Polycyclic aromatic hydrocarbons in air on small spatial and temporal scales – II. Mass size distributions and gas-particle partitioning

Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72 h in July 2008 using a high time resolution (5 samples per day) with the aim to study gas-particle partitioning, aerosol mass size distributions and to explore the potential of a higher time resolution (4 h-sampling).In the particulate phase the mass median diameters of the PAHs were found almost exclusively in the accumulation mode (0.1–1.0 μm of size). These were larger for semivolatile PAHs than for non-volatile PAHs. Gas-particle partitioning of semivolatile PAHs was strongly influenced by temperature. The results suggest that the Junge–Pankow model is inadequate to explain the inter-species variation and another process must be significant for phase partitioning which is less temperature sensitive than adsorption. Care should be taken when interpreting slopes m of plots of the type log K_p = m log p_L⁰ + b based on 24 h means, as these are found sensitive to the time averaging, i.e. tend to be higher than when based on 12 h-mean samples.     

The use of physiological characteristics for comparison of organic compounds phytotoxicity

The influence of intact (FLT) and photomodified (phFLT) fluoranthene (0.05, 0.5 and 5 μmol l⁻¹) and herbicide Basagran (5, 20, 35 and 50 nmol l⁻¹) on the germination, growth of seedlings and photosynthetic processes in pea plants (Pisum sativum L., cv. Garde) was investigated. The germination was significantly inhibited already by the lowest concentration (0.05 μmol l⁻¹) of FLT and phFLT, while Basagran caused inhibition only in higher concentrations (35 and 50 nmol l⁻¹). The growth of roots was significantly inhibited by higher concentration 5 μmol l⁻¹ of both FLT and phFLT and the shoot of seedlings was significantly influenced only by photomodified form. The length of root and shoot was inhibited already by concentration 5 nmol l⁻¹ of Basagran. Organic compounds applied on chloroplasts suspension influenced primary photochemical processes of photosynthesis. In chlorophyll fluorescence parameters, the significant increase of F₀ values and the decrease of F_V/F_M and Φ_II values by application of FLT (0.5 and 5 μmol l⁻¹) and phFLT (0.05, 0.5 and 5 μmol l⁻¹) was recorded. The maximum capacity of PSII (F_V/F_M) was influenced by the highest (50 nmol l⁻¹) and the effective quantum yield of PSII (Φ_II) already by the lowest (5 nmol l⁻¹) concentration of Basagran. Hill reaction activity decreased and was significantly inhibited by higher concentration (0.5 and 5 μmol l⁻¹) of FLT and phFLT and already by the lowest concentration (5 nmol l⁻¹) of Basagran.     

Trends in background levels of persistent organic pollutants at Kosetice observatory, Czech Republic.2) Part II. Aquatic and terrestrial environments 1996-2005

A multimedia sampling of ambient air, wet deposition, surface water, sediment, soil and biota has been performed at Kosetice background observatory in the southern Czech Republic since 1988. An integrated monitoring approach was applied to assess the current state, anthropogenic impacts, and possible future changes of terrestrial and freshwater environments. Average PCB concentrations in the individual matrices calculated from ten years of sampling on multiple sites varied between 2 ng g(-1) in sediment and 7 ng g(-1) in soil or moss. DDT concentrations were lower in moss and needles (2 ng g(-1) and 4 ng g(-1), respectively) than in sediment (11 ng g(-1)) and soil (20 ng g(-1)), while the HCH level was higher in moss and needles (5 ng g(-1) and 6 ng g(-1), respectively) than in soil or sediment (1 ng g(-1) and 2 ng g(-1), respectively). The highest average level of PAHs was found in soil (600 ng g(-1)), while it was lower in needles (230 ng g(-1)), moss (210 ng g(-1)) or sediment (210 ng g(-1)). Time related trends of concentration levels of persistent organic pollutants in all matrices were investigated. Moss and needle trend patterns resembled those of the ambient air, showing a slight concentration decrease of all compounds, except for hexachlorobenzene. The soil, water and sediment concentrations showed a similar decrease of PAHs, PCBs, and HCHs, but there was no clear trend for DDTs and HCB.     

Metal/metalloid contamination and isotopic composition of lead in edible mushrooms and forest soils originating from a smelting area

High metal contents in edible mushrooms growing in severely contaminated industrial areas pose an important toxicological risk. In the presented study, trace element (Pb, Cd, Zn, Cu, Ag, As, Se) contents were determined in caps and stipes of three different edible mushroom species (Boletus edulis Bull. Fr., Xerocomus badius Fr. Gilb., Xerocomus chrysenteron Bull. Quél.). Additionally, information about the chemical fractionation of metals in separate soil horizons and Pb isotopic data from soils and fruiting bodies allowed a more detailed insight on the uptake mechanisms of metals by the studied mushroom species. Total metal and metalloid concentrations in the organic soil horizons reached 36234 mg Pb kg(-1); 11.9 mg Cd kg(-1); 519 mg Zn kg(-1); 488 mg Cu kg(-1); 25.1 mg Ag kg(-1); 120 mg As kg(-1) and 5.88 Se mg kg(-1). In order to evaluate the accumulation capacity of the studied species, bioconcentration factors (BCF) were calculated for separate trace elements. For selected metals (Pb, Cd, Zn, Cu), a modified BCF calculation (using EDTA-extractable concentrations of metals in soil) was proposed. High contents of Pb (up to 165 mg kg(-1)) and Cd (up to 55 mg kg(-1)) exceeded all the regulatory limits in all the studied species. This was also the case for Se (up to 57 mg kg(-1)) in B. edulis. Intensive consumption of this species grown in such polluted areas can therefore pose toxicological risks for human health. A novel finding was that X. badius can act as an Ag accumulating species when grown at polluted sites due to the high concentrations of Ag (up to 190 mg kg(-1)) in caps. Pb isotopic data showed that Pb originating from the recent air pollution control residues is present mainly in the exchangeable/acid-extractable fraction of the organic horizons and is taken up by fruiting bodies; especially in the case of B. edulis, where fast Pb accumulation occurs. Due to the high species-dependent variations of metal contents, the studied mushrooms are not suitable as bioindicators of environmental pollution.     

HPLC-FLD determination of 4-nonylphenol and 4-<Emphasis Type="Italic">tert</Emphasis>-octylphenol in surface water samples

A simple, sensitive and reliable HPLC-FLD method for the routine determination of 4-nonylphenol, 4-NP and 4-tert-octylphenol, 4-t-OP content in water samples was developed. The method consists in a liquid–liquid extraction of the target analytes with dichloromethane at pH  3.0–3.5 followed by the HPLC-FLD analysis of the organic extract using a Zorbax Eclipse XDB C8 column, isocratic elution with a mixed solvent acetonitrile/water 65:35, at a flow rate of 1.0 mL/min and applying a column temperature of 40°C. The method was validated and then applied with good results for the determination of 4-NP and 4-t-OP in Ialomi?a River water samples collected each month during 2006. The concentration levels of 4-NP and 4-t-OP vary between 0.08–0.17 μg/L with higher values of 0.24–0.37 μg/L in the summer months for 4-NP, and frequently <0.05 μg/L but also between 0.06–0.09 μg/L with higher values of 0.12–0.16 μg/L in July and August for 4-t-OP and were strongly influenced by sesonial and anthropic factors. The method was also applied on samples collected over 2 years 2007 and 2008 from urban wastewaters discharged into sewage or directly into the rivers by economic agents located in 30 Romanian towns. Good results were obtained when the method was used for analysis of effluents discharged into surface waters by 16 municipal wastewater treatment plants, during the year 2008.     

Flood monitoring in a semi-arid environment using spatially high resolution radar and optical data

The geographic term "Niger Inland Delta" stands for a vast plain of approximately 40,000 km(2), which is situated in the western Sahel (Republic of Mali). The Inland Delta is affected by yearly inundation through the variable water levels of the Niger-Bani river system. Due to a good availability of (surface) water, the ecosystem at the Niger Inland Delta serves as resting place stop-over for many migrating birds and other wildlife species as well as economic base for farmers and pastoral people. To foster the sustainable usage of its natural resources and to protect this natural heritage, the entire Niger Inland Delta became RAMSAR site in 2004. This paper aims to test to which extent texture analysis can improve the quality of flood monitoring in a semi-arid environment using spatially high resolution ASAR imaging mode data. We found the Gray Level Dependence Method (GLDM) was most suitable proceeding for our data. Several statistical parameters were calculated via co-occurrence matrices and were used to classify the images in different gradation of soil moisture classes. In a second step we used additional information from spatially high resolution optical data (ASTER) to improve the separability of open water areas from moisture/vegetated areas.     

Kosetice, Czech Republic--ten years of air pollution monitoring and four years of evaluating the origin of persistent organic pollutants

The regional observatory Kosetice is a central European background station. Unique continuous monitoring from 1988 on is held here. POP (persistent organic pollutant) concentration values of air samples from Kosetice taken between 1996 and 2005 were statistically processed. Values of Czech ambient air quality standards were not exceeded. Concentrations of polycyclic aromatic hydrocarbons reached two maxima, in 1996 and 2001-2002. Polychlorinated biphenyls concentrations reached the highest values in 1997 and 1998 and hexachlorocyclohexanes concentrations in 1998. DDTs, hexachlorobenzene and pentachlorobenzene were analysed as well. Long-range transport of pollutants between 2002 and 2005 was evaluated using the Potential Source Contribution Function hybrid receptor model. Indicated potential source areas of PCBs coincide with many well-known urban and industrialised areas, while the indicated potential source areas of HCHs and DDTs coincide with many agricultural and/or forested regions and the potential source areas of HCB comprise all land use types.     

Residues of organochlorinated pesticides in soils from the Czech Republic

National POPs inventories carried out currently in many countries as a part of the implementation of Stockholm Convention revealed the need for detailed information about a distribution of pollutants in various regions. Screening for the residues of selected organochlorinated pesticides (chlordane, heptachlor, dieldrin, aldrin, endrin, isodrin, endosulfan I, endosulfan II, methoxychlor, mirex) in soil and biotic samples from the Czech Republic was performed. Although these pesticides have never been used in large quantities in this region, results indicate that their residues still persist in the top layer soils more than 20 years after they have been banned. The fact that their soil concentrations in the mountains are generally higher than those in agricultural areas, and detection of the traces of pesticides that have never been used in this region suggest on their occurrence in soils due to the atmospheric redistribution rather than as a result of direct application.