Barbara Walna

Research on the variability of physico-chemical parameters characterising acid precipitation at the Jeziory Ecological Station in the Wielkopolski National Park (Poland).

Here the water quality of precipitation at the Adam Mickiewicz University Ecological station is presented for the period 1992-1997 to examine one of the main factors causing the degradation of the natural environment of the Weilkopolski National Park. In the course of daily observations the amount of rainfall, its electrical conductivity and pH were measured. As much as 61% of the tested precipitation had a pH < 4.6, and 92% had a pH < 5.6; some very low pH values, even below 3.0, were occasionally observed. The annual volume-weighted average pH during the full period was 4.28 and the lowest yearly average was 3.92 (1994). The chemical composition of precipitation showed the dominance of sulphate and calcium ions. Fluoride ions also contributed significantly to the anion charge. There were also small amounts of heavy metals and polycyclic aromatic hydrocarbons. A chemical analysis of throughfall showed a considerably increased concentration of some ions, in particular potassium.

The impact of acid rain on calcium and magnesium status in typical soils of the Wielkopolski National Park

Abstract The previous investigation of the chemical characteristics of precipitation within the Wielkopolski National Park has shown its high acidity which sometimes drops below pH 3.0. This paper deals with calcium and magnesium ion leaching by acid rain from typical soils of the area. Laboratory experiments were conducted on soil monoliths (15 cm in diameter, 50 cm high) with acid solutions of pH 3.0, pH 2.0 and a water control of pH 5.6. The sprinkling lasted 30 days, simulating a rainfall of 400 mm. The eluates were analysed every day. The soil properties and forms of calcium and magnesium were determined before and after treatment. The investigations show that quite large amounts of Ca 2+ and Mg 2+ can be leached from soil — in the very acid treatment (pH 2.0) leaching amounted to about 100 mg Ca 2+ and 17 mg Mg 2+ per kg of soil. The leaching of these elements was several times less in the pH 3.0 and 5.6 treatments. The differences in the dynamics of the process is shown on the leaching curves — their shapes are smooth when pH is 5.6 and 3.0, while a sharp peak is present at pH 2.0.

The Impact of Acid Rain on Potassium and Sodium Status in Typical Soils of the Wielkopolski National Park (Poland)

A previous investigation of thechemical characteristics of precipitation in theWielkopolski National Park has shown its high acidity,which sometimes drops below pH 3.0. This paper dealswith the leaching of potassium and sodium ions by acidrain from typical soils of the study area. Laboratoryexperiments were conducted on undisturbed soil cores(15 cm in diameter, 50 cm high) with acid solutions of pH 3.0, pH 2.0 and with water of pH 5.6 (control). The sprinkling lasted 30 days simulating a rainfall of 400 mm. The eluates were analysed daily. Soil propertiesand forms of potassium and sodium were determinedbefore and after treatment. The investigations showthat quite significant amounts of K+ andNa+ can be leached from the soil: in the very acidtreatment (pH 2.0) about 4 mg K+ and 3 mgNa+ per kg of soil. The leaching of these elementswas smaller in the pH 3.0 and 5.6 treatments.Differences in the dynamics of the process are shownin the leaching curves. In the case of potassium theirshapes are smooth when pH is 5.6 and 3.0, while at pH2.0 the curves rise sharply. The leaching curves inthe case of sodium do not show sharp peaks, whichmeans that the leaching is slow and equalised.

Heavy metals in fluvial sediments of the Odra River flood plains - introductory research

Heavy metals in fluvial sediments of the Odra River flood plains - introductory research The article presents the results of research on concentrations of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in fluvial sediment samples collected in the flood plains of the Odra River. The samples were collected from the presently flooded area and from the area which was formerly flooded. The extraction of sediment samples was conducted using aqua regia and four other extractants: 0.01M CaCl2, 0.1M HCl, 0.005M DTPA and 0.02M EDTA. The analysis of the results revealed different concentration values for particular sample collection sites situated along the course of the Odra River. The differentiation of metal concentrations in the investigated samples depending on the extractants was also observed. The concentrations of metals were determined using the technique of atomic absorption spectrometry with flame atomization (F-AAS).

Multivariate statistics as means of tracking atmospheric pollution trends in Western Poland

This study was carried out over a period of 4 years (2002–2005) at 2 sites located in western Poland differing as regards to human impact by analysis of chemical composition of bulk precipitation. The aim of the study was to determine the sources of pollutions and assess their quantitative contribution to the bulk precipitation composition and to analyse long term-changes in the chemical quality of precipitation. Based on this information the possible transboundary impacts of pollution were also determined. The samples were characterized by determining the values of pH, electrolytic conductivity and concentration levels of Cl−, F−, SO4 2−, NO3 −, Na+, K+, Mg2+, Ca2+ and NH4 +. Analytical measurements were connected with application of principal component regression (PCR) and time series analysis (TS). Based on PCR results three major sources of pollutants in central part of Poland have been identified and quantitatively assessed as follows: “combined” (Poznań – 31%, WNP – 32%), “soil-particulates” (Poznań – 2%, WNP – 26%), “anthropogenic-fossil fuels” (Poznań – 43%, WNP – 23%). Time series analysis enabled discovering 12-month time cycle for NO3 −, NH4 +, Cl−, F− and SO4 2− in average monthly concentration values in bulk precipitation collected in Wielkopolski National Park. Seasonal variation in the emission of precursors of NO3 − and NH4 + was caused by changes in intensity of fertilizer application in agriculture and automobile exhaust emissions. Decreasing trend was visible for sulphates, nitrates, chlorides and fluorides which is an important indication of the acid rain reduction in the ecologically protected area and in Poznań.

Composition and variability of soil solutions as a measure of human impact on protected woodland areas

A study was made of the sandy and loamy soils of the woodland areas of the Wielkopolski National Park (Poland) affected by acid rain. The basic properties of the soils were determined, revealing their strong acidification, poor buffering power, and the possibility of aluminium release. An analysis was made of the content of soluble, exchangeable, organic, amorphous, and free forms of aluminium. The concentration of exchangeable aluminium exceeded that of the form dissolved in soil water several times to tens of times.In soil solutions Ca/Al ratios in some horizons show very low values that could induce a nutrient deficit. In the sandy profiles the ratio even drops below the critical level of 0.1. In the surface horizon the dominant cation at all the sites is the aluminium ion.An analysis of anions shows a dominance of sulphate and chloride ions. In autumn nitrites were recorded at all depth levels, while in spring only in the surface layers. The highest fluoride concentrations were found to occur in profiles situated the closest to the emission source of fluorine compounds. The markedly higher concentrations of ammonium than nitrate ions can lead to increased acidification and eutrophication of the soil.

Human impact on atmospheric precipitation in a protected area in Western Poland. Results of long–term observations: Concentrations, deposition and trends

The paper presents the results of long–term measurements of rain chemistry in the woodland area of the Wielkopolski National Park (Western Poland) experiencing some human impact. The ions predominating in precipitation turned out to be those of ammonium and sulfates, which is indicative of human impact related with agriculture and animal breeding as well as with SO2 emissions. In the period 2002–2013 it is possible to identify, for both precipitation and throughfall, statistically significant decreasing trends in the concentrations and deposition of sulfates, ammonium and potassium, and an increasing trend for fluoride. Both bulk deposition and throughfall of N was higher than that of S. The deposition of nitrogen with throughfall was near to the critical load. High levels of acid–forming ions were observed in both, the winter and late–spring seasons, which proves not only the impact of heating but also of the local industry. Notable is the simultaneous occurrence of extremely high levels of acid–forming ions in some precipitation events, which might have many important implications for the soil, water and biota. There was a change in the pattern of atmospheric chemistry observed as a statistically significant downward trend in the rates of ionic concentration equivalents.

Chemometrics in the assessment of local and trans-boundary air pollution

This paper provides the results and assessment of local and transboundary pollution in the Pozna metropolitan area and at the Wielkopolski National Park, Poland. Precipitation that occurred simultaneously in both locations was collected and the analyses such as H+, F−, Cl−, NO3−, SO42−, Na+, K+, Mg2+, Ca2+ and NH4+ and conductivity were determined. The results were subjected to full statistical evaluation and chemometrical analysis: Time Series (TS), Correlation Analysis, Principal Component Analysis (PCA) and Analysis of Variance (ANOVA). TS analysis allowed the observation of noncorresponding peaks on TS graphs and the occurrence of local pollution effects. Correlation analysis and PCA indicated a strong correlation between the concentrations of analytes determined in samples collected at both sites, especially those that originate from anthropogenic sources. This indicates that pollutants emitted in the metropolitan area or from remote sources might significantly influence the nearby area. ANOVA, supported with the prevailing wind direction analysis, showed a minor influence of the cross-border transport of pollutants.

Physico-Chemical Parameters Determining the Variability of Actually and Potentially Available Fractions of Heavy Metals in Fluvial Sediments of the Middle Odra River

Abstract The occurrence of heavy metals (Cd, Cr, Cu, Ni, Pb, Zn) has been determined in the fluvial sediment samples collected along three transects in the Middle Odra River (western Poland) with a width of 360 m. The total concentrations of the metals were obtained after HNO3 microwave digestion and the available fractions of heavy metals were determined by single extraction procedures using two extractants: 0.01M CaCl2 and 0.05M EDTA. The measurement of physico-chemical parameters was also performed. The determination of total and available fractions of heavy metals, except potential available fractions of Cr, revealed high concentrations of studied elements detected in the sediment samples characterized by high content of coarse and very coarse-grained sand fraction and high content of organic matter. It was found that the concentrations of total and available fractions of metals could increase along with the content of organic matter, Eh values and concentrations of H+. Apart from the above, those concentrations become the lowest, the higher the content of medium grain size fractions is. Furthermore, the amounts of CaCl2 and EDTA extractable metals increase in the sediments samples characterized by the lowest total and available concentrations of heavy metals.

Reliability and comparability – crucial aspects of research on atmospheric precipitation

The paper presents some research problems concerning the use of different methodologies, particularly focusing on reliability and comparability based on the authors’ own research and some literature. The differences involving such factors as the place, mode and frequency of sampling, kinds of samples taken, duration and method of storage from the time of sampling to the time of analysis, preparation of samples for analysis, and verification and interpretation of the results, were investigated. The most significant changes were observed in precipitation samples obtained as a result of different collecting procedures – both in terms of method and frequency. The differences in concentrations of some ions for the corresponding samples of wet and bulk deposition exceeded 100%. On the other hand, the equalisation of samples and results led to the differences in results reaching 20%. The results of analyses of precipitation samples collected within a certain time sequence (monthly) poured together in amounts proportional to the precipitation events, differed from the figures obtained for samples collected on a daily basis and averaged. The greatest differences were observed in the pH and in concentrations of , , and Ca2+. The changes of the composition of precipitation samples stored at a variety of conditions were also investigated. The greatest changes were observed for , and concentrations. Changes in pH during storage could even range over 1.6 units, which corresponded to more than a 15-fold difference in H+ concentrations. Evaluation of analytical methods applied with the verification of the validation parameters has been also presented. Moreover, data verification and interpretation by a different method, e.g. comparing the measured value of conductivity with the calculated one or balancing the determined cations and anions, as well as use of statistics (including chemometric techniques), are presented.