable biochemical processes causing eutrophication would develop in the reservoir bowl. This must be carried out in compliance with the Water Act [45], which says that “at designing, construction and maintenance of water devices one should follow the principle of sustainable development, preserving good ecological state of water”. For many years people have been looking for methods to prevent eutrophication. One of them is based on the use of pre-dams [3–5, 30, 36, 49, 51]. The aim of this study is to analyze hydrochemical parameters of water in the Sto- brawa River to evaluate the possibilities of storing it in the planned Kluczbork water reservoir. A preliminary assessment of the reservoir water quality and its usability was made, as well as some actions to improve the quality of water feeding the designed reservoir were presented. Construction of a pre-dam in the backwater of Kluczbork reservoir was proposed.

CHARACTERISTICS OF KLUCZBORK RESERVOIR AND THE STOBRAWA RIVER CATCHMENT

Kluczbork reservoir will be located at the 61.5 km of the Stobrawa River (right tributary of the Odra River), about 1000 m eastwards, above the town of Kluczbork. From the administrative point of view it will be situated in Opolskie Voivodeship (Southern Poland), Figure 1. Kluczbork reservoir will be used for the following purposes: irrigation, reduction of flood wave, electric energy generation, fire protection for rural areas and forests, sports and recreation [32, 44]. The area where the reservoir is to be constructed is flat, covered with meadows, scrubs and fallow lands. On the right and left sides of the bowl there are gravel pits (old and new gravel pit) filled with water [44] (Fig. 1). HYDROCHEMICAL CONDITIONS FOR LOCALIZATION OF SMALL WATER RESERVOIRS... 131

Fig. 1. Location of the planned Kluczbork storage reservoir on the Stobrawa River A) reservoir catchment, B) reservoir bowl with hydrochemical measuring point

In the reservoir catchment there are Quaternary formations, mainly sand and gravel, accumulated on Tertiary silts. The area of the valley is covered with organic soil, alluvion and peat [44]. The depth of the permeable layer at the front dam varies from 3.7 to 10.5 m. Such geological structure imposes the necessity of constructing a tight, deep barrier reaching the impermeable layer [32]. In the vicinity of Kluczbork reservoir surface water a Main Groundwater Reservoir (GZWP) called Dolina Kopalna Stobrawy is located. These are four groundwater intakes providing water for the town. A part of the bowl of the future reservoir will be situated in the area of indirect protection of groundwater intakes, the northern border of which is formed by the Stobrawa River [38]. In this context the sealing must be made very carefully so that no exchange of surface- and groundwater would occur. In 2007 a sewerage system was provided to the villages in the direct catchment of the constructed reservoir. Other villages and towns of the reservoir catchment are to be provided with sewerage system from the Cohesion Fund to the year 2013. The main elements of Kluczbork reservoir are: front dam, spillway-discharge system and small water power plant. To improve the quality of water feeding Kluczbork reservoir the construction of a pre-sedimentation tank is planned. The area of the reservoir at a normal water lifting level will be 55.7 ha and at a maximum lifting level – 56.7 ha. The water lifting ordinate at the normal lifting level will be 186.00 m a.s.l., and at the maximum lifting level – 187.00 m a.s.l. The reservoir volume at the normal lifting level will be 1.1 mln m3 and at the maximum level – 1.683 mln m3. The average depth at the normal lifting level – 2 m and at the maximum level – 3 m. The length of the reservoir will be about 1400 m and its width – about 400 m [32]. The Stobrawa River in the planned reservoir cross-section is not controlled hydrological. The catchment area in the dam profile is 126 km2. Characteristic flows in this section are the following: average discharge SSQ = 0.574 m3·s-1, average low discharge 3 -1 3 -1 SNQ = 0.08 m ·s and inviolable flow Qo = 0.04 m ·s . Average annual precipitation in Kluczbork in the period of 1971–2000 is 650 mm and the average air temperature – about 8°C [22]. There are many fish ponds and hydrotechnical structures in the catchment. 132 MIROSŁAW WIATKOWSKI

METHODS

Water quality assessment in the Stobrawa River at the outlet to the planned reservoir was carried out based on the hydrochemical analyses performed at the measuring point located at the 63.5 km of the river course (Fig. 1). The analyses were made from May 2005 to April 2008. Thirty four water samples were collected. Water was collected from the subsurface river current. The following in- - - + dicators were taken into consideration in the water quality assessment: NO3 , NO2 , NH4 , 3- PO4 , BOD5, COD-Cr, water temperature, dissolved oxygen (DO), water pH, electrolytic conductivity and total suspended solids (TSS). Laboratory tests were performed in compliance with Polish standards [14]. Apart from water quality analyses also hydrometric measurements were made. Flow rate curve was determined. Based on the obtained water quality values and hydrometric measurements loads of contaminants carried out from the Stobrawa River catchment in the cross-section of the designed Kluczbork reservoir [kg] were calculated. Due to variable meteorological conditions two seasons were distinguished: the winter season (1 November – 30 April) and the summer season (1 May – 31 October). Physicochemical indicators were determined both for the whole year and for the above-mentioned seasons. A statistical analysis of concentrations of particular physicochemical water quality indicators was performed. For the obtained results location measures (average measures) and dispersion (variability) values were calculated, which allowed to present differences in the values of the analyzed indicators. As a location measure an arithmetic mean was assumed and as a dispersion measure – interval and standard deviation [18]. Moreover, average monthly loads and their ranges for nitrates, nitrites, ammonium and phosphates were compared. Correlations between flow rate and the Stobrawa water quality indicators were also analyzed. A statistical pres- entation of the correlations was made using a Pearson’s linear correlation coefficient [47]. It was assumed that the correlation was statistically significant in the case of p < 0.05. The quality of the Stobrawa water was assessed according to the Ordinance of the Minister of the Environment establishing way of classifying the state of uniform parts of surface waters [40] and water eutrophication process was assessed according to the Or- dinance [41]. Water usability in the context of the possibility of its lifting in the designed reservoir was determined by comparison of the analyzed indicators with limit values for water suitable for fish [39] and bathing [42].

RESULTS AND DISCUSSION

In the investigated period the discharge values in the analyzed cross-section varied from 0.150 to 1.880 m3·s-1. The average discharge value was 0.446 m3·s-1 and was lower than the one assumed in [32]. The highest discharge value was recorded in March 2006 and the lowest one in July 2006. The analyses of the selected physicochemical indicators in the Stobrawa water were carried out in the cross-section of the designed reservoir from May 2005 to April 2008. The characteristic of these parameters is presented in Table 1. HYDROCHEMICAL CONDITIONS FOR LOCALIZATION OF SMALL WATER RESERVOIRS... 133

Table 1. Water quality of the Stobrawa River in the cross-section of the designed reservoir (63.5 km of the river course)

Value Standard Pollution indicator Period Range Min. Max. Average deviation year 0.30 44.00 13.95 43.70 10.14 Nitrates summer 0.30 27.00 10.58 26.70 7.90 [mg NO -·dm-3] 3 winter 0.68 44.00 17.12 43.32 11.18 year 0.07 3.40 0.24 3.39 0.61 Nitrites summer 0.02 0.36 0.09 0.34 0.09 [mg NO -·dm-3] 2 winter 0.16 3.40 0.34 3.38 0.77 year 0.002 2.70 0.57 2.69 0.58 Ammonia summer 0.002 1.76 0.38 1.75 0.43 [mg NH +·dm-3] 4 winter 0.05 2.70 0.75 2.65 0.66 year 0.10 0.82 0.46 0.72 0.17 Phosphates summer 0.10 0.70 0.48 0.60 0.18 [mg PO 3-·dm-3] 4 winter 0.22 0.82 0.44 0.59 0.18 year 0.55 10.00 3.07 9.45 2.99 BOD summer 0.55 8.14 2.46 7.59 2.70 [mg O ·dm-3] 2 winter 1.00 10.00 3.46 9.00 3.23 year 3.70 66.00 23.89 62.30 17.91 COD summer 3.70 63.00 18.45 59.30 16.68 [mg O ·dm-3] 2 winter 7.20 66.00 28.49 58.80 18.24 year 0.50 20.30 9.56 19.80 5.73 Water temperature summer 6.00 20.30 14.33 14.30 4.10 [°C] winter 0.50 14.50 5.90 14.00 3.75 year 7.00 10.90 8.49 3.90 1.24 Dissolved oxygen summer 7.00 9.60 8.04 2.60 0.98 [mg O ·dm-3] 2 winter 7.20 10.90 8.94 3.70 1.39 year 6.13 8.20 7.22 2.07 0.62 Reaction summer 6.13 7.70 6.81 1.57 0.51 pH winter 6.42 8.20 7.53 1.78 0.56 year 155 803 394.57 648 114.25 Electrolytic conductivity summer 268 422 374.16 154 44.30 [μS·cm-1] winter 155 803 409.87 648 16.53 year 1.00 316 46.74 315.00 68.66 Total suspended solids summer 1.00 120 35.33 119.00 36.99 [mg·dm-3] winter 3.00 316 55.86 313.00 86.49

Table 1 shows that average concentrations of the analyzed physicochemical indicator s were the highest in the winter season. The only exceptions were: concentration of phosphates and water temperature. Higher average values corresponded with higher intervals and deviations, which indicates higher variability of results. Concentrations of the main biogenes in the water of the Stobrawa River are presented in Figures 2 and 3. Nitrate concentrations in the investigated period varied significantly (Fig. 2). The - -3 highest values were observed in the winter season (14 January 2008) – 44 mg NO3 ·dm . It can be assumed that the high concentrations of this indicator came from area flows. The lowest concentrations of nitrates were recorded in s ummer, when the concentrations of this indicator were regulated by vege. 134 MIROSŁAW WIATKOWSKI

Fig. 2. Changes of nitrate concentrations in the Stobrawa River in the cross-section of the designed Kluczbork reservoir (May 2005 – April 2008)

Fig. 3. Changes of phosphate concentrations in the Stobrawa River in the cross-section of the designed Kluczbork reservoir (May 2005 – April 2008)

The highest concentrations of nitrites were observed in spring and winter (Tab. 1). The highest content of nitrite nitrogen was recorded in December 2006 (3.4 mg - -3 NO2 ·dm ). The occurrence of this form of nitrogen in water testifies to penetration of household contaminants from villages located in the Stobrawa River catchment. Ammonia concentrations in the Stobrawa River varied from 0.002 do 2.70 mg + -3 NH4 ·dm , and the average value of this indicator in the entire research period was 0.57 + -3 mg NH4 ·dm (Tab. 1). Just like in the case of nitrite concentrations, the concentration of ammonia in winter season was higher than in summer. The ammonia content in water is HYDROCHEMICAL CONDITIONS FOR LOCALIZATION OF SMALL WATER RESERVOIRS... 135 an important indicator of contamination with albuminous substances which usually occur in great amounts in wastes. As far as phosphates are concerned (Fig. 3), the lowest concentrations were ob- 3- -3 served in September 2006 (0.1 mg PO4 ·dm ). The highest concentrations were recorded 3- -3 3- -3 in March 2007 (0.796 mg PO4 ·dm ) and December 2007 (0.82 mg PO4 ·dm ). This may have resulted from the release of this chemical to water through the frozen land cover and from household wastes. Another reason for the increase of these compounds is aging and dying of macrophytes, which only in spring and summer take up nitrogen and phosphate compounds. Biogenes are nutrients for them [17]. In winter and spring the increase of phosphate, nitrate nitrogen and ammonium nitrogen loads can be observed, which in turn begin to decrease in summer due to macrophytes. -3 BOD5 concentration in the Stobrawa River varied from 0.55 to 10.00 mg O2·dm

(Tab. 1). Higher BOD5 values were observed in the winter season (the highest recorded value was on 16 March 2008). Higher water contamination with easily degradable organic matter and higher BOD5 values could be observed. COD-Cr concentration in the Sto- -3 brawa water during the investigated period varied from 3.70 to 66.0 mg O2·dm (Tab. 1). The carried out research showed that the Stobrawa water temperature in the period 2005–2008 varied from 0.5°C to 20.3°C (Tab. 1). -3 Oxygen concentration in the Stobrawa River ranged from 7.00 to 10.90 mg O2·dm . The average content of DO at the measuring point in the investigated period of -3 2005–2008 was 8.49 mg O2·dm (Tab. 1). Higher DO values were observed in months of lower temperatures (February, March, April) than in summer and autumn. Water pH in the Stobrawa River varied from 6.13 to 8.20. The lowest pH was observed in September 2007 and the highest pH values – in March 2008 (Tab. 1). Electrolytic conductivity of water depends on the content of dissolved ions and water temperature [10]. Electrolytic conductivity of the Stobrawa River ranged from 155 to 803 μS·cm-1 (Tab. 1). The highest concentration of the total suspension (316 mg·dm-3) was recorded at a high water stage in the Stobrawa River catchment in March 2006 (Fig. 2). Therefore, it can be concluded that in the Stobrawa River catchment higher values of suspension were caused by spring thaw rather than by rainfalls. Higher concentrations were observed in the winter season (Tab. 1). Graphic comparison of average values and load ranges of the selected indicators for the Stobrawa River is presented in Figures 4–7. From the graphic analysis it can be concluded that the highest values of average monthly loads of nitrates, nitrites, ammonia and phosphates were observed in the winter period. In each analyzed case higher values of the interval and deviation corresponded with the higher average. In Table 2 statistical significance of the correlation between water flow rate and water quality indicators in the Stobrawa River in the cross-section of the planned reservoir is presented. The analysis of the linear correlation between the above-mentioned water quality indicators showed that some of them were significantly correlated. A statistically significant - negative correlation was found between nitrates NO3 and BOD5. A positive significant correlation was observed between ammonia and COD. In the case of COD a positive significant correlation was also found in the case of TSS. Water flow was positively correlated with COD, water temperature and TSS. 136 MIROSŁAW WIATKOWSKI -1 kg month

Fig. 4. Graphic comparison of average monthly loads of nitrates and their ranges in the Stobrawa River water in the cross-section of the designed Kluczbork reservoir (May 2005 – April 2008) -1 kg month

Fig. 5. Graphic comparison of average monthly loads of nitrites and their ranges in the Stobrawa River water in the cross-section of the designed Kluczbork reservoir (May 2005 – April 2008) HYDROCHEMICAL CONDITIONS FOR LOCALIZATION OF SMALL WATER RESERVOIRS... 137 -1 kg month

Fig. 6. Graphic comparison of average monthly loads of ammonia and their ranges in the Stobrawa River water in the cross-section of the designed Kluczbork reservoir (May 2005 – April 2008) -1 kg month

Fig. 7. Graphic comparison of average monthly loads of phosphates and their ranges in the Stobrawa River water in the cross-section of the designed Kluczbork reservoir (May 2005 – April 2008) 138 MIROSŁAW WIATKOWSKI

12. 1.00 p = – 0.000

11. 1.00 0.64 p = – =

p 10. 1.00 0.08 0.32 p = – p = 0.726 p = 0.093 9. 1.00 0.22 0.32 0.29 p = – p = 0.266 p = 0.172 p = 0.135 8. 0.11 1.00 0.15 0.12 p = – -0.20 p = 0.557 p = 0.753 p = 0.653 p = 0.710 7. 0.05 0.22 1.00 p = – -0.32 -0.50 -0.55 p = 0.373 p = 0.808 p = 0.442 p = 0.015 p = 0.007 0.006 0.003 6. 0.58 0.57 1.00 0.13 p = – -0.19 -0.22 -0.01 = = p = 0.961 p = 0.491 p = 0.472 p = 0.652 p p 5. 0.09 1.00 -0.11 p = – -0.19 -0.19 -0.05 -0.18 -0.09 p = 0.472 p = 0.798 p = 0.480 p = 0.482 p = 0.833 p = 0.714 p = 0.764 4. 0.03 0.02 0.54 0.17 1.00 0.18 0.19 0.39 p = – -0.31 p = 0.104 p = 0.068 p = 0.880 p = 0.398 p = 0.916 p = 0.068 p = 0.469 p = 0.383 3. 0.11 0.23 1.00 0.42 0.14 0.46 0.03 p = – -0.24 -0.18 -0.30 p = 0.911 p = 0.373 p = 0.178 p = 0.219 p = 0.495 p = 0.176 p = 0.162 p = 0.518 p = 0.025 (63.5 km of the river course), correlation coefficient significant for p < 0.05 is bolded 2. 0.21 0.14 1.00 0.12 0.00 0.03 0.24 0.06 p = – -0.01 -0.08 -0.17 p = 0.529 p = 0.460 p = 0.336 p = 0.772 p = 0.959 p = 0.529 p = 0.903 p = 0.506 p = 0.995 p = 0.713 1. 0.11 0.27 0.14 1.00 0.06 0.10 0.04 0.23 0.36 p = – -0.16 -0.47 -0.08 p = 0.167 p = 0.469 p = 0.416 p = 0.064 p = 0.431 p = 0.717 p = 0.749 p = 0.575 p = 0.833 p = 0.593 p = 0.050 - - + 3- 3 2 4 4 Indicator Table 2. Statistical significance of the correlation between water flow rate and quality indicators in Stobrawa River cross-section planned reservoir Table Conductivity pH Discharge PO NO DO TSS NH BOD COD Temp. NO HYDROCHEMICAL CONDITIONS FOR LOCALIZATION OF SMALL WATER RESERVOIRS... 139

PRELIMINARY ASSESSMENT OF WATER QUALITY IN KLUCZBORK RESERVOIR

Out of 11 investigated indicators of the Stobrawa River quality 9 were considered in water quality classification [40]. The analysis of the water quality showed that water temperature, dissolved oxygen, pH and conductivity did not exceed the limit values for class - + I. However, concentrations of N-NO3 , N-NH4 , BOD5, COD and total suspended solids were higher than the limit values for water quality indicators for uniform parts of surface waters in natural watercourses such as rivers, typical of class II [40]. Waters in the Stobrawa River in the cross-section of the designed Kluczbork reservoir were classified as eutrophic waters. At this point the average annual concentration -3 of nitrates exceeded the limit value (10 mg NO3·dm ) for this indicator defined in the Ordinance [41]. It was found out that the Stobrawa River waters were not sensitive to contamination with nitrogen compounds from agricultural sources as the annual average concentration of nitrates was lower than the value recommended in the Ordinance (50 mg - -3 NO3 ·dm ) [41]. From the performed analysis it can be concluded that Kluczbork reservoir will be affected by large biogenic contaminants carried by the Stobrawa River. As presented in [53] the quality of contaminated water flowing through such a small reservoir may get worse. The analyses of the Stobrawa River showed that such indicators as water temperature, dissolved oxygen and pH met the requirements for inland waters constituting natural habitat for salmon- and carp-like fishes. The most unfavorable conditions for fish are - -3 caused by: nitrites, which exceed the value of 0.01 mg NO2 ·dm for salmon-like species - -3 and 0.03 mg NO2 ·dm for carp-like species, as determined in [39], ammonium nitrogen + + -3 N-NH4 , which exceeds the value of 0.78 mg N-NH4 ·dm for salmon- and carp-like fishes, -3 -3 BOD which exceeds the value of 3 mg O2·dm for salmon-like and 6 mg O2·dm for carp-like fishes and total suspended solids exceeding the annual average value of25 mg·dm-3 defined in [40]. Taking into account BOD, suspended solids and phosphate values the quality of the Stobrawa River does not meet the requirements for bathing in inland waters, either [42]. If compared with water quality results for the Stobrawa River in the cross-section of the planned reservoir which were presented in [48], some lower concentrations of nitrates, phosphates and slightly lower nitrite values can be observed. However, values of ammonia, BOD, water temperature and electrolytic conductivity increased. Calculations were made to assess to what extent Kluczbork reservoir would be affected by eutrophication. Based on Vollenweider’s criterion [46], in Benndorf’s modifica- tion [2] and taking into account that the concentration of phosphates in the cross-section 3- -3 of the designed reservoir was 0.46 mg PO4 ·dm (Tab. 1), it was found out that the phos- -1 2 phorus load was 2.06 Mg P-PO4·a . The amount of phosphorus per 1 m of the reservoir -2 -1 was 3.7 g P-PO4·m ·a , whereas the ratio of the reservoir average depth of 2 m (assumed according to [32]) to retention time was 0.078 a-1 (calculated based on data provided in -1 [32]). Inorganic nitrogen load flowing to the reservoir is 76.3 Mg N·a . Therefore, the designed Kluczbork reservoir was classified as an polytrophic reservoir. There is no doubt that at this biogene load and the reservoir parameters the polytrophic process will occur. Similar conclusions were presented in [38]: “significant deterioration of the water quality will occur in the reservoir”. The content of dissolved oxygen in water will decrease and the increase of water temperature and pH will be observed”. 140 MIROSŁAW WIATKOWSKI

PROPOSAL FOR WATER PROTECTION OF KLUCZBORK RESERVOIR USING A PRE-DAM

Since the calculated biogene loads are too high and the reservoir will undergo eutrophication it would be advisable to increase its morphometric parameters, volume or depth. The only difficulty may be a too flat valley of the Stobrawa River at the place of the future reservoir. In this context all options for improvement of water quality of the Stobrawa River must be considered. The improvement can be achieved by reduction of point, diffuse and area pollution sources in the catchment. The main task here is rearrangement of water and wastewater management in the catchment. So far a sewerage system has been provided to villages adjacent to the future reservoir. Another option for water quality improvement is construction of a pre-dam with a macrophyte filter. There are several arguments for the construction of the pre-dam. First and foremost – low cost and short construction time. The pre-dam should be located at the inlet to the reservoir, in its backwater part. The quality of water in the reservoir should improve as all contaminants flowing with the river will accumulate in the pre-dam. According to the literature survey a properly built and used pre-dam can extend the lifetime of the reservoir and its proper operation [3, 4, 8, 49, 51]. Dimensions of the pre-dam suggested by the investor, area – ca. 2 ha and average depth – ca. 0.5 m, seem to be too low for the biogene loads flowing with the Stobrawa River [48]. Therefore, construction of a bigger pre-dam should be taken into consideration. Its dimensions should be selected very carefully so that it could function properly throughout the whole exploitation period. Based on the criteria described in [5, 7] draft working dimensions of the pre-dam were calculated. The average discharge (SQ) in the Stobrawa River is 0.446 m3·s-1 and assuming the water retention time in the pre-dam Dt = 5 days, the required volume of Kluczbork pre-dam should be: 3 Vpre-dam-5 = 86400·Dt·SQ = 0.1927 mln m (1) Assuming the retention time in the pre-dam Dt = 11 days: 3 Vpre-dam-11 = 86400·Dt·SQ = 0.4239 mln m (2) Another criterion determining the operating volume of the pre-dam refers to high flows. In order to store a 2 years’ high flow50% Q in the pre-dam (without the volume of the assumed sediments) for 12 hours, and assuming : 3 − volume of the main reservoir Vres = 1.100 mln m , 3 -1 − high flow Q50% = 5.33 m ·s [32], 3 − volume of accumulated sediments Vs = 0.01·Vres = 0.011000 mln m then the volume of the pre-dam should be: 3 Vpre-dam = Q50%·0.5·86400 + Vs = 0.230256 mln m (3) The volume of the pre-dam, calculated according to equations 1–3, should be 0.2– 0.4 mln m3. It should be stressed here that constructing a too big pre-dam is not advisable as the planned rearrangement of the water and wastewater management in the catchment will reduce the amount of contaminants flowing to the reservoir. To ensure proper control of flood waters in the pre-dam (which are usually quite contaminated) a by-pass channel should be constructed. At the above-mentioned parameters of the pre-dam a preliminary reduction of inorganic nitrogen can be determined. It depends on ratio N:P (inorganic nitrogen to phosphates) at the inflow to the pre-dam and on the average water retention time. Functional dependencies describing this process were presented by Pütz and Benndorf [35, 36]. The HYDROCHEMICAL CONDITIONS FOR LOCALIZATION OF SMALL WATER RESERVOIRS... 141 relationship between reduction of inorganic nitrogen and the average retention time (N:P) can be widely applied in determining average reductions of nitrogen for future pre-dams. Based on the data obtained from Kluczbork reservoir, the ratio between inorganic nitrogen and phosphates N:P = 25:1 and retention time t = 7.8 days (at the volume 0.3 mln m3), a significant reduction of inorganic nitrogen (by ca. 20–30%) can be expected in the pre- dam. According to the available literature, additional biological barriers and plant filters can contribute to the increased efficiency of the pre-dam. From [51] it can be concluded that in water flowing through the pre-dam that consists of a sedimentation tank and a plant filter, nitrate values decreased by 66.5% and phosphates by 52.8%. Similar results were presented in [8, 12, 13]. Authors of [43], however, found out that a pond located on a watercourse decreased concentrations and loads of phosphorus in the flowing water.

CONCLUSIONS

Hydrochemical conditions occurring in the cross-section of the designed Kluczbork reservoir are unfavorable for it. From the point of view of eutrophication process water of the Stobrawa River flowing to the reservoir shows high content of biogenes: nitrates – - -3 3- -3 13.95 mg NO3 ·dm , phosphates – 0.56 mg PO4 ·dm . Among the investigated indicators the concentrations of nitrate nitrogen, ammonium nitrogen, BOD5, COD and suspension exceeded the limit values defined for water quality indicators for uniform parts of surface waters in natural watercourses, typical of class II. A negative impact on the life of salmon- and carp-like fishes is exerted by nitrites, ammonia, BOD5 and total suspended solids. The water quality of the Stobrawa River does not meet the criteria established for bathing due to the content of BOD5, TSS and phosphates. In order to avoid eutrophication it is necessary to reduce the content of biogenes in the water flowing to the reservoir. One of the basic solutions is rearrangement of water and wastewater management systems in the reservoir catchment, which must be com- pleted before the construction of the reservoir. Another solution is construction of the pre-dam with a macrophyte filter, which will facilitate the improvement of water quality in the reservoir and extend its lifetime. These solutions should be considered both while designing new reservoirs and in the existing ones (if location permits). Due to great importance of small water reservoirs in regional water management monitoring of water purity in the river feeding the reservoir, both at the stage of planning, construction and operation, seems to be essential. More regular research, extended by analyses of other water quality indicators, should be continued in the catchment of the designed Kluczbork reservoir so that it could contribute to a more detailed water quality assessment.

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Received: March 25, 2009; accepted: September 22, 2009.

UWARUNKOWANIA HYDROCHEMICZNE LOKALIZACJI MAŁYCH ZBIORNIKÓW WODNYCH NA PRZYKŁADZIE ZBIORNIKA KLUCZBORK

W pracy przedstawiono analizę warunków hydrochemicznych wody rzeki Stobrawy (prawostronny dopływ Odry) dla określenia możliwości jej retencjonowania w planowanym zbiorniku retencyjnym Kluczbork. Przed- stawiono wstępną ocenę jakości wody zbiornika i oceniono jej walory użytkowe. Podstawowe funkcje zbiornika to ochrona przed powodzią, nawodnienia rolnicze i rekreacja, dlatego ważnym zagadnieniem jest jakość wody zbiornika. Scharakteryzowano jakość wody rzeki Stobrawy pod względem wskaźników fizyko-chemicznych: - - + 3- NO3 , NO2 , NH4 , PO4 , BZT5, ChZTCr, tlenu rozpuszczonego, temperatury wody, pH, przewodności elektroli- tycznej i zawiesiny ogólnej. Obliczono podstawowe statystyki opisowe dla badanych wskaźników jakości wody 144 MIROSŁAW WIATKOWSKI i ładunków. Analizie statystycznej poddano związki korelacyjne pomiędzy wszystkimi badanymi wskaźnikami jakości wody i przepływem wody. Analiza ta wykazała, że niektóre wskaźniki są ze sobą wzajemnie i z przepływem skorelowane na poziomie istotności p < 0,05. Przeprowadzone badania wykazały, że zanieczyszczenie wody rzeki Stobrawy w przekroju planowanego zbiornika jest znaczne, w związku z czym woda ta może pogorszyć jakość wody zbiornika. W pracy przedstawiono propozycje zabiegów, które mogą się przyczynić do poprawy jakości wody w zbiorniku. Jednym z podstawowych rozwiązań jest uporządkowanie gospodarki wodno-ściekowej w zlewni zbiornika. Musi ono poprzedzać budowę zbiornika. Drugim rozwiązaniem jest budowa zbiornika wstępnego, który będzie wpływał na poprawę jakości wody w zbiorniku i wydłuży czas jego istnienia. CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN ... 145

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 145 - 158 2009 PL ISSN 0324-8461

CHANGES IN WATER QUALITY OF ZAGREB WATER-PUMPING SITES

MLADEN ZELENIKA1, BOŽO SOLDO2, BOJAN ĐURIN2

1 University of Mostar, Faculty of Civil Engineering Kralja Zvonimira 14, 88000 Mostar, Bosnia & Herzegovina e-mail: [email protected] 2 University of Zagreb, Geotechnical Faculty Hallerova aleja 7, 42000 Varaždin, Croatia e-mail: [email protected]; [email protected]

Keywords: Aquifer, underground water, piezometer, water-pumping site, quality, wells, incrustation, corrosion.

Abstract: The paper deals with changes of water quality of the aquifer in the valley of the Sava River at Za- greb, capital of Croatia, with respect to the depth of aquifer, laterally and temporally, during several years. The impact of water quality on the appearance of incrustation and corrosion in wells has also been analyzed. There are also presented procedures for preventing incrustation and corrosion. The basis for this paper are the results of analyses of the water samples taken from different wells, new piezometers and those previously carried out at water-pumping sites of different embedding depths.

INTRODUCTION

During the 125-year long tradition of the Zagreb water supply system, the underground water has been examined at numerous sites in the valley of the Sava River, from Bregana to Črnkovec, and also on the slopes of Medvednica and Samobor hills. Extensive and very complex research was conducted, the results of which have enabled the increase of retention and consumption of water from the initial small amounts (in 1878) to the current 150 mln m3 of drinking water per year. A large number of exploration and observation boreholes and production wells have been done, and water-pumping sites with its safety zones arranged (Fig. 1). The goal of the water supply system is the safe supply of drinking water for about 850 000 citizens in the area of about 800 km2. Through complex and long lasting research, favorable natural hydro-geological features of the aquifer in the valley of the Sava for the Zagreb water supply have been determined. Because of the voluminous aquifer with the water quality that meets the criteria for potable water, the location of Zagreb is considerably more favorable than that of the majority of other cities in the world. Great financial means have been spent on research- ing the aquifer, building and equipping water-pumping sites and the aggregative water supply system, and it needs to be preserved, protected and conserved for permanent use. The consumption of water in Zagreb is increasing. Therefore, immaculate conservation of wells and control and protection of the quality of intake water is necessary in order to 146 MLADEN ZELENIKA, BOŽO SOLDO, BOJAN ĐURIN

Fig. 1. Water-pumping sites location map [6] ensure increased amount of water for the sake of appeasing growing needs for drinking water. Methodical measurements of underground water level (UWL) and analysis of water samples quality are conducted for all water-pumping sites. The data are recorded, analyzed, commented on and presented to the authorized institutions and governmental departments in Zagreb. Thus determined were considerable reduction of UWL and changes of water quality in certain wells and observation water-pumping sites (piezometers).

RESEARCH AND FEATURES OF WATER-PUMPING SITES

The water supply system in Zagreb nowadays uses mainly the four dominant sites (systems) in the Sava valley, as shown in Figure 1. These are: − Mala Mlaka water-pumping site, with a pre-pump water station of the Velika Gorica system (38%); − Petruševec water-pumping site (21%); − Sašnak water-pumping site (20%); − Strmec water-pumping site (13%). The other well systems provide the remaining 8%: Zapruđe with 280 dm3/s, Slapnica 80 dm3/s, Žitnjak 80 dm3/s, and Bregana 30 dm3/s. Mala Mlaka has 18 wells, Petruševec 5, Sašnak 6, Zapruđe 3, Strmec 6, and 1 well is at the Žitnjak water-pumping site. The specialized departments in charge (Vodoopskrba i odvodnja d.o.o. Zagreb (ViO), Meteorological and Hydrological Service, Hrvatske vode, and their engaged services in Zagreb), regularly monitor the change of quality and quantity of water consumed by the city on daily, monthly and yearly basis. Water levels and outflows of surface waters are systematically monitored, as well as the running of active wells, water quality and CHANGES IN WATER QUALITY OF ZAGREB WATER-PUMPING SITES 147 changes of UWL at all active water-pumping sites, those previously used and water- pumping sites that are just being examined for future use (Kosnica) [2]. The quaternary aquifer in the valley of Sava has been interdisciplinary and it was thoroughly examined under many research programs financed by state and city institutions [7, 9]. In particular, a large number of structural piezometer boreholes were done for the purpose of determining the features of aquifers on various depths of quaternary sediments, and the change of UWL and water quality at particular locations has been monitored. The results of monitoring the changes of water quality and UWL in previously carried out piezometer boreholes and wells provide the basis for assessment of features of quaternary aquifer in the valley of the Sava River. In order to note thoroughly the possible changes of UWL, lithological structure, water conductivity features of aquifer and water quality (in depth and lateral), two more structural piezometer boreholes were drilled at the Mala Mlaka water-pumping site (PB-24 and PB-29). Those two piezometers helped choose the location for two other wells. Drilling samples provided through core drilling during the drilling of the two structural piezometer boreholes were interpreted, and 14 + 15 = 29 samples of the water-carrying sediments were taken into laboratory for granulometric analysis. By comparing sizes of grains in different samples from different locations and depths of sampling, changes of water conductivity features of sediments, laterally and vertically, were provided. A final plot of construction of piezometers and wells was made, and the fill-up intended for the stabilization of annular space [14] was defined. A great diversity of thickness of sediment grains was ascertained; from clay particles 0.0002 mm in size to pebbles of 56 mm in diameter, collected during drilling. Filtration characteristics of samples taken from shallower layers (up to 15 m of depth) are better than the ones from deeper intervals of sediments. The grain uniformity coefficient (d60/d10) is diverse and ranges between 32 and 457. The structural piezometer boreholes are lined with polyethylene (HDPE) tubes of 110/100 mm in diameter. The wells are equipped with stainless steel water-permeable filters and massive tubes in dry and water-non-permeable sediments. The annular space of structural piezometer boreholes, as well as that of wells, is filled up with gravel of adequate sizes of grains, for stabilizing the surrounding sediments and other important functions. Installed in this way, the piezometers and wells are treated with prescribed procedures and used for trial pumping of the newly made wells. No stratigraphic and geophysical research data on previous boreholes performed at Mala Mlaka water-pumping site have been found. Figure 2 shows the profile across four boreholes in the area around Prečko water-pumping site. In those drills, logging measurements of gamma, gamma-gamma and neutron values by depth were conducted, as well as stratigraphic interpretation of sediments [8]. Figure 2 shows the three erosion discordances which separate sediment groups I, II, III, and IV. The two deeper and a part of the third group of sediments belong to Pleistocene, while the upper part of the third and the fourth group of sediments are interpreted as Holocene sediments. On the basis of the comparison of the features of lithological profiles of structural piezometer boreholes and wells at particular water-pumping sites with profiles and marked routes of erosion discordances in Figure 2, one can estimate the depth of Holocene at water-pumping sites as follows: 148 MLADEN ZELENIKA, BOŽO SOLDO, BOJAN ĐURIN

Fig. 2. Schematic correlative profiles across BP-5, BP-2, BP-3 and PP-1 boreholes conducted in the area around Prečko [3]

− Strmec 8–13 m, − Ježdovac 9.4–10.5 m, − Mala Mlaka 12.5–18 m, − Zapruđe 11.7–12.7 m, − Petruševec 20.5–30.4 m. The depths of Holocene estimated in this way should be explored during possible future exploration work. Concerning better filtration features of Holocene sediments, it is valuable to emphasize the impact of the change of the static level of underground water (SLUW), in particular wells, on the value of their specific abundance [dm3/(s·m)]. Changes of UWL and the amount of pumping output in wells BZ-3 and BZ-4 at Zapruđe water-pumping site in February and March 2004 were measured at the exact point of the increase of water level of the Sava River and the increase of UWL in the aquifer and the above mentioned wells. The Zapruđe water-pumping site is near the Sava valley; therefore, the increase of the water level of the Sava resulted in the increase of UWL in the aquifer in a short while. Thus, the interval of the aquifer with the best water conductivity and retention features (Holocene) was suddenly filled with water, which caused multiple increases of specific abundance in the observed wells [dm3/(s·m)]. The structural piezometrical boreholes are equipped (HDPE) with polyethylene tubes 110/100 mm in diameter and filled up in annular space with gravel of adequate features. Striped filters with 3.0 x 50.0 mm cuts and nets of 2 x 2 mm openings are built into intervals of 11.50–27.50 m in the PB-24 borehole, and intervals of 11.00–13.00 and 15.00–28.50 m in the PB-29 borehole. The bottom of the sediment tube lies at the depth of 29.5 m in PB-24 and 30.5 m in PB-29 (Figs 3 and 4). The piezometers were treated suc- CHANGES IN WATER QUALITY OF ZAGREB WATER-PUMPING SITES 149 cessfully, followed by taking samples of water from different depths. The results received by conducting structural piezometrical boreholes comprise the main basis for choosing the construction of exploitation wells. The choice of the filters and protection tubes is based on the three most important factors: − required mechanical resistance of filters and tubes in given circumstances of installation and using of wells; − features of aquifer and quality of underground water concerning corrosion and incrustation; − potential possibility of appearance of ferruginous bacteria.

Fig. 3. Geotechnical cross-section of research-piezometer borehole PB-24/1 [12] 150 MLADEN ZELENIKA, BOŽO SOLDO, BOJAN ĐURIN

Fig. 4. Geotechnical cross-section of research-piezometer borehole PB-29/1 [12]

CHANGES IN WATER QUALITY BY DEPTH

The samples of underground water, i.e. groundwater at Mala Mlaka were taken several times by pumping with Grundfos pump at three levels (Tab. 1). On May 19, 2004 sampling was conducted by taking samples from greater to lesser depths, while on July 29, 2004 sampling was conducted by taking samples from lesser to greater depths, immediately after dipping the tube (acceptable treating of piezometer and clear flow of underground water through the piezometer filters was presupposed) [2]. CHANGES IN WATER QUALITY OF ZAGREB WATER-PUMPING SITES 151

Table 1. Sampling depths and pumping times Pumping Pumping Location Sampling date Pumping depth time power

PB-24/1, PB-24/2, PB- 19.05.2004 14 m, 18 m, 22 m 5 min 350 Hz 24/3 29.07.2004 14 m, 18 m, 22 m immediately 250 Hz

PB-29/1, PB-29/2, PB- 19.05.2004 14 m, 20 m, 24 m 5 min 350 Hz 29/3 29.07.2004 14 m, 20 m, 24 m immediately 250 Hz

The water samples were analyzed using standard methods and techniques prescribed for analysis of drinking water. The results are shown in Tables 2 and 3.

Table 2. Results of PB-24 borehole analysis

PB-24 PB-24 PB-24 Location 14 m 18 m 22 m Date 19.05.2004 29.07.2004 19.50.2004 29.07.2004 19.05.2004 29.07.2004 Indicator Water level [cm] 1125 1176 1125 1176 1125 1176 Temperature [°C] 13.2 12.9 13.0 12.9 13.5 12.9 pH-value 7.15 7.01 7.16 7.01 7.16 7.03 Electrical implementation 895 885 895 900 895 900 [mS/cm] Fluorides [mg/dm3] 0.04 0.04 0.04 0.04 0.04 0.04 Chlorides [mg/dm3] 27.1 29.5 27.0 27.2 26.9 27.5 Nitrates [mg/dm3] 7.3 7.6 7.1 7.1 7.1 7.2 Sulphates [mg/dm3] 2.9 34.2 42.9 41.4 42.8 41.4 Na [mg/dm3] 13.1 17.0 13.1 12.5 13.1 12.4 K [mg/dm3] 1.3 2.9 1.3 1.3 1.3 1.2 Ca [mg/dm3] 142.4 140.8 142.4 140.8 142.4 140.8 Mg [mg/dm3] 34.0 34.0 34.0 34.0 34.0 34.0 Fe [μg/dm3] 4.5 24.0 0.0 0.6 6.7 0.0 Mn [μg/dm3] 0.4 0.4 0.7 0.2 0.5 0.4 Pb [μg/dm3] 7.0 14.0 1.0 1.0 4.0 12.0 Total org. C 0.44 0.46 0.38 0.39 0.44 0.43 [mg/dm3] Evaporated residue 600 630 560 620 570 640 105°C [mg/dm3] Annealing residue 400 360 400 370 370 360 [mg/dm3] Dissolved CO 2 49.3 66.0 49.3 66.0 49.3 66.0 [mg/dm3] 152 MLADEN ZELENIKA, BOŽO SOLDO, BOJAN ĐURIN

Table 3. Results of PB-29 borehole analysis PB-29 PB-29 PB-29 Location 14 m 20 m 24 m Date 19.05.2004. 29.07.2004. 19.05.2004. 29.07.2004. 19.05.2004. 29.07.2004. Indicator Water level [cm] 928 1045 928 1043 928 1043 Temperature [°C] 12.7 12.4 12.7 12.3 12.8 12.3 pH-value 7.28 7.14 7.25 7.15 7.28 7.14 Electrical implementation 735 755 735 755 735 755 [mS/cm] Fluorides [mg/dm3] 0.06 0.06 0.06 0.06 0.06 0.05 Chlorides [mg/dm3] 20.2 22.9 20.2 22.9 20.3 22.9 Nitrates [mg/dm3] 9.4 8.1 9.4 8.1 9.4 8.1 Sulphates [mg/dm3] 20.8 21.6 20.9 21.8 21.2 21.8 Na [mg/dm3] 8.9 10.0 8.9 12.1 8.9 10.1 K [mg/dm3] 1.4 1.4 1.4 1.4 1.4 1.4 Ca [mg/dm3] 108 108 108 108 108 108 Mg [mg/dm3] 31.1 31.1 31.1 31.1 31.1 31.1 Fe [mg/dm3] 5.1 7.7 12.9 33.6 22.5 90.1 Mn [mg/dm3] 0.5 0.3 0.4 0.5 1.1 1.7 Pb [mg/dm3] 2.0 2.0 5.0 8.0 5.0 0 Total org. C 0.37 0.98 0.38 0.55 0.38 0.83 [mg/dm3] Evaporated residue 450 480 460 490 460 530 105°C [mg/dm3] Annealing residue 330 280 320 300 310 330 [mg/dm3] Dissolved CO 2 32.6 45.8 33.4 45.8 32.6 45.8 [mg/dm3]

The water samples were taken from PB-24 and PB-29 piezometers twice (in May and July 2004), at three different depths. During the May sampling, a five minute pumping session was conducted, and the results of analysis clearly showed that the figures of the examined indicators are of equal values, i.e., that there is practically no difference in the quality of water depending on the level of pumping; this was true for both locations. The second sampling was organized in July 2004, but this time attention was placed on immediate sampling from every particular level, and the results clearly showed that the figures for most examined indicators significantly differ depending on the sampling depth. At PB-24 piezometer site there are noticeable differences in concentration depending on the sampling depth for most indicators, although the differences point to the conclusion that the water is of the same quality throughout the entire layer. At the location of PB-29 piezometer there are also noticeable differences in concentration depending on the sampling depth, but for iron and manganese indicators the difference becomes considerable with depth: in the 14 m layer, the concentration of iron was 7.7 mg/dm3, while at the depth of 24 m, the concentration was 90.1 mg/dm3. A similar CHANGES IN WATER QUALITY OF ZAGREB WATER-PUMPING SITES 153 ratio was ascertained for the concentration of manganese: at the depth of 14 m, the concentration was 0.3 mg/dm3, while at the depth of 24 m, the concentration was 1.7 mg/dm3. The increased amounts of manganese and iron are evident in the water sample taken from the deepest interval (24 m), in PB-29 piezometer. This is similar at the Petruševec water-pumping site, which was examined and analyzed by the scientific team at the Fac- ulty of Mining and Geology [3]. Because of the appearance of manganese in water in certain wells at the Petruševec water-pumping site larger than MDK, five samples of sediment received from different depths of the borehole were analyzed. The samples were marked with numbers and the intervals of the borehole from which they were taken: 2 (5–6 m), 4 (15–16 m), 5 (19–20 m), 6 (23–24 m) and 8 (34–35 m). In Sample 6 taken from the 23–24 m depth interval of the borehole, the largest content of reductive fraction related to the manganese oxides was determined, containing concentration of Mn(MN) = 787.89 ppm. The sample contains the largest reductive fraction related to the amorphous iron oxides Mn(AF) = 181.5 ppm and carbonate fraction Mn(CC) = 115.42 ppm. The sample has also indicated the highest contents of Fe, Zn, Co, Cu, Cr, Ba, Ni, V, Al, Ti and Pb, as well as the highest content of quartz and the lowest content of calcite in relation to other samples [3].

CHANGES IN GROUNDWATER QUALITY, LATERALLY AND TEMPORALLY

The quality of surface and underground waters depends on several different factors, such as the intensity and quality of precipitation, the intensity of evaporation, the soil and rocks the water flows through, the supplements to the soil for the purpose of fertilization and protection from weeds, substances contained in waste water from industrial drives and other various activities, and from the settlements [5]. Table 4 contains the mean values of several component contents in water samples taken in the period between 1998 and 2002 at the water-pumping sites Petruševec, Sašnak, Mala Mlaka, Strmec and Zapruđe. The average contents of individual components in water vary from site to site. Distances between them, as well as their distance from the Sava water-pumping site, are illustrated in Figure 1. Table 4 shows significant differences in the content of individual components in the water in piezometers, measured at approximate distances of 2 km at the same water-pumping site, at approximately the same depths of water sampling. Table 4 shows the largest content of manganese at water-pumping sites Petruševec and Strmec. Therefore, a drive for demanganising water from the wells B-4 and B-5a was built in the year 2002 on the water-pumping site Strmec. Water from the well B-5 had the largest content of manganese, which placed the well out of use. The largest content of dis- solutions was found in the water at the Sašnak water-pumping site prompting in 1987 the first, and in 1993 the second phase of installing equipment for removing trichlorethane and tetrachlorethane compounds from the water by absorption with active coal. Figure 5 shows diagram values of changes of the concentration of nitrates found in the groundwater samples from four observation wells on the Mala Mlaka water-pumping site during the 10-year period of observation, from 1991 to 2000. Two trends are obvious: the trend of increased concentration of nitrates, from 7 mg N/dm3 in September 1991 to 15 mg N/dm3 in March 1994, and the trend of decreased content of nitrates, from higher values in March 1994 to 6–7 mg N/dm3 in December 2000. 154 MLADEN ZELENIKA, BOŽO SOLDO, BOJAN ĐURIN

Table 4. Results of analysis of water samples from specific wells at five water-pumping sites Petruševec Sašnak-teglica Mala Mlaka Strmec Zapruđe Water-pumping site B5a B1 B29 B6 B1 Temperature [°C] 13.7 13.9 12.6 12.4 13.3 UBB37 in 1 cm3 0 1 0 0 0 NBK in 100 cm3 0 < 1 < 1 < 1 < 1 Nitrates [mg N/dm3] 1.12 3.55 5.50 2.15 0.91 pH value 7.48 7.18 7.21 7.19 7.45 El. implementation 468 773 742 709 453 [mS/cm] Cl [mg/dm3] 9.4 25.0 19.1 9.7 7.6 3 Dissolved O2 [mg/dm ] 2.0 6.4 7.6 4.2 2.8 Sulphates [mg/dm3] 20.2 48.8 30.9 39.6 19.1 Na [mg/dm3] 6.67 16.84 10.66 8.01 6.51 K [mg/dm3] 2.01 3.25 2.57 3.47 2.17 Ca [mg/dm3] 72.19 113.96 112.43 110.08 71.12 Mg [mg/dm3] 18.94 29.47 30.71 33.03 17.43 Fe [μg/dm3] 1.90 2.68 1.99 3.36 1.19 Mn [μg/dm3] 1.5 0.66 0.51 1.06 0.77 Pb [μg/dm3] 2.31 3.20 3.53 3.23 2.30 Spent Salt brine p 0.34 1.01 0.91 0.97 0.36 [Mmol/dm3] Carbonate hardness 218.5 330.8 332.70 345.3 212.7 [mg/dm3] 3 CO2 [mg/dm ] 15.02 44.34 40.54 42.59 15.79 Annealing residue 279.38 473.33 459.33 444.67 264.67 Redox pot. [mV] 172.1 305.5 395.6 459.4 194.8

Fig. 5. Changes of concentration of nitrates in groundwater samples at Mala Mlaka during 10-year observations [11] CHANGES IN WATER QUALITY OF ZAGREB WATER-PUMPING SITES 155

INCRUSTATION AND CORROSION IN WELLS

As the grain size distribution in samples of aquifer has crucial importance in choosing the openings of filters and granulometric content of stabilizer of sediments, so the quality of underground water is of crucial importance for choosing the materials for the construction of wells, and especially for the types of filters and pumps. To avoid harmful corrosive and incrustation effects, selection of both size and adequate type of the filter, as well as regular control and well maintenance, are of great importance. The best known authors of literature specialized in technology of construction and servicing of wells conducted in alluvial sediments consider incrustation and corrosion the most harmful manifestations which jeopardize the lasting efficiency of retaining underground water through wells. Based on the results of analyses shown in Table 1, filters, protective tubes and centralizers made of stainless steel SS-304L 800/8 mm were the ones chosen. Filter openings are 2 and 4 mm, and the stabilizers of sediments are of grain sizes 1–3.15 mm and 3.15–8 mm respectively, in terms of the known principles [13]. Incrustation is the appearance of accumulations of silt, clay, biomass, carbonate, iron, manganese and other substances non-dissolvable in water. Accumulations of the above mentioned substances (incrustation) lead to plugging of the entrance part of the well that consists of a filter, a built-in gravel cover, and sediments (aquifer) near to the filter. The appearance of a more intense incrustation increases resistance of the water entering the well, thus reducing the specific abundance to a half of the initial abundance within 2–5 years [4]. Reducing specific abundances of wells can cause corrosion of wells and filters. Cor- rosion of particular metal parts or of the whole construction of wells is expected and actu- alized during the capitation of the corrosive underground water. Because of the corrosion of filters and/or protective columns, increased openings appear in wells through which particles of aquifer sediments (sand) can intrude. Intrusions of sand can cause very harmful abrasion of parts of pumps and other equipment in the water supply system. Intrusion of sand can fill in the filters and a large part of the well, thereby bringing into question the abundance and stability of the well. Clarke and Barnes researched the appearance of corrosion and incrustation in the wells in the valley of the river Ind in Pakistan during the 1960s and published their es- timations, which proved to be accurate [1]. The basic indicators of incrustation are the following features of water: − pH value > 7.5; − carbonate hardness > 300 mg/dm3; − iron content in water Fe > 0.5 mg/dm3; − manganese content Mn > 0.2 mg/dm3. Basic indicators of water corrosion are: − pH value < 7.0; − content of total dissolved substances TDS > 1000 mg/dm3; − appearance of dissolved oxygen in water > 2 mg/dm3; 3 − appearance of H2S even lower than 1 mg/dm ; 3 − CO2 content > 50 mg/dm ; − chloride content > 500 mg/dm3. [4] Corrosiveness of water is stronger when two or more of the above mentioned conditions are met. Higher values of pH and the presence of oxygen in water hasten the incrus- 156 MLADEN ZELENIKA, BOŽO SOLDO, BOJAN ĐURIN tation in the case of a significant presence of iron and manganese. Table 5 shows values of electric implementation in units mS/cm – approximately 35% smaller than the value of the total TDS (Total Dissolved Solids, i.e. total mineralization of water, measured in mg/dm3) mineralization. The requested and received data on the quality of the water in wells can be provided by supervising service. The results of physical and chemical analyses of water distributed in the water supply system are shown in Table 5. The table shows only the main features that characterize the water concerning the prediction of appearance of incrustation at the portion of the well through which groundwater enters it at the increased speed of flow, and corrosion of the metal parts of the construction of the well.

Table 5. Laboratory results of analysis of the content of components which are indicators of incrustation and corrosion of water in wells at several water-pumping sites

Carbonate Electric pH Fe Mn O CO Chlorides Well hardness 2 implementation 2 value [mg/dm3] [mg/dm3] [mg/dm3] [mg/dm3] [mg/dm3] [mg/dm3] [mS/cm] SB-5 7.08 385 0.0 0.2 5.4 800 57.2 10.8 SB-7 7.08 380 0.0 0.3 4.7 795 52.8 11.8 SB-8 7.17 365 0.0 0.8 4.7 760 44.0 10.5

Strmec SB-9 7.21 315 0.0 0.8 2.5 660 35.2 10.5 SB-4 7.08 390 0.0 0.2 3.5 810 52.8 15.4 BZ-3 7.47 215 0.9 0.0 2.9 445 17.6 9.1 BZ-4 7.45 220 5.3 0.3 2.1 445 18.5 8.8

Zapruđe BZ-1 7.47 176 3.9 0.2 2.5 445 17.6 8.8 MB-1 7.10 315 0.9 0.6 7.1 710 41.4 19.9 MB-2 7.12 330 0.7 0.5 8.2 735 44.0 22.1 MB-3 7.03 365 0.0 0.8 8.9 825 53.7 23.5 MB-4 7.13 385 0.8 0.2 6.5 870 49.3 28.7 MB-5 7.3 360 3.3 0.6 9.3 840 44.0 31.1 MB-6 7.17 385 0.0 0.3 7.5 785 39.6 23.1 MB-7 7.24 335 0.0 0.2 8.2 730 32.6 17.8 MB-8 7.19 350 0.0 0.4 7.7 770 37.0 19.2 MB-9 7.30 305 0.0 0.3 9.0 675 26.4 14.7 Mala Mlaka MB- 7.34 290 0.8 0.7 8.7 640 22.9 11.2 10 PB- 7.15 4.5 0.5 4.7 895 49.3 27.1 24 PB- 7.28 5.1 0.5 6.5 735 32.6 20.2 29 BP-5 7.46 222.50 1.75 28.08 1.50 471.59 16.25 8.17

BP-5a 7.46 230.00 0.45 41.07 2.10 475.00 28.20 6.68 Petruševec

The above mentioned factors and the data in Table 5 are used for estimating the potential for corrosion and/or incrustation of groundwater at water-pumping sites. Ta- ble 5 shows the pH values of groundwater samples larger than 7; therefore, incrustation does not favor these pH values. The pH values of water in the wells at water-pumping CHANGES IN WATER QUALITY OF ZAGREB WATER-PUMPING SITES 157 sites Mala Mlaka, Zapruđe and Petruševec are near 7.5, thus indicating the possibility of incrustation. The carbonate hardness of water is over 300 mg/dm3 in almost all wells at water-pumping sites Strmec and Mala Mlaka, which also favors the appearance of incrustation. The content of iron and manganese in the water is lower than 0.5 and 0.2 mg/dm3 respectively, and the content of dissolved oxygen in the water is high, which may favor the appearance of incrustation, as well as corrosion [4].

H2S has not been found in any of the analyzed water samples. All water samples have a confirmed lower content of chlorides and values of dissolved substances (TDS) than that indicating corrosiveness of water. The content of dissolved oxygen (O) is larger 3 than 2 mg/dm in most of the wells, and the content of dissolved CO2 is larger than 50 mg/dm3, but only in the water samples from the wells MB-3, SB-4, SB-5, and SB-7.

A larger content of dissolved oxygen and CO2 causes corrosion of the wells’ metal construction. Since the filters, i.e. the wire winds are the most exposed to the impact of corrosion, most wells contain wires made from stainless steel. Most wells have installed in them a cathode protection of the metal parts from corrosion, which can cause increased incrustation in the wells; thus, this area needs to be studied with special care. Moreover, wells need to be protected from incrustation using various prevention measures. Table 5 shows a data comparison characteristic of incrustation and corrosion features of water in the old wells and the two new piezometers. One can notice the increased carbonate hardness, content of iron, and the decreased content of dissolved oxygen, as well as the increased electric implementation of the water samples in the new piezometers in relation to the water in the old wells at the Mala Mlaka water-pumping site.

CONCLUSION

Two structural piezometer boreholes and two pumping wells at the Mala Mlaka water- pumping site were done in 2004, at the locations near old wells of lesser water quantities. After treating the new PB-24 and PB-29 piezometers, samples of water from different depths were taken and analyzed in May 2004. The samples were extracted after inten- sive pumping of water at every interval; therefore, the results of sample analyses did not differ in samples from different depths. For this reason, it was decided in August to collect the samples once again, from depths of 14 to 28 m, but without mixing the water in piezometers through pumping, because the piezometers were treated long enough, and clear water was received. Increased manganese content in the water samples taken from the deepest intervals of piezometer PB-29 is similar to the one at the Petruševec water- pumping site, which was investigated and analyzed by the scientific team at the Faculty of Mining and Geology [3]. Although the fear from incrustation in wells is larger than that from corrosion, the right decisions concerning the preventive protection of future wells from incrustation and the impact of corrosion on the filters, pumps, wires, etc. will be reached on time. In addition to the cathode (anticorrosion) protection of metal components in wells, ViO is taking significant preventive measures against the impact of incrustation on filters [4], these being: − reducing incoming speed of groundwater into the well; − well treated wells; − reducing the amount of pumping [m3/h] and increasing hours per day; 158 MLADEN ZELENIKA, BOŽO SOLDO, BOJAN ĐURIN

− carrying out more wells smaller in diameter and capacity; − more frequent actions of methodical control and cleaning of wells. Also recommended is isolation of the intervals with increased presence of iron, manganese and other possibly harmful components in groundwater in cases when they are ascertained beyond doubt by structural borehole(s). This way the quality of water in the well/water-pumping site can be efficiently protected. Keeping in mind the locations of the abandoned water-pumping sites in relation to the known polluters in their inflow area in the valley of the Sava, an adequate approach to the programming and realization of the research of the relevant parts of alluvial aquifer is recommended for the purpose of a more accurate determination of the cause of groundwater pollution, as well as profitable procedures for enhancement of the water quality. Also explored should be the possibilities of profitable use of water from certain abandoned water-pumping sites for various technical purposes which do not demand the standard of quality that drinking water does.

REFERENCES

[1] Clarke F.E., I. Barnes: Evaluation and control of corrosion and incrustation in tube wells of the Indus Plains, West Pakistan, U.S. Geol. Survey Openfile, Report 69-P, 1969. [2] DHMZ – Državni hidrometerološki zavod Republike Hrvatske – Služba za hidrologiju: Sliv Save – Izvještaj o mjerenju i obradi podataka razine podzemne vode u 2002. godini, Zagreb 2003. [3] Durn G., S. Miko, D. Slovenec, D. Aljinović: Vodocrpilište Petruševec: Ispitivanje sedimenata iz istražne bušotine na lokaciji piezometra PB-5/3, ViO d.d., Zagreb 1997. [4] Fletcher G.D.: Groundwater and Wells, 2nd edition, St. Paul, Minnesota 1995. [5] Hall R.L., S.J. Allen, P.T.W. Risier, et al.: Hydrogeological effects of short rotation energy coppice, ETSU B/W5/00275/Rep.:204, 1996. [6] http://maps.google.com/maps?f=q&hl=hr&geocode=&q=zagreb&ie=UTF8, 2009. [7] Miletić P., D. Perković: EGPV prilog, Hrvatska vodoprivreda br.114, Zagreb 2002. [8] Velić J., G. Durn: Alternating Lacustrine-Marsh Sedimentation and Subaerial Exposure Phases During Quaternary: Prečko, Zagreb, Croatia, Geol. Croat., 46/1, 71–90, Zagreb 1993. [9] Velić J., B. Saftić: Dubinskogeološki odnosi područja smetlišta “Jakuševec” – čimbenik sanacije, Gospo- darenje otpadom, 197–205, Zagreb 1996. [10] Vodoopskrba i odvodnja (ViO): Rezultati fizikalno kemijskih analiza vode vodoopskrbnog sustava Za- greb, Zagreb 2004. [11] Vodoopskrba i odvodnja (ViO): Promjene koncentracije nitrata u podzemnoj vodi u Maloj Mlaci, Godišnja izvješća, 1991–2000, Zagreb 2001. [12] Zelenika M., B. Grđan, B. Soldo: Well design for the Petruševec well system, 54(1), 31–42, Nafta, Zagreb 2003. [13] Zelenika M.: Tehnologija izrade bušotina, Textbook, Geotehnički fakultet Sveučilišta u Zagrebu, Varaždin 1995. [14] Zelenika M.: Izvješće o projektantskom nadzoru izvedbe novih pijezometara i zdenaca na crpilištu Mala Mlaka, Arhiv ViO d.d., Zagreb 2005.

Received: November 21, 2008; accepted: September 28, 2009. CHANGES OF PHYSICOCHEMICAL PARAMETERS AND PHYTOPLANKTON IN ... 159

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 no. 4 pp. 159 - 164 2009 PL ISSN 0324-8461

PROFILE DIFFERENCES OF ZINC, COPPER, AND NICKEL CONTENTS IN FOREST SOILS ON SOUTH-PODLASIE LOWLAND

DOROTA KALEMBASA*, MARCIN BECHER, KRZYSZTOF PAKUŁA

University of Podlasie, Department of Soil Science and Plant Nutrition ul. Prusa 14, 08-110 Siedlce, Poland * Corresponding author e-mail: [email protected]

Keywords: Zinc, copper, nickel, forest soils, South-Podlasie Lowland.

Abstract: The profile differences of zinc, copper, and nickel contents in forest podzolic soils on South-Podlasie Lowland were studied. Their considerable differentiation was found. Contents and differentiation of analyzed heavy metals in studied soil horizons were determined by: parents rock and soil-forming processes (mainly podzolization) characteristic for those soils.

INTRODUCTION

Among all environmental elements, the soil is commonly considered as the most important medium for accumulating the heavy metals originating from natural (parents rocks) and anthropogenic sources (industry, energy production, transport, plant pesticides, fertilizers, municipal wastes) [3, 6, 8, 11]. Forest soils (namely those with low level of an- thropopression) may be a reference (standard) for comparison in ecological, soil science, and screening studies upon the environment. Determination of zones (genetic horizons), where heavy metals are deposited, as well as conditions and opportunities of their transfer within soil profile, are very important question in an aspect of their bio-geochemistry and potential threats for natural environment. The aim of present study was to determine zinc, copper, and nickel contents in forest podzolic soils on South-Podlasie Lowland as well as to evaluate the influence of lithogenic, pedogenic, and anthropogenic factors on the amount and distribution of these heavy metals within soil profiles.

MATERIAL AND METHODS

The soil study was carried out within three regions (Siedlce Upland, Łuków Plain, Pod- lasie Bug River Gorge) of South-Podlasie Lowland. Twelve soil outcrops were made in forests of Siedlce, Łuków, and Sarnaki Forest Inspectorates, within habitat types that dominated on those areas: fresh coniferous forest (FCF), fresh mixed coniferous forest (FMCF), and fresh mixed deciduous forest (FMDF). The outcrops were made in sites with possibly weak anthropogenic influences on pedogenic processes (nature reserves: 160 DOROTA KALEMBASA, MARCIN BECHER, KRZYSZTOF PAKUŁA

Gołobórz, Zabuże, and Jata, as well as old forests not covered by reserve protection). The studied soils were counted to Dystric Arenosols (4 profiles), Albic Podzols (5 profiles) and Haplic Podzols (3 profiles) developed from fluvioglacial and boulder sands, accumu- latively associated with the Warta river stadial of middle-Polish glaciations. The collected soil samples were subjected to determinations of: granulometric composition - areomet- ric method; bulk density – dryer-weight method; organic carbon content (Corg) - elemen- tal analyzer CHN equipped in thermal conductivity detector (TCD) (in organic horizons), as well as oxidation-titrimetric method (in mineral horizons); pH - potentiometry in 1 M KCl; sorption capacity (CEC) - Kappen’s method. Heavy metals (Zn, Cu, Ni) contents, as well as iron and aluminum, were determined by applying atomic emission spectrometry combined with inductively coupled plasma (ICP–AES) after combustion (at 450°C) and preparing extracts in 20% HCl. It is accepted that hydrochloric acid dissolves mainly the weathered part of soil mineral matter, while constituents soluble in HCl can be gradually taken by plants for a longer time. Partial dissolving of the soil samples is applied in environmental studies, among others, to determine the level of soil contamination. Underestimated (for mineral material) or close (for plant material) levels of elements in reference to their total contents in studied material are then determined [4, 5]. Moreover, total concentrations of iron and aluminum were analyzed taking into account the pedogenesis of studied soils. Studies were performed in three replications, and the obtained results were calculated in reference to absolute dry matter of soils. The paper presents mean values and ranges (for soil sub-types and genetic horizons with similar genesis). For particular genetic horizons, coefficients of enrichment (w.w.) in heavy metals (in reference to parents rock) were calculated on the basis of metals content (in mg·dm-3). The obtained results were statistically processed and expressed as simple correlation coefficients.

RESULTS AND DISCUSSION

Well developed organic horizons characteristic for forest soils of mor and moder types of humus were found in studied soils, which may indicate continuous soil-forming processes for a longer time. Morphology and basic properties of soils (Tab. 1) are typical for taxonomic units of Polish Lowlands [1, 9, 10]. The examined soils were characterized by acidic and very acidic reaction, considerable accumulation of organic matter in organic horizons as well as characteristic profile variability of iron and aluminum contents determined by soil-forming processes. Parents rocks of studied Dystric Arenosols, Albic Podzols and Haplic Podzols had similar concentrations of determined heavy metals (mean values in mg·kg-1: Cu – 1.28; Zn – 6.89; Ni – 2.32). These contents were lower than average levels cited by Czar- nowska [2] for geochemical background of different-genesis sands from northern and middle Poland. In organic horizons (Tab. 2) the higher copper content (1.35–1.73 mg·dm-3, on the average) was found in Ofh, Of, Oh (with greater extent of processed organic matter) com- -3 pared to Ol horizons (0.392–0.427 mg·dm , on the average). In mineral horizons with continuous soil-forming processes (A, B, and E) copper content was recorded on the average from 1.01 to 2.18 mg·dm-3. In Haplic Podzols, profile copper distribution was modified by podzolization process, which was indicated by PROFILE DIFFERENCES OF ZINC, COPPER, AND NICKEL CONTENTS IN FOREST SOILS ON...161

Table 1. Some properties of investigated soils (ranges)

Soil, genetic Soil Fe Al Bulk Fraction horizon organic CEC pH density Ø < 0.02 mm (thickness KCl matter [cmol(+)·kg-1] [g·kg-1] [g·cm-3] [%] [cm])* [%]** Dystric Arenosols

Ol (2) 3.8–4.8 75.9–86.0 103–166 0.95–2.08 0.46–1.15 0.059–0.066 –

Ofh (3) 3.3–4.5 30.5–56.0 62.6–100 1.93–3.24 1.31–2.09 0.135–0.248 – AB (15) 2.7–3.5 2.29–4.29 8.5–12.1 1.48–3.40 1.51–2.93 1.13–1.32 8–10

Bv (42) 3.9–4.5 0.09–0.76 2.59–3.90 1.19–3.18 1.95–3.43 1.43–1.55 3–7 C (74) 3.7–4.8 0.03–0.09 1.28–6.07 0.95–2.57 1.13–3.17 1.52–1.64 2–15 Albic Podzols

Ol (2) 2.7–5.2 63.4–88.3 123–245 0.81–1.49 0.84–2.80 0.049–0.068 –

Of, Oh, Ofh (7) 2.5–5.1 35.0–64.5 104–85 1.74–3.35 1.05–3.97 0.155–0.284 – AE (11) 2.4–2.9 1.51–6.72 5.96–13.9 1.05–2.64 1.94–3.52 1.12–1.39 6–18

BfeBv (38) 3.5–4.4 0.03–1.11 2.61–5.87 2.21–4.47 3.89–5.54 1.41–1.62 3–19 C (70) 3.6–4.9 0.04–0.15 1.32–6.62 0.42–1.80 0.96–1.96 1.59–1.68 2–11 Haplic Podzols

Ol (2) 3.6–4.7 82.8–90.3 109–162 0.45–0.88 0.61–0.93 0.042–0.050 –

Of, Oh, Ofh (8) 2.5–3.6 40.9–60.3 82–176 2.09–2.58 1.99–2.97 0.177–0.266 – A (14) 2.3–3.1 2.90–5.74 9.64–14.8 0.63–1.07 0.85–1.29 1.20–1.35 7–9

Ees, AE (16) 2.3–4.3 0.30–3.47 3.22–11.6 0.17–0.38 0.40–0.60 1.35–1.56 4–11

Bhfe, Bh, Bfe (17) 3.5–3.9 0.55–1.86 4.35–9.96 1.49–2.81 2.01–3.72 1.54–1.67 6–10 C (70) 3.0–4.8 0.04–0.36 2.54–5.46 1.13–2.40 1.43–1.97 1.60–1.71 2–6

* – mean, ** – soil organic matter [%] = Corg [%]·1.724 low value of enrichment coefficient in eluvial horizons. Due to the fact that copper is bound by many soil components (organic matter, clay, Fe and Al hydroxides), this element is a metal with long duration in the soil and weakly migrates within the soil profile. In very acidic soils, lability of its cationic forms is potentially increased – as similar as in the case of copper binding with low-molecular organic compounds formed from soil organic matter decomposition [6]. Profile differentiated zinc content was found in studied soils. Less of that metal was -3 recorded in organic horizons (namely Ol horizons) (4.63 mg·dm , on the average) in relation to mineral horizons (10.4 mg·dm-3, on the average). Podzolization process had a modifying effect on profile zinc amount differentiation. Zinc is an element with great lability in the soil, namely in acidic environment, where mobile mineral-organic complexes are formed. The metal is also strongly bound by soil organic matter and iron and manganese compounds [6]. The nickel concentration zones were found in illuvial horizons (B) and parents rocks (C) of all twelve studied soils. Considerable influence of podzolization process on profile nickel distribution was also recorded, namely in Podzols. Nickel bound to organic matter (including mobile chelates) dominated in the soil environment, while in mineral horizons, it was additionally sorbet by Fe and Mn hydroxides: its solubility and mobility increases along with the acidity increase [6]. 162 DOROTA KALEMBASA, MARCIN BECHER, KRZYSZTOF PAKUŁA 0.11 0.17 0.68 0.17 0.12 0.74 0.19 0.78 0.92 1.33 0.38 0.49 0.84 w.w. ] -3 1.41 1.83 3.14 3.70 2.77 0.49 3.01 4.08 2.93 3.46 5.00 3.76 0.341 0.694 0.694 0.714 [mg·dm Ni ] -1 [mg·kg 7.05 (3.24–12.0) 8.60 (3.46–15.7) 1.54 (0.90–2.50) 2.20 (1.03–3.40) 2.27 (1.30–3.63) 10.1 (2.09–17.1) 15.5 (5.98–29.1) 0.57 (0.52–0.61) 0.31 (0.14–0.57) 2.06 (0.56–3.93) 2.40 (1.07–4.19) 12.5 (3.10–25.6) 17.7 (3.24–37.9) 2.89 (0.57–4.73) 3.50 (1.51–5.92) 2.28 (0.57–7.10) 0.44 0.57 0.95 1.03 0.39 0.69 0.61 0.44 1.09 0.29 0.68 0.98 1.47 w.w. ] -3 ] -3 11.6 11.6 5.34 6.95 12.6 12.2 3.04 7.14 10.3 15.5 10.5 4.52 8.00 7.08 5.10 12.6 [mg·dm Zn ] -1 Albic Podzols Haplic Podzols [mg·kg Dystric Arenosols Dystric 93.6 (31–123) 8.82 (4.33–13.5 68.1 (15.8–117) 8.56 (3.89–11.9) 39.6 (34.5–45.3) 9.75 (8.81–12.4) 7.43 (2.62–12.9) 52.7 (36.8–64.3) 43.0 (28.3–67.0) 7.97 (4.19–13.4) 10.8 (5.20–17.6) 6.38 (1.75–16.7) 45.5 (25.8–54.6) 5.74 (4.20–7.61) 3.42 (2.13–5.54) 6.85 (3.84–12.5) 0.16 0.70 0.53 0.71 0.24 0.76 0.71 1.23 0.20 0.78 0.67 0.48 0.87 w.w. ] -3 1.73 1.30 1.74 2.45 1.35 1.27 2.18 1.78 1.64 1.41 1.01 1.83 2.10 0.427 0.420 0.392* [mg·dm Table 2. Content of heavy metals and value enrichment coefficient in investigated soils Table Cu ] -1 [mg·kg 0.82 (0.6–1.13) 7.5 (6.50–9.15) 10.5 (5.72–14.2) 1.09 (0.94–1.35) 1.51 (0.61–3.56) 8.19 (5.23–10.4) 1.06 (0.36–1.67) 1.53 (0.09–4.33) 1.08 (0.04–4.65) 6.93 (1.59–9.79) 9.61 (4.06–13.6) 1.15 (0.28–2.44) 0.64 (0.38–0.94) 1.25 (0.54–2.20) 1.24 (0.27–2.51) 6.6*(3.77–9.06)** fe fh fh , B h , O , O h h v , B horizon Genetic B , AE , , O , O l fh l f l f v fe hfe es O O AB B C O AE B C O A E C O B O * – mean, ** – range, w.w. – enrichment coefficient calculated on the basis of metals content [mg·dm * – mean, ** range, w.w. PROFILE DIFFERENCES OF ZINC, COPPER, AND NICKEL CONTENTS IN FOREST SOILS ON...163

In others papers the contents of heavy metals in forest soils are expressed in mg·kg-1 more often than in mg·dm-3. Other authors also observed similar tendencies and similar contents of profile distribution of studied metals in podzolic soils [3, 9–11, 14]. In podzolic soils, there are factors that immobilize heavy metals (humus accumulation in organic and humus horizons, active Fe, Al, and Mn forms), and on the other hand, those increasing its migration (high acidity, permeability and slight content of soil mineral colloids). The Polish norms, concerning heavy metals contents in soils, present permissible levels also expressed in mg·kg-1. The comparison of the amounts of studied metals with their published permissible levels may be the measure of anthropogenization intensity. So far, no norms that would take into account the specificity of forest soils, were defined. Ac- cepting values of contamination for arable soils given by Kabata-Pendias et al. [7], it can be concluded that mineral horizons of studied forest soils contained low “natural” levels of heavy metals. These authors also gave the limiting values of metals for organic soils, to which organic horizons of forest soils could be compared (to some extent). In reference to those limits, the studied soils did not show excessive values of heavy metals. Taking into account the norms included in the Decree of Environmental Ministry [12], heavy metals contents in the analyzed soils were within the range of permissible values for forest soils. Konecka-Betley et al. [10] suggested preliminary, limiting contents of some heavy metals in organic sub-horizons; when these limits would be exceeded, concentrations should be related to as “elevated”, i.e. Cu – 30, Zn – 75, Ni – 35 mg·kg-1. In reference to these values, their slight excess was recorded in particular organic horizons only for Zn (in litter organic horizons) and for Ni (in a single case). Statistical analysis of the obtained results revealed many significant correlation dependencies (differing between organic and mineral genetic horizons) for Cu, Zn, Ni contents and selected soil properties (Tab. 3). Values of correlation coefficients suggest that the content of studied heavy metals in organic horizons is mainly a function of the organic matter amount, while in mineral horizons – the content of the finest granulometric fractions (statistically significant values of the coefficient). In mineral horizons, strong (positive) correlations were found between contents of studied heavy metals and iron and aluminum concentrations, which indirectly confirm the influence of soil-forming processes on distribution of studied metals in mineral genetic horizons of examined soils.

Table 3. Values of correlation coefficients between content of Cu, Zn, Ni and same soils properties

Organic horizons n = 33 Mineral horizons n = 71 Parameter Cu Zn Ni Cu Zn Ni

pHKCl 0.05 0.29 0.46* -0.03 0.08 0.26* Soil organic matter 0.34* 0.45* -0.45* 0.11 0.13 -0.34* CEC 0.08 0.14 -0.11 0.32* 0.21 -0.25* Fe -0.01 -0.01 -0.59* 0.59* 0.42* 0.41* Al 0.17 0.15 -0.63* 0.40* 0.39* 0.30* Ø < 0.02 mm – – – 0.68* 0.51* 0.29* Cu x 0.68* -0.17 x 0.60* 0.49* Zn x x -0.38* x x 0.65*

* – significant at α = 0.05 164 DOROTA KALEMBASA, MARCIN BECHER, KRZYSZTOF PAKUŁA

CONCLUSIONS

The copper, zinc, and nickel contents in the studied 12 forest podzolic soils localized on South-Podlasie Lowland were mostly determined by poor parents rock. Profile distribution of the studied heavy metals was differentiated by pedological processes, namely forming the organic and humus horizons as well as podzolization process (impoverishment of eluvial vs. enrichment of illuvial horizons) as well as rusting (to a lesser extent). In organic horizons of the studied soils, the strongest correlations were recorded between Cu, Zn, Ni contents and organic matter amount; in mineral horizons – between these metals contents vs. < 0.02 mm fraction, iron and aluminum contents.

REFERENCES

[1] Brożek S., M. Zwydak: Atlas gleb leśnych Polski, CILP, Warszawa 2003. [2] Czarnowska K.: Ogólna zawartość metali ciężkich w skałach macierzystych, jako tło geochemiczne gleb, Rocz. Gleb., 47 supl., 43–50 (1996). [3] Gworek B., M. Degórski: Przestrzenne i profilowe rozmieszczenie pierwiastków śladowych i żelaza w glebach zbiorowisk borowych, Rocz. Gleb., 48, 1/2, 19–30 (1997). [4] Gworek B., D. Maciaszek, U. Pieńkowska, E. Polubiec: Klasyczna i mikrofalowe sposoby mineralizacji próbek botanicznych w celu oznaczania mikro i makroskładników – badania porównawcze, Rocz. Gleb., 52, 1/2, 89–97 (2001). [5] Gworek B., D. Maciaszek, U. Pieńkowska, E. Polubiec: Zastosowanie techniki mikrofalowej do oznaczania pierwiastków w materiale glebowym – badania porównawcze, Rocz. Gleb., 50, 1/2, 127–134 (1999). [6] Kabata-Pendias A., H. Pendias: Biogeochemia pierwiastków śladowych, PWN, Warszawa 1999. [7] Kabata-Pendias A., M. Piotrowska, H. Motowicka-Terelak, B. Maliszewska-Kordybach, K. Filipek, A. Krakowiak, C. Pietrzak: Podstawy oceny chemicznego zanieczyszczenia gleb, Biblioteka Monitoringu Środowiska, 1–41 (1995). [8] Kalembasa D., M. Becher, K. Pakuła: Profilowe zróżnicowanie zawartości ołowiu, chromu i kadmu w leśnych glebach bielicoziemnych na Nizinie Południowopodlaskiej, Zesz. Probl. Post. Nauk Rol., 520, 465–472 (2007). [9] Konecka-Betley K., D. Czępińska-Kamińska, E. Janowska, M. Okołowicz: Gleby stref: ochrony ścisłej i częściowej w rezerwacie biosfery „Puszcza Kampinoska”, Rocz. Gleb., 53, 3/4, 5–21 (2002). [10] Konecka-Betley K., D. Czępińska-Kamińska, E. Janowska: Przemiany pokrywy glebowej w Kampi- noskim Parku Narodowym, Rocz. Gleb., 50, 4, 5–29 (1999). [11] Kwasowski W., J. Chojnicki, M. Okołowicz, T. Kozanecka: Metale ciężkie w glebach powierzchni wzor- cowych (GPW) w Puszczy Białej, Rocz. Gleb., 51, 3/4, 85–95 (2000). [12] Rozporządzenie Ministra Środowiska w sprawie standardów jakości gleb oraz standardów jakości ziemi, Dz. U. nr 165, poz. 1359 z 2002 r. [13] Skwaryło-Bednarz B.: Ogólna zawartość wybranych metali ciężkich w glebach leśnych Roztoczańskiego Parku Narodowego (RPN), Acta Agrophysica, 8, 3, 727–733 (2006). [14] Uziak S., Z. Klimowicz, J. Chodorowski, J. Melke: Badania zanieczyszczeń gleb Parku krajobrazowego Lasy Janowskie, Annalles UMCS Lublin, 54, 11, 201–216 (1999).

Received: December 12, 2008; accepted: September 17, 2009.

PROFILOWE ZRÓŻNICOWANE ZAWARTOŚCI CYNKU, MIEDZI I NIKLU W LEŚNYCH GLEBACH BIELICOZIEMNYCH NA NIZINIE POŁUDNIOWOPODLASKIEJ

Badano profilowe zróżnicowanie zawartości miedzi, cynku i niklu w leśnych glebach bielicoziemnych na Nizinie Południowopodlaskiej. Stwierdzono znaczne ich zróżnicowanie. Na zawartość i zróżnicowanie w pro- filu analizowanych metali ciężkich w badanych glebach największy wpływ miały: mało zasobna skała macie- rzysta oraz charakterystyczne dla tych gleb procesy glebotwórcze (głównie bielicowanie). 165

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 Numbers: 1–4 2009

CONTENTS OF VOL. 35 (2009)

No. 1

Fractional Composition of Dust Emitted From Boilers with Circulating Fluidized Beds – Jan Konieczyński, Jacek Żeliński ...... 3 Air Quality Index and Its Significance in Environmental Health Risk Communication – Małgorzata Kowalska, Leszek Ośródka, Krzysztof Klejnowski, Jan EZejda, Ewa Krajny, Marek Wojtylak ...... 13 Distribution of Polyporus Fungi in Czaplinek (Drawsko Lake District, North- Western Poland) – Magdalena Kaczorkiewicz, Edward Ratuszniak . . . . 23 Role of Recycled Sludge Age in Coagulation of Colored Water – Jolanta Gumińska, Marcin Kłos ...... 33 The Effect of Some Technological Parameters on the Diversity of Immobilized Microorganisms – Magdalena Zielińska, Agnieszka Cydzik-Kwiatkowska, Irena Wojnowska-Baryła ...... 45 Seasonal Changes in the Number of Sulphate-Reducing Bacteria in the Water, Soil and Plant of the Wetlands near Olsztyn – Stanisław Niewolak, Renata Brzozowska, Karolina Czechowska, Zofia Filipkowska, Ewa Korzeniewska 55 Changes of Photosynthetic Pigments Concentration in the Synchronous Culture of Chlorella Vulgaris as an Indicator of Water Quality in Goczałkowice Reservoir – Anna Czaplicka-Kotas, Jolanta Lodowska, Adam Wilczok, Zbigniew Ślusarczyk ...... 65 Changes of Chosen Chemical Elements Concentration in Alluvial Sediments: An Example of the Lower Course of the Obra River (Western Poland) – Marcin Słowik, Tadeusz Sobczyński, Zygmunt Młynarczyk ...... 75 Geochemical Groups of Alluvial Sediments of the Lower Course of the Obra River: An Example of Using Cluster Analysis – Marcin Słowik, Tadeusz Sobczyński, Zygmunt Młynarczyk ...... 87 Influence of Soil Contamination with Nickel and Liming on Lead and Manganese Contents in Red Clover Biomass – Beata Kuziemska, Stanisław Kalembasa 95 Disinfection of Meat Industry Equipment and Production Rooms with the Use of Liquids Containing Silver Nano-Particles – Michał Konopka, Zygmunt Kowalski, Zbigniew Wzorek ...... 107 Stabilization of Post-Galvanic Sludge Using Portland Cement and Silica Fume – Małgorzata Osińska, Agnieszka Ślosarczyk ...... 117 166 CONTENTS OF VOL. 35 (2009)

No. 2

Structure of Atmospheric Aerosol in the Upper Silesian Agglomeration (Poland) – Contribution of PM2.5 to PM10 in Zabrze, Katowice and Częstochowa in 2005–2007 – Krzysztof Klejnowski, Wioletta Rogula-Kozłowska, Andrzej Krasa ...... 3 Advanced Oxidation of Diclofenac in Various Aquatic Environments – Ewa Felis, Jarosław Wiszniowski, Korneliusz Miksch ...... 15 Influence of Fishery Management and Environmental Factors on Occurrence of Heterotrophic, Hemolytic and Mesophilic Bacteria and Aeromonas Hydrophila in Waters of the Drwęca River, Poland – Iwona Gołaś, Karol Korzekwa, Monika Harnisz, Izabella Zmysłowska, Mariusz Teodorowicz, Elżbieta Terech-Majewska, Wiesława Rodziewicz, Mariola Bieńkowska . . . 27 Characteristic of Granulated Activated Sludge Fed with Glycerin Fraction from Biodiesel Production – Agnieszka Cydzik-Kwiatkowska, Andrzej Białowiec, Irena Wojnowska-Baryła, Lech Smoczyński ...... 41 Formation of the Activated Sludge Biocenosis during Landfill Leachate Pre-Treat- ment in SBR – Mirosław Szyłak-Szydłowski, Anna Grabińska-Łoniewska . 53 Phosphorus Release from Lake Bottom Sediments Affected by Abiotic Factors – Tadeusz Sobczyński ...... 67 Effects of Gneiss Mining on Water Quality – Mladen Zelenika, Božo Soldo, Damir Štuhec ...... 75 Technogenic and Geogenic Magnetic Susceptibility of Mountain Forest Soils on Example of Forest Division Kamienna Góra – Adam Łukasik, Zygmunt Strzyszcz ...... 87 Heavy Metals and Selected Physicochemical Properties of Rendzic Leptosols of the Ponidzie Region (Southern Poland) – Anna Świercz ...... 97 The Influence of the Method of Reclamation and Selection of Tree Species for Afforestation on Changes in Landscape Degraded by Fire – Elżbieta Jolanta Bielińska, Agnieszka Mocek-Płóciniak ...... 105 The Removal of Cr(VI) from the Aqueous Solution by Granular Ferric Hydroxide (GFH) – Bai Yuan, Bronisław Bartkiewicz ...... 115 Polychlorinated Dibenzo-p-Dioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) Compounds in Sediments of Two Shallow Reservoirs in Central Poland – Magdalena Urbaniak, Marek Zieliński, Wiktor Wesołowski, Maciej Zalewski ...... 125

No. 3

Biodegradation of Methyl Isobutyl Ketone (MIBK) by Fusarium Solani – Krystyna Przybulewska, Andrzej Wieczorek ...... 3 The Use of Disintegrated Foam to Accelerate Anaerobic Digestion of Activated Sludge – Alicja Machnicka, Klaudiusz Grűbel, Jan Suschka ...... 11 Wastewater Purification by an Organic Soil and Grass-Mixture – Urszula Kotowska, Teresa Włodarczyk, Barbara Witkowska-Walczak, Cezary Sławiński ...... 21 CONTENTS OF VOL. 35 (2009) 167

Generation and Management of Wastewater from Ground Water Treatment – Krzysztof Piaskowski ...... 35 Fractionation of Chosen Heavy Metals in Bottom Sediments of Small Water Reser- voirs – Marek Madeyski, Marek Tarnawski, Czesława Jasiewicz, Agnieszka Baran ...... 47 Qualitative and Quantitative Characteristics of Organic Matter in the Water of a Small Reservoir – Katarzyna Parszuto, Renata Tandyrak, Jarosław Galik . . . 59 Appraisal of Bottom Sediment Pollution with Heavy Metals of Small Water Reservoirs Located in South Poland – Bogusław Michalec, Marek Tarnawski . 73 Effect of Type and Proportion of Different Structure-Creating Additions on the Inactivation Rate of Pathogenic Bacteria in Sewage Sludge Composting in a Cybernetic Bioreactor – Agnieszka Wolna-Maruwka, Jacek Dach ...... 87 Impact of Uncontrolled Waste Dumping on Soil Chemical and Biochemical Properties – Elżbieta Jolanta Bielińska, Agnieszka Mocek-Płóciniak . . . 101 Possibility of Using Permeable Reactive Barrier in Two Selected Dumping Sites – Tomasz Suponik, Marcin Lutyński ...... 109 Solid Phase Anaerobic Bioremediation of Soil from the “Tomb” Area Contaminated with Chlorinated Pesticides – Tomasz Baczyński . . . . . 123 Some Heavy Metals Accumulation and Distribution in Typha Latifolia L. from Lake Wielkie in Poland – Agnieszka Klink, Józef Krawczyk, Barbara Leta- chowicz, Magdalena Wisłocka ...... 135

No. 4

The Occurrence of Selected Trace Elements in Grain Fractions of Dust Emitted from Power, Coke and Cement Plants – Jan Konieczyński, Katarzyna Stec . . . 3 Measurements of Aerosol Size Distribution in Urban Areas of Upper Silesia – Krystian Skubacz ...... 23 Environmental Levels of Nitro-PAHs in Total Suspended Particulate Matter in Upper Silesia (Poland) – Marzena Zaciera, Wojciech Mniszek, Jolanta Kurek ...... 35 The Influence of Air-Conditioning System and Presence of Students on the Aerosol Concentration in the Auditorium – Bernard Połednik, Marzenna Dudzińska, Mariusz Skwarczyński ...... 45 Study of Aluminium Sulphate Complexes of Surface Water and Fractionation of Aluminium from Bottom Sediment – Marcin Frankowski, Anetta Zioła- Frankowska, Jerzy Siepak ...... 55 Occurrence Study of Agro-Chemical Pollutants in Waters of Supraśl Catchment – Katarzyna Ignatowicz ...... 69 Changes of Physicochemical Parameters and Phytoplankton in Water of a Submountain Dam Reservoir – Effect of Late Summer Stormflow – Ewa Szarek-Gwiazda, Grażyna Mazurkiewicz-Boroń, Elżbieta Wilk-Woźniak . 79 The Structure of Macrozoobenthos Assemblages in the Area of Sewage- Treatment Plant in Jurata – Jastarnia (The Puck Bay Coastal Zone) – Krystian Obolewski, Anna Jarosiewicz ...... 91 168 CONTENTS OF VOL. 35 (2009)

Sewage Sludge and Foam Management in Enhanced Biological Nutrients Removal Plant (EBNRP) – Jan Suschka, Eligiusz Kowalski ...... 105 The Effect of Microwave Radiation on Waste Treatment in a Reactor with a Biofilm – Marcin Zieliński, Mirosław Krzemieniewski ...... 119 Hydrochemical Conditions for Localization of Small Water Reservoirs on the Example of Kluczbork Reservoir – Mirosław Wiatkowski ...... 129 Changes in Water Quality of Zagreb Water-Pumping Sites – Mladen Zelenika, Božo Soldo, Bojan Đurin ...... 145 Profile Differences of Zinc, Copper, and Nickel Contents in Forest Soils on South- Podlasie Lowland – Dorota Kalembasa, Marcin Becher, Krzysztof Pakuła . . 159 Contents of vol. 35 (2009) ...... 165 Authors Index of vol. 35 (2009) ...... 170 169

ARCHIVES OF ENVIRONMENTAL PROTECTION vol. 35 Numbers: 1–4 2009

AUTHORS INDEX OF VOL. 35 (2009)

Baczyński Tomasz 123, nr 3, 2009 Klejnowski Krzysztof 3, nr 2, 2009 Baran Agnieszka 47, nr 3, 2009 Klink Agnieszka 135, nr 3, 2009 Bartkiewicz Bronisław 115, nr 2, 2009 Kłos Marcin 33, nr 1, 2009 Becher Marcin 159, nr 4, 2009 Konieczyński Jan 3, nr 1, 2009 Białowiec Andrzej 41, nr 2, 2009 Konieczyński Jan 3, nr 4, 2009 Bielińska Elżbieta Jolanta 105, nr 2, 2009 Konopka Michał 107, nr 1, 2009 Bielińska Elżbieta Jolanta 101, nr 3, 2009 Korzekwa Karol 27, nr 2, 2009 Bieńkowska Mariola 27, nr 2, 2009 Korzeniewska Ewa 55, nr 1, 2009 Brzozowska Renata 55, nr 1, 2009 Kotowska Urszula 21, nr 3, 2009 Cydzik-Kwiatkowska Kowalska Małgorzata 13, nr 1, 2009 Agnieszka 45, nr 1, 2009 Kowalski Eligiusz 105, nr 4, 2009 Cydzik-Kwiatkowska Kowalski Zygmunt 107, nr 1, 2009 Agnieszka 41, nr 2, 2009 Krajny Ewa 13, nr 1, 2009 Czaplicka-Kotas Anna 65, nr 1, 2009 Krasa Andrzej 3, nr 2, 2009 Czechowska Karolina 55, nr 1, 2009 Krawczyk Józef 135, nr 3, 2009 Dach Jacek 87, nr 3, 2009 Krzemieniewski Mirosław 119, nr 4, 2009 Dudzińska Marzenna 45, nr 4, 2009 Kurek Jolanta 35, nr 4, 2009 Đurin Bojan 145, nr 4, 2009 Kuziemska Beata 95, nr 1, 2009 Felis Ewa 15, nr 2, 2009 Letachowicz Barbara 135, nr 3, 2009 Filipkowska Zofia 55, nr 1, 2009 Lodowska Jolanta 65, nr 1, 2009 Frankowski Marcin 55, nr 4, 2009 Lutyński Marcin 109, nr 3, 2009 Galik Jarosław 59, nr 3, 2009 Łukasik Adam 87, nr 2, 2009 Gołaś Iwona 27, nr 2, 2009 Machnicka Alicja 11, nr 3, 2009 Grabińska-Łoniewska Anna 53, nr 2, 2009 Madeyski Marek 47, nr 3, 2009 Grűbel Klaudiusz 11, nr 3, 2009 Mazurkiewicz-Boroń Grażyna 79, nr 4, 2009 Gumińska Jolanta 33, nr 1, 2009 Michalec Bogusław 73, nr 3, 2009 Harnisz Monika 27, nr 2, 2009 Miksch Korneliusz 15, nr 2, 2009 Ignatowicz Katarzyna 69, nr 4, 2009 Młynarczyk Zygmunt 75, nr 1, 2009 Jarosiewicz Anna 91, nr 4, 2009 Młynarczyk Zygmunt 87, nr 1, 2009 Jasiewicz Czesława 47, nr 3, 2009 Mniszek Wojciech 35, nr 4, 2009 Kaczorkiewicz Magdalena 23, nr 1, 2009 Mocek-Płóciniak Agnieszka 105, nr 2, 2009 Kalembasa Dorota 159, nr 4, 2009 Mocek-Płóciniak Agnieszka 101, nr 3, 2009 Kalembasa Stanisław 95, nr 1, 2009 Niewolak Stanisław 55, nr 1, 2009 Klejnowski Krzysztof 13, nr 1, 2009 Obolewski Krystian 91, nr 4, 2009 170 AUTORS INDEX OF VOL. 35 (2009)

Osińska Małgorzata 117, nr 1, 2009 Tandyrak Renata 59, nr 3, 2009 Ośródka Leszek 13, nr 1, 2009 Tarnawski Marek 47, nr 3, 2009 Pakuła Krzysztof 159, nr 4, 2009 Tarnawski Marek 73, nr 3, 2009 Parszuto Katarzyna 59, nr 3, 2009 Teodorowicz Mariusz 27, nr 2, 2009 Piaskowski Krzysztof 35, nr 3, 2009 Terech-Majewska Elżbieta 27, nr 2, 2009 Połednik Bernard 45, nr 4, 2009 Urbaniak Magdalena 125, nr 2, 2009 Przybulewska Krystyna 3, nr 3, 2009 Wesołowski Wiktor 125, nr 2, 2009 Ratuszniak Edward 23, nr 1, 2009 Wiatkowski Mirosław 129, nr 4, 2009 Rodziewicz Wiesława 27, nr 2, 2009 Wieczorek Andrzej 3, nr 3, 2009 Rogula-Kozłowska Wioletta 3, nr 2, 2009 Wilczok Adam 65, nr 1, 2009 Siepak Jerzy 55, nr 4, 2009 Wilk-Woźniak Elżbieta 79, nr 4, 2009 Skubacz Krystian 23, nr 4, 2009 Wisłocka Magdalena 135, nr 3, 2009 Skwarczyński Mariusz 45, nr 4, 2009 Wiszniowski Jarosław 15, nr 2, 2009 Sławiński Cezary 21, nr 3, 2009 Witkowska-Walczak Barbara21, nr 3, 2009 Słowik Marcin 75, nr 1, 2009 Włodarczyk Teresa 21, nr 3, 2009 Słowik Marcin 87, nr 1, 2009 Wojnowska-Baryła Irena 45, nr 1, 2009 Smoczyński Lech 41, nr 2, 2009 Wojnowska-Baryła Irena 41, nr 2, 2009 Sobczyński Tadeusz 75, nr 1, 2009 Wojtylak Marek 13, nr 1, 2009 Sobczyński Tadeusz 87, nr 1, 2009 Wolna-Maruwka Agnieszka 87, nr 3, 2009 Sobczyński Tadeusz 67, nr 2, 2009 Wzorek Zbigniew 107, nr 1, 2009 Soldo Božo 75, nr 2, 2009 Yuan Bai 115, nr 2, 2009 Soldo Božo 145, nr 4, 2009 Zaciera Marzena 35, nr 4, 2009 Stec Katarzyna 3, nr 4, 2009 Zalewski Maciej 125, nr 2, 2009 Strzyszcz Zygmunt 87, nr 2, 2009 Zejda Jan E. 13, nr 1, 2009 Štuhec Damir 75, nr 2, 2009 Zelenika Mladen 75, nr 2, 2009 Suponik Tomasz 109, nr 3, 2009 Zelenika Mladen 145, nr 4, 2009 Suschka Jan 11, nr 3, 2009 Zielińska Magdalena 45, nr 1, 2009 Suschka Jan 105, nr 4, 2009 Zieliński Marcin 119, nr 4, 2009 Szarek-Gwiazda Ewa 79, nr 4, 2009 Zieliński Marek 125, nr 2, 2009 Szyłak-Szydłowski Mirosław 53, nr 2, 2009 Zioła-Frankowska Anetta 55, nr 4, 2009 Ślosarczyk Agnieszka 117, nr 1, 2009 Zmysłowska Izabella 27, nr 2, 2009 Ślusarczyk Zbigniew 65, nr 1, 2009 Żeliński Jacek 3, nr 1, 2009 Świercz Anna 97, nr 2, 2009