Iwona Kurzyca

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.

Water ecosystems affected by human impact within the protected area of the Tatra National Park (Poland).

Water ecosystems affected by human impact within the protected area of the Tatra National Park (Poland) The subjects of the study were two high-mountain lakes, Morskie Oko and Czarny Staw pod Rysami, in the Tatra range of the Carpathian Mountains located within the protected area of the Tatra National Park. This paper presents results of the analytical study of the lake water composition and compares this with relevant data from earlier years. The impact of the following factors was distinguished and discussed: atmospheric deposition (dry and wet), migration of pollutants with runoff water supplying both reservoirs, tourism (hiking, climbing), and the influence of mountain hostels. The resistance and sensitivity of the lakes to human impact is described in terms of water quality changes and characteristics of the catchments and the region.

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.

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.

Simultaneous speciation analysis of inorganic nitrogen with the use of ion chromatography in highly salinated environmental samples.

We present the development of a method for the simultaneous determination of inorganic nitrogen species in oxidized (NO2 (-) , NO3 (-) ) and reduced (NH4 (+) ) forms using ion chromatography with diode-array detection (205, 208, and 425 nm, respectively). The oxidized forms were determined directly after the separation in the anion exchanger, while the reduced form was determined in the column hold-up time after derivatization with the Nessler reagent. The use of an appropriate modifier (Seignette reagent) and mobile phase (NaCl) enabled the determination of inorganic nitrogen species in highly salinated environmental samples (water, sediments). Moreover, low detection limits were obtained of 0.04 mg/L for NH4 (+) and 0.006 and 0.005 mg/L for NO2 (-) and NO3 (-) , respectively. The analysis of environmental samples indicated NH4 (+) contents of up to 1161 ± 47 mg/kg and NO3 (-) of up to 148 ± 6 mg/kg for sediment samples, as well as the NH4 (+) concentrations of up to 0.98 ± 0.10 mg/L, NO2 (-) of up to 24 ± 1 mg/L and NO3 (-) of up to 20 ± 1 mg/L for water samples.

Matrix Influences on the Determination of Common Ions by using Ion Chromatography Part 1—Determination of Inorganic Anions

Ion chromatography is the most popular instrumental analytical method used for the determination of anions and cations in water and wastewater. Isocratic ion chromatography with suppressed conductivity detection is frequently used in laboratories carrying out routine analyses of inorganic anions. The paper presents the results of the research into the influence of selected inorganic anions dominant in environmental samples (Cl(-), NO(3)(-), SO(4)(2-)) on the possibility of simultaneous determination of F(-), Cl(-), NO(2)(-), NO(3)(-), PO(4)(3-) and SO(4)(2-) with the application of this most popular ion chromatography type in standard separation conditions. Four Dionex and four Metrohm anion-exchange columns were tested in standard separation conditions recommended by their manufacturers with both standard solutions and environmental samples with complex matrix.

Tendencies of changes in the chemical composition of precipitation in the Wielkopolski National Park

Tendencies of changes in the chemical composition of precipitation in the Wielkopolski National Park The results are presented of chemical studies on precipitation based on multi-year observations (1992-2007) carried out in the Wielkopolski National Park (WNP). They are compared with the monitoring data obtained by stations grouped in the European Monitoring and Evaluation Programme (EMEP) network. It was found that over the study period the pH of precipitation tended to grow systematically, thus contributing to a decrease of the annual deposition of (H+) ions. The trend lines of changes in the deposition of hydrogen ions have similar slope coefficients, which indicates similar rate of changes. The year with the lowest pH was 1994, in which the mean annual pH was 3.92. In turn, the acidification level was the lowest in 2006 with pH - 4.80. The deposition of hydrogen ions at all stations often exceeded 20 mg·m-2·year-1, and at the WNP station it even reached 70 mg·m-2 in 1994. The deposition of acid-forming ions was also analysed. Predominant among them were sulphate ions, but their deposition showed a declining tendency with time. Their maximum values were recorded in precipitation in the WNP - 707 mg S-SO4·m-2 (2002) and 260 mg N-NO3·m-2 (2007). It was found that the NO3/SO4 eq/eq ratio tended to increase, which is indicative of changes in the composition structure of precipitation. This effect resulted from the decrease in SO2 emission in the Wielkopolska region and from the increase in NOx emission caused by car traffic in the Park and along its border. Calcium dominated among the deposited alkaline cations - its share exceeded 50%. The figures recorded for potassium and calcium deposition by lowland EMEP stations were several times lower than those obtained in the WNP and lower than the mean for Poland. Over the last years one can note a stabilisation in the amount of deposited cations. Kierunki zmian składu chemicznego opadów atmosferycznych w Wielkopolskim Parku Narodowym Przedstawiono wyniki badań chemicznych opadów atmosferycznych, opartych na wieloletnich obserwacjach (1992-2007), prowadzonych w Wielkopolskim Parku Narodowym (WPN) i porównano z rezultatami badań monitoringowych stacji, będących w europejskiej sieci EMEP. Stwierdzono, że w tym czasie pH opadów ulegało systematycznemu podwyższeniu powodując obniżenie rocznej depozycji jonów [H+]. Linie trendu zmian depozycji jonów wodorowych charakteryzują się zbliżonym współczynnikiem nachylenia, co wskazuje na podobne tempo zmian. Rokiem o najniższym pH był 1994 r., w którym średnie roczne pH osiągnęło wartość 3,92. Natomiast rokiem o najmniejszym zakwaszeniu okazał się 2006 r. - pH 4,80. Depozycja jonów wodorowych we wszystkich stacjach monitoringu EMEP w Polsce często przekraczała wartość 20 mg·m-2·rok-1, a w WPN osiągnęła w 1994 r. wartość 70 mg·m-2. Przeanalizowano depozycję jonów kwasotwórczych. Wśród nich dominowała depozycja jonów siarczanowych, wykazując wartości malejące w kolejnych latach. Wartości maksymalne wyniosły - 707 mg S·m-2 (2002) i 260 mg N-NO3·m-2 (2007). Stwierdzono wzrastający współczynnik NO3/SO4 eq/eq, wskazujący na zmiany w strukturze składu anionów. Wśród deponowanych kationów alkalicznych najwyższe wartości przyjmuje wapń stanowiąc ponad 50%. Stacje nizinne EMEP charakteryzują się wartościami depozycji potasu i wapnia kilkukrotnie niższymi niż uzyskane w WPN oraz niższymi niż średnie dla Polski. W ostatnich latach obserwuje się stabilizację ilości deponowanych kationów.