Toxicity and biodegradability of sulfonamides and products of their photocatalytic degradation in aqueous solutions

The photocatalytic degradation of sulfacetamide, sulfathiazole, sulfamethoxazole and sulfadiazine in water solutions during their illumination of UV radiation (lambda(max) 366 nm) with TiO2 catalyst was examined. The growth-inhibition effect of sulfonamides and intermediate products theirs photodegradation was investigated in aqueous solution with the green alga Chlorella vulgaris. The biodegradability of the investigated compounds was determined in the illuminated solutions and is expressed as Biochemical Oxygen Demand. It was found that all of the investigated sulfonamides in the initial solutions were resistant to biodegradation and were toxic relative to C. vulgaris. The toxicity (EC50 values) relative to C. vulgaris increased in the following order sulfacetamide, sulfathiazole, sulfamethoxazole, sulfadiazine. All of the investigated sulfonamides undergo photocatalytic degradation. The toxicity of intermediate products of the sulfonamides degradation was significantly lower than the toxicity of sulfonamides in the initial solutions and was dependent on illumination time and degradation rate. The intermediate products of photocatalysis in contrast to the initial sulfonamides, might be mineralized using biological methods.     

LC-MS/MS method validation for determination of selected neonicotinoids in groundwater for the purpose of a column experiment

The work was carried out to develop and validate a method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous detection and quantification of five neonicotinoid insecticides: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam in groundwater samples for the purpose of a further column experiment. This experiment will be used to analyze breakthrough curves of neonicotinoids under a saturated water flow to set transport parameters, where the reliability of the results of chemical analysis plays an important role. The validation was performed in a concentration range from 0.09?µg L^?1 to 100?µg L^?1 using an Infinity 1290 (Agilent, USA) chromatograph coupled with a QTrap 5500 mass spectrometer (Sciex, Canada). The calibration curves were obtained on the basis of the results of six standard solution analyses. Linearity was not lower than 0.998. The limit of detection was set at the lowest concentration which can be determined with an acceptable accuracy and precision. All pesticides had recoveries in the range 85–109% with relative standard deviation values less than 8.1%. The estimated measurement uncertainty did not exceed 30%, so the LC-MS/MS method fits for the intended purpose.     

In vitro effects of various xenobiotics on Fusarium spp. strains isolated from cereals

This study aimed to determine the susceptibility of Fusarium spp. strains isolated from cereals to selected heavy metals, fungicides and silver nanoparticles. The experiments were conducted using 50 Fusarium strains belonging to five species: F. graminearum, F. culmorum, F. oxysporum, F. sporotrichioides and F. avenaceum. The strains were found to be highly resistant to Pb²⁺ and Zn²⁺. Medium resistance to Cu²⁺ and Mn²⁺ and low resistance to Cd²⁺ and Fe³⁺ was also observed. Among the tested fungicides, formulations containing azoxystrobin, prochloraz and tebuconazole proved to be the most effective in inhibiting the growth of fungi, as they affected fungal growth in each of the applied doses. Susceptibility of Fusarium spp. to nanosilver, demonstrated in this study, shows the legitimacy of using nanostructures as fungicidal agents. The results confirm high diversity of the analyzed fungal species in terms of susceptibility to the tested substances, and encourage to continue research on the resistance of Fusarium spp. to various fungicidal agents.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in cord blood from women in Poland

The purpose of this study was to assess human exposure in the prenatal period to selected PBDEs (BDE-47, BDE-99, BDE-153) and PCBs (CB-77, CB-101, CB-118, CB-126, CB-138, CB-153, CB-170, CB-180) basing on the analysis of these compounds in cord blood. The experimental material consisted of 89 cord blood samples taken from women resident in Warsaw and its vicinity. In over 90% of all tested samples the presence of congeners CB-153, CB-138, CB-180 and BDE-47 was identified. The least frequently found were CB-126 and BDE-153, which were present at relatively low concentration levels. Among all analysed PCBs, the highest average concentrations were found in the case of congeners CB-138 (11.8 ng/g of fat) and CB-153 (43.4 ng/g of fat), whereas the lowest was in the case of CB-170 (0.4 ng/g of fat) and CB-126 (0.1 ng/g of fat). In the case of PBDEs the greatest share in the total concentration was that of the congeners BDE-47 and BDE-99, whereas the smallest share was that of the higher brominated congener BDE-153. These results suggest that human exposure to the examined compounds begins already in the period of intrauterine life. The comparison of our own results with the findings of other authors indicates that the PCBs and PBDEs levels in cord blood of women living in Poland do not differ from the respective concentrations in cord blood of other female inhabitants of Europe.     

The sensitivity of soil enzymes,microorganisms and spring wheat to soil contamination with carfentrazone-ethyl

Herbicides pose a significant threat to the natural environment, in particular in soils that are most exposed to plant protection agents. Prolonged herbicide use leads to changes in soil metabolism and decreases soil productive potential. In this study, the influence of carfentrazone-ethyl (CE) on the microbiological and biochemical properties of soil and the yield of Triticum aestivum L. was evaluated. Carfentrazone-ethyl was applied to sandy loam (pH_KCl – 7.0) in doses of 0.000, 0.264, 5.280, 10.56, 21.18, 42.24, 84.48 and 168.96 µg kg^?1 DM soil. Soil samples were subjected to microbiological and biochemical analyses on experimental days 30 and 60. Carfentrazone-ethyl disrupted the biological equilibrium in soil by decreasing the abundance and biodiversity of soil-dwelling microorganisms, the activity of soil enzymes, the values of the biochemical activity indicator and spring wheat yields. Carfentrazone-ethyl had the most adverse effects when applied in doses many fold higher than those recommended by the manufacturer. The toxic effects of CE were also determined by its soil retention time. Soil treated with CE was characterized by higher counts of oligotrophic bacteria, organotrophic bacteria, bacteria of the genus Azotobacter, actinomycetes and fungi on day 60, and spore-forming oligotrophic bacteria on day 30. The activity of dehydrogenases, urease, alkaline phosphatase and β-glucosidase was higher on day 30 than on day 60.     

Do morphometric parameters and geological conditions determine chemistry of glacier surface ice? Spatial distribution of contaminants present in the surface ice of Spitsbergen glaciers (European Arctic)

The chemism of the glaciers is strongly determined by long-distance transport of chemical substances and their wet and dry deposition on the glacier surface. This paper concerns spatial distribution of metals, ions, and dissolved organic carbon, as well as the differentiation of physicochemical parameters (pH, electrical conductivity) determined in ice surface samples collected from four Arctic glaciers during the summer season in 2012. The studied glaciers represent three different morphological types: ground based (Blomlibreen and Scottbreen), tidewater which evolved to ground based (Renardbreen), and typical tidewater glacier (Recherchebreen). All of the glaciers are functioning as a glacial system and hence are subject to the same physical processes (melting, freezing) and the process of ice flowing resulting from the cross-impact force of gravity and topographic conditions. According to this hypothesis, the article discusses the correlation between morphometric parameters, changes in mass balance, geological characteristics of the glaciers and the spatial distribution of analytes on the surface of ice. A strong correlation (r = 0.63) is recorded between the aspect of glaciers and values of pH and ions, whereas dissolved organic carbon (DOC) depends on the minimum elevation of glaciers (r = 0.55) and most probably also on the development of the accumulation area. The obtained results suggest that although certain morphometric parameters largely determine the spatial distribution of analytes, also the geology of the bed of glaciers strongly affects the chemism of the surface ice of glaciers in the phase of strong recession.     

Potential toxicity of leachate from the municipal landfill in view of the possibility of their migration to the environment through infiltration into groundwater

Environmental Geochemistry and Health - Leachate from landfills is a product of complex biological and physicochemical processes occurring during waste storage. In the present study, the toxicity...     

Spatial distribution of major and trace elements in the water of Swarzędzkie Lake (Poland)

In order to characterize the contamination of the Swarzedzkie Lake and generate elemental distribution patterns 18 elements have been determined in samples of water, taken just above the bottom sediments. Analyses were carried out using two instrumental techniques - ICP-OES and ICP-MS. Two main sources of contamination were identified - diffuse pollution from agriculture and stormwater from the town. Three separate groups of elements were distinguished using cluster analysis and two groups using principal component analysis. These three groups are characterized as geogenic elements (Ag, As, Mg and Sb), elements supplied by the agricultural catchment (Ca, Mn, Sr, Na, K and Al) and elements originated from the urban contamination (Ni, Cr, Cu, Fe, V, Ba, Zn and Pb). PCA differentiated the above group of urban elements from the rest, originated from diffuse sources, with exception of alluminium, which was situated between two distinguished groups.     

Differentiation in low molecular weight organic acids exudation into rhizosphere and their creation in Ulmus laevis Pall organs treated by As – pot experiment

Two-year old Ulmus laevis Pall (U. laevis) seedlings were cultivated in a three-month hydroponic experiment with inorganic (aresenite – As(III) and arsenate – As(V)) and organic (dimethylarsenic acid – DMA(V)) arsenic forms, at 0.06 and/or 0.6?mM concentrations. Further, the profile and content of total low molecular weight organic acids (LMWOAs) were investigated in the rhizosphere, roots and leaves of U. laevis. Obtained results showed that the addition of As(III) or As(V) individually or in a mixture led to increased LMWOAs concentration in the rhizosphere, especially of oxalic and malonic acids, in comparison to the control, while in roots the overall content of the profiled LMWOAs decreased. In both rhizosphere and roots, addition of the DMA(V) form resulted in the inhibition of LMWOAs exudation into the rhizosphere and their creation in plant roots. Leaves were characterised by a higher content of LMWOAs than in the rhizosphere and roots for all experimental systems, where the profile and content of LMWOAs was strictly correlated with the analysed As forms. Our study indicated that creation of LMWOAs in U. laevis organs and their exudation to the rhizosphere could be responsible for the As toxicity tolerance of the plants.     

Dissipation of S-metolachlor in plant and soil and effect on enzymatic activities

The present study aimed at evaluating the dissipation of S-metolachlor (S-MET) at three doses in maize growing on diverse physico-chemical properties of soil. The effect of herbicide on dehydrogenase (DHA) and acid phosphatase (ACP) activity was estimated. A modified QuEChERS method using LC-MS/MS has been developed. The limit of quantification (0.001 mg kg^?1) and detection (0.0005 mg kg^?1) were very low for soil and maize samples. The mean recoveries and RSDs for the six spiked levels (0.001–0.5 mg kg^?1) were 91.3 and 5.8%. The biggest differences in concentration of S-MET in maize were observed between the 28th and 63rd days. The dissipation of S-MET in the alkaline soil was the slowest between the 2nd and 7th days, and in the acidic soil between the 5th and 11th days. DT₅₀ of S-MET calculated according to the first-order kinetics model was 11.1–14.7 days (soil) and 9.6–13.9 days (maize). The enzymatic activity of soil was higher in the acidic environment. One observed the significant positive correlation of ACP with pH of soil and contents of potassium and magnesium and negative with contents of phosphorus and organic carbon. The results indicated that at harvest time, the residues of S-MET in maize were well below the safety limit for maize. The findings of this study will foster the research on main parameters influencing the dissipation in maize ecosystems.