Trace element distribution in the snow cover from an urban area in central Poland.

This work presents the first results from winter field campaigns focusing on trace metals and metalloid chemistry in the snow cover from an urbanized region in central Poland. Samples were collected between January and March 2013 and trace element concentrations were determined using GF-AAS. A large inter-seasonal variability depending on anthropogenic emission, depositional processes, and meteorological conditions was observed. The highest concentration (in µg L(-1)) was reported for Pb (34.90), followed by Ni (31.37), Zn (31.00), Cu (13.71), Cr (2.36), As (1.58), and Cd (0.25). In addition, several major anthropogenic sources were identified based on principal component analysis (PCA), among which the most significant was the activity of industry and coal combustion for residential heating. It was stated that elevated concentrations of some trace metals in snow samples were associated with frequent occurrence of south and southeast advection of highly polluted air masses toward the sampling site, suggesting a large impact of regional urban/industrial pollution plumes.

From soil to leaves--aluminum fractionation by single step extraction procedures in polluted and protected areas.

The paper presents the fractionation of aluminum in the samples of soil and plants of different species using a selective single-step extraction method. The study was conducted in the area located near a chemical plant, which for many years served as a post-crystallization leachate disposal site storing chemical waste (sector I), and in the area around the site: in Wielkopolski National Park, Rogalin Landscape Park and toward the infiltration ponds at the "Debina" groundwater well-field for the city of Poznan (Poland) (sector II). The results of aluminum fractionation in samples of soil, leaves and plants showed heavy pollution with aluminum, especially in the water soluble aluminum fraction - Alsw (maximum concentration of aluminum in soil extract was 234.8 ± 4.8 mg kg(-1), in the leaves of Betula pendula it was 107.4 ± 1.8 mg kg(-1) and in the plants of Artemisia vulgaris (root) and Medicago sativa (leaves) it amounted to 464.7 ± 10.7 mg kg(-1)and 146.8 ± 1.2 mg kg(-1) respectively). In addition, the paper presents the problem of organic aluminum fractionation in biological samples and it shows the relationship between aluminum concentration in soil and the analysed woody and herbaceous species.

Determination of aluminium in groundwater samples by GF-AAS, ICP-AES, ICP-MS and modelling of inorganic aluminium complexes.

The paper presents the results of aluminium determinations in ground water samples of the Miocene aquifer from the area of the city of Poznan (Poland). The determined aluminium content amounted from <0.0001 to 752.7 µg L(-1). The aluminium determinations were performed using three analytical techniques: graphite furnace atomic absorption spectrometry (GF-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of aluminium determinations in groundwater samples for particular analytical techniques were compared. The results were used to identify the ascent of ground water from the Mesozoic aquifer to the Miocene aquifer in the area of the fault graben. Using the Mineql+ program, the modelling of the occurrence of aluminium and the following aluminium complexes: hydroxy, with fluorides and sulphates was performed. The paper presents the results of aluminium determinations in ground water using different analytical techniques as well as the chemical modelling in the Mineql+ program, which was performed for the first time and which enabled the identification of aluminium complexes in the investigated samples. The study confirms the occurrence of aluminium hydroxy complexes and aluminium fluoride complexes in the analysed groundwater samples. Despite the dominance of sulphates and organic matter in the sample, major participation of the complexes with these ligands was not stated based on the modelling.

Atmospheric particulate mercury at the urban and forest sites in central Poland.

Particulate mercury concentrations were investigated during intensive field campaigns at the urban and forest sites in central Poland, between April 2013 and October 2014. For the first time, quantitative determination of total particulate mercury in coarse (PHg2.2) and fine (PHg0.7) aerosol samples was conducted in Poznan and Jeziory. The concentrations in urban fine and coarse aerosol fractions amounted to < MDL ± 77.1 pg m(-3) and < MDL ± 604.9 pg m(-3), respectively. Aerosol samples collected during the whole study period showed statistically significant differences for particulate mercury concentrations. A strong impact of meteorological conditions (wind velocity, air mass direction, air temperature, and precipitation amount) on particulate mercury concentrations was also observed. In particular, higher variation and concentration range of PHg0.7 and PHg2.2 was reported for wintertime measurements. An increase in atmospheric particulate mercury during the cold season in the study region indicated that coal combustion, i.e., residential and industrial heating, is the main contribution factor for the selected particle size modes. Coarse particulate Hg at the urban site during summer was mainly attributed to anthropogenic sources, with significant contribution from resuspension processes and long-range transport. The highest values of PHg0.7 and PHg2.2 were found during westerly and southerly wind events, reflecting local emission from highly polluted areas. The period from late fall to spring showed that advection from the southern part of Poland was the main factor responsible for elevated Hg concentrations in fine and coarse particles in the investigated region. Moreover, September 2013 could be given as an example of the influence of additional urban activities which occurred approx. 10 m from the sampling site-construction works connected with replacement of the road surface, asphalting, etc. The concentrations of particulate Hg (>600.0 pg m(-3)) were much higher than during the following months when any similar situation did not occur. Our investigations confirmed that Hg in urban aerosol samples was predominantly related to local industrial and commercial emissions, whereas the main source of Hg in particulate matter collected at the forest site was connected with regional anthropogenic processes. This paper provides the results of the first long-term measurements of size-fractionated particulate mercury conducted in central Poland, which could be an important insight into atmospheric Hg processes within such a scarcely investigated part of Europe.

Assessment of potentially reactive pools of aluminium in poor forest soils using two methods of fractionation analysis.

The research was carried out in a pine-covered area of the Wielkopolski National Park (Poland), for years exposed to acid rain. The soils under study are sands and loamy sands with a pH of 3.3-4.4. To assess potentially reactive pools of aluminium in those soils, two methods were employed: sequential and single extraction. For the exchangeable form the results obtained by single extraction using KCl greatly exceeded the figures yielded by sequential extraction, in which the conditions under which the process was executed (pH 7) led to an underestimation of the results. The soil profile displayed a lithogenically dichotomous structure which was reflected in the aluminium content, especially in Al extracted by pyrophosphate (single extraction) and in the so-called oxidisable fraction (sequential extraction). In both cases there was a jump in Al concentrations resulted from the release of aluminium from interlayer spaces of clay minerals. The labile percentage obtained for mean values in the profile amounted from 8.1% for single extraction to 12.1% for sequential extraction, which may indicate the metal's considerable pool of potentially reactive aluminium. Single extraction seems to be more reliable in evaluating Al forms.

Seasonal variations of dissolved organic carbon in precipitation over urban and forest sites in central Poland.

Spatial and temporal variability of carbon species in rainwater (bulk deposition) was studied for the first time at two sites located in urban area of Poznan City and protected woodland area (Jeziory), in central Poland, between April and December 2013. The mean concentration of total carbon (TC) for the first site was 5.86 mg L(-1), whereas for the second, 5.21 mg L(-1). Dissolved organic carbon (DOC) concentration accounted for, on average, 87 and 91 % of total carbon in precipitation at urban and non-urban sites, respectively. Significant changes in TC concentrations in rainwater were observed at both sites, indicating that atmospheric transformation, transport, and removal mechanisms of carbonaceous particles were affected by seasonal fluctuations in biogenic/anthropogenic emission and meteorological conditions (i.e., precipitation height and type, atmospheric transport). During the warm season, the DOC concentration in rainwater was mostly influenced by mixed natural and anthropogenic sources. In contrast, during the cold season, the DOC concentration significantly increased mainly as a result of anthropogenic activities, i.e., intensive coal combustion, domestic wood burning, high-temperature processes, etc. In addition, during the winter measurements, significant differences in mean DOC concentration (Kruskal-Wallis test, p < 0.05) were determined for rain, mixed rain-snow, and snow samples. It was found that rainwater TOC concentration measured in Poznan and Jeziory reflected a combination of local, regional, and distant sources. Backward trajectory analysis showed that air masses advected from polluted regions in western Europe largely affect the DOC amount in rainwater, both at urban and non-urban sites. These data imply that carbonaceous compounds are of crucial importance in atmospheric chemistry and should be considered as an important parameter while considering wet deposition, reactions with different substances, especially over polluted environments.

Mercury in precipitation over the coastal zone of the southern Baltic Sea, Poland.

An investigation of atmospheric mercury was conducted in the urban coastal zone of the Gulf of Gdansk (Baltic Sea, Poland) in 2008. Rainwater samples were collected in bulk samplers and Hg concentration was determined using AAS method. Total mercury concentration ranged from 1.9 to 14.8 ng l(-1) (the mean was 8.3 ng l(-1) with standard deviation ±3.7), out of which about 34 % were water-soluble Hg(II) forms. Distribution of Hg species in rainwater was related to both the emission source and the atmospheric processes. During the sampling period, two maxima of Hg concentration in precipitation were observed: the first in the cold season and the second one in the warm season. Elevated concentrations of Hg in wintertime precipitation were generally the result of local urban atmospheric emission connected with the following anthropogenic sources: intensive combustion of fossil fuels in domestic furnaces, individual power/heat generating plants, and motor vehicles. During summertime, Hg° re-emitted from contaminated land and sea surfaces was photochemically oxidized by active atmospheric substances (e.g., hydroxyl radicals, hydrogen peroxide, halogens) and could be an additional source of atmospherically deposited Hg. The results presented in this work indicate that rainwater Hg concentration and deposition values are not much higher in comparison with other urban locations along the Baltic Sea basin and other coastal cities. However, the elevated mercury concentration in rainwater and, consequently, higher deposition ratio could appear occasionally as an effect of intensive anthropogenic emissions (domestic heating) and/or photochemical reactions.

Development of a new analytical method for online simultaneous qualitative determination of aluminium (free aluminium ion, aluminium-fluoride complexes) by HPLC-FAAS.

The paper presents a novel method for simultaneous online examination of inorganic forms of aluminium: AlF(2)(+), AlF(2+,) and Al(3+) by means of the high performance liquid chromatography hyphenated with a detection by the atomic absorption spectrometry with flame atomization (HPLC-FAAS) without post-column reaction. The application of optimization procedure conditions of chromatographic separation of inorganic forms of aluminium was achieved by the analytical column IonPac CS5A (Dionex) with guard column IonPac CG5A (Dionex) and an aqueous ammonium chloride mobile phase, at pH about 3 with gradient elution. The separation of Al forms with nominal charge of 1+, 2+, 3+ required a run time of less than 8 min during a single analysis. The proposed method has been successfully used for the examination of aluminium forms formation AlF(n)((3-n)+) in environmental samples.

A new tool for inorganic nitrogen speciation study: simultaneous determination of ammonium ion, nitrite and nitrate by ion chromatography with post-column ammonium derivatization by Nessler reagent and diode-array detection in rain water samples.

The paper presents a new method for a simultaneous determination of inorganic nitrogen species in the oxidized (NO2-, NO3-) and reduced (NH4+) form in rain water samples. The method is based on a system of nitrogen species separation employing ion exchange and diode-array detection. The ions are separated in a strong ion-exchanger, nitrites and nitrates are determined directly at 208 and 205 nm, respectively, while the ammonium ions are determined in the column hold-up time after a post-column derivatization by the Nessler reagent, at 425 nm. The use of a diode-array detector permits a simultaneous identification of the inorganic nitrogen species in 8 min. The detection limits obtained are: NO2-, 0.1 mg L(-1); NO3-, 0.05 mg L(-1); NH4+, 1 mg L(-1). The method proposed has been successfully used for speciation analysis of inorganic nitrogen in precipitation.