Gas–particle partitioning of persistent organic pollutants in the Western Balkan countries affected by war conflicts

Background, aim, and scope  

Bombing and destruction of the industrial and military targets accompanied by complete or incomplete combustion during the war conflict and NATO operation in former Yugoslavia caused the emission of persistent organic pollutants into the atmosphere, water, and soil. A total of 129 ambient air samples from 24 background, urban, and industrial sites, including hot spots, were collected to assess a gas–particle partitioning behavior of various persistent organic pollutants.     

Solubilities of selected organic electronic materials in pressurized hot water and estimations of aqueous solubilities at 298.15 K

Increasing production and disposal of organic light-emitting diode (OLED) displays for smartphones and tablets may have impact on the environment depending on the aqueous solubility of the pertinent chemicals. Here, aqueous solubilities are presented for several compounds, mostly aromatic amines, used as hole transport materials in the OLED displays. Solute selection includes 1,4-bis(diphenylamino)benzene, tetra-N-phenylbenzidine, 4,4′-bis(N-carbazolyl)-1,1′-biphenyl, 1,3,5-tris(diphenylamino)benzene, and 9,10-bis(phenylethynyl)anthracene. The solubilities are those in pressurized hot water (PHW), i.e., measured at elevated temperature (up to 260 °C) and pressure. The semi-quantitative estimates of room-temperature solubilities of the solutes have been obtained from extrapolations of the solubilities in PHW. For the compounds studied, the estimated aqueous solubilities at room temperature do not exceed 2 × 10^?11 g of the solute per 1 kg of water. Aqueous solubilities of triphenylamine have also been measured and used to upgrade a recent group-contribution model of aqueous solubilities of organic nonelectrolytes with the parameters for the nitrogen atom in aromatic amines.     

Alterations in the rabbit lymphoid tissue after bendiocarb administration

Various pesticides have immuno-suppressive effects, and thus the organisms become responsive to viral, bacterial and parasitic diseases and neoplasm. The aim of the study was to observe the structure of the small intestine (height of enterocytes and crypts), mucosal lymphoid tissue (Payer's patches, lymphocytes in lamina propria) and a lymph node after administration of bendiocarb (2,2-dimethyl-1,3-benzodioxol-4-yl-methylcarbamate) on days 3, 10, 20, 30 and 60 of the experiment. The height of the observed enterocytes showed an increasing tendency. On days 20, 30 and 60 we also observed an increase in diameter of crypts located in intestinal epithelium. The number of cells in lamina propria mucosae was significantly reduced on days 20 and 30 after administration of bendiocarb. Observations of the lymph node showed that on days 10 and 20 there was a significant increase in relative volume of medulla at the expense of the relative volume of the cortex and a decrease in the number of lymphocytes. However, we recorded an increase in diameter of lymphocytes. The intracellular parasite Toxoplasma gondii (T. gondii) belongs to the most common pathogenic parasites in the world and it can cause serious health complications in pregnant and immunodeficient individuals. DNA isolation, standard polymerase chain reaction (PCR) and visualization in a 2.5 % agarose gel, the presence of DNA T. gondii was detected in no examined rabbit brain samples. Using real time PCR T. gondii DNA was detected and quantified in the three rabbit brain samples (10 %).     

Micronucleus frequency in sheep lymphocytes after in vitro exposure to fungicide tolylfluanid

The fungicide tolylfluanid (N - dichlorofluoromethylthio-N′, N - dimethyl - N - p - tolylsulfamide), was investigated by cytokinesis-block micronucleus assay. Tolylfluanid at the lowest concentration (1 × 10^{? 6}mol L^{? 1})did not influence significantly the frequency of micronuclei in sheep lymphocyte cultures in comparison with control (32.33 ± 3.51/1000 binucleated cells versus 30.33 ± 2.82/1000 binucleated cells in dimethylsulfoxide (DMSO) control, P = 0.44). Higher tolylfluanid concentrations (1 × 10^{? 4} and, 1 × 10^{? 5} mol L^{? 1}) resulted in a significant dose-dependent increase in the number of micronuclei in comparison with control (74.00 ± 13.00/1000 binucleated cells and 52.67 ± 10.12/1000 binucleated cells versus 30.33 ± 2. 82/1000 binucleated cells in DMSO control, P = 0.005 and 0.02, respectively, ANOVA followed by Tukey test P < 0.05). Many of the treated cells also possessed multiple micronuclei. Tolylfluanid did not affect the nuclear division index at all treatment concentrations. Our in vitro results thus demonstrate that tolylfluanid had a significant genotoxic effect at only the highest concentration tested.     

Recycling of EDTA solution after soil washing of Pb, Zn, Cd and As contaminated soil

Soil washing with EDTA is known to be an effective means of removing toxic metals from contaminated soil. A practical way of recycling of used soil washing solution remains, however, an unsolved technical problem. We demonstrate here, in a laboratory scale experiment, the feasibility of using acid precipitation to recover up to 50% of EDTA from used soil washing solution obtained after extraction of Pb (5330 mg kg⁻¹), Zn (3400 mg kg⁻¹), Cd (35 mg kg⁻¹) and As (279 mg kg⁻¹) contaminated soil. Up to 100% of EDTA residual in the washing solution and 100%, 97%, 98% and 100% of initial Pb, Zn, Cd and As concentration in the solution, respectively, were removed in an electrolytic cell using a graphite anode. We employed the recovered EDTA and treated washing solution to prepare recycled soil washing solution with the same potential for extracting toxic metals from soil as the original. The efficiency of soil washing depends on the EDTA concentration. Using twice recycled 30 mmol EDTA kg⁻¹ soil, we removed 44%, 20%, 53% and 61% of Pb, Zn, Cd and As, respectively, from contaminated soil.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Seasonal Differences in the Levels of Gaseous Air Pollutants in the Vicinity of a Waste Dump

Hydrogen sulphide, ammonia, nitrogen dioxide, mercaptans and sulphur dioxide (H₂S, NH₃, NO₂, R-SH, SO₂) concentrations were measured at the location in the vicinity of the waste dump to determine the air pollution level of these pollutants prior to the operation of the Mobile Thermal Treatment Plant. Samples were collected over one year period. Seasonal differences, and the influence of meteorological parameters (temperature, relative humidity, pressure and wind direction) on the air pollution levels were studied. Results show relatively low concentrations of H₂S, NO₂, R-SH and SO₂, while NH₃ levels were higher compared to the guideline values. Good weather conditions (high air pressure and low relative humidity) are connected to long range transport of NO₂, while higher temperatures result in elevated NH₃ and R-SH concentrations. Because of the predominant northeast wind direction (the same as the waste dump direction), the contribution of air pollution from the direction of the waste dump at the measuring site is significant, but that does not necessarily mean that the pollutants originated from that source.     

The reproduction of Enchytraeus sp.—technical improvement for the counting of juveniles

Soil-dwelling annelids of the genus Enchytraeus are used in ecotoxicology for testing of chemicals mixed in artificial soil or for testing of wastes and soils of unknown quality. ISO 16387 describes a method for determining the effects of substances or contaminated soils on survival and reproduction of Enchytraeus albidus or of the smaller species Enchytraeus buchholzi or Enchy-traeus crypticus. After the total test duration of 6 (or 4)?weeks, the juveniles hatched in the meantime are counted. There are several possible extraction techniques, which are always followed by counting the juveniles by hand, but none of them seems easy to handle. We proposed a new modification of the worm extraction method using flotation of fixed and stained juveniles followed by taking a photograph. The digital image of the juveniles is evaluated by computer processing. It makes the counting of juveniles much easier and less labor intensive.     

Fate of saline ions in a planted landfill site with leachate recirculation

Recirculation of leachate on a covered landfill site planted with willows or other highly evapotranspirative woody plants is an inexpensive option for leachate management. In our study, a closed landfill leachate recirculation system was established on a rehabilitated municipal solid waste landfill site with planted landfill cover. The main objective of the study was to evaluate the sustainability of the system with regard to high hydraulic loads of the landfill leachate on the landfill cover and high concentrations of saline ions, especially potassium (K⁺), sodium (Na⁺) and chloride (Cl^?), in leachate.The results of intensive monitoring, implemented during May 2004 and September 2007, including leachate, soil and plant samples, showed a high sustainability of the system regarding saline ions with the precipitation regime of the studied region. Saline ion concentrations in leachates varied between 132 and 2592 mg Cl^? L^?1, 69 and 1310 mg Na⁺ L^?1 and between 66 and 2156 mg K⁺ L^?1, with mean values of 1010, 632 and 686 mg L^?1, respectively. Soil salinity, measured as soil electrical conductivity (EC), remained between 0.17 and 0.38 mS cm^?1 at a depth between 0 and 90 cm. An average annual precipitation of 1000 mm provided sufficient leaching of saline ions, loaded by irrigation with landfill leachate, from the soil of the landfill cover and thus prevented possible salinity shocks to the planted willows.