Analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particles by direct sample introduction thermal desorption GC/MS

The technique of thermal desorption (TD)–GC/MS was evaluated for measuring airborne, 4–6 ring polycyclic aromatic hydrocarbons (PAHs) collected onto quartz filters. TD provides a more readily automated and sensitive alternative to traditional solvent extraction, decreasing the time/cost of analysis and reducing the risk of analyte loss or sample contamination. The developed method was successfully applied to the analysis of PAH standard solutions loaded on sorbent tubes packed with quartz wool and the graphitized carbon black sorbent Carbograph2. The optimized method showed high desorption efficiency over the whole range of target PAHs with good precision, linearity and sensitivity. The proposed method was verified on an urban dust Standard Reference Material (SRM 1649a); the experimentally determined concentrations agreed with the certified ranges (95% confidence limit) for all target compounds except benzo[a]anthracene, which fell just outside the narrow certified range. The desorption efficiency and the reproducibility of the method was evaluated by analysing pieces of real sample filters sampled from urban air for a period of 24 h. The results confirmed the homogeneity of the filter and showed high recovery efficiencies for all target PAHs.     

Root penetration through sealing layers at mine deposit sites.

To prevent acid mine drainage arising from oxygen and water penetration of sulphide-rich mine tailings, the tailings are covered with layers of dry sealing material. Plant roots have a great ability to penetrate dense materials, and if the roots are able to penetrate the sealing layer of a tailings deposit, its oxygen-shielding properties could be reduced. The objective of this study was to evaluate whether plant roots are able to penetrate sealing layers covering mine tailings deposits. Root penetration into layers of various sealing materials, such as clayey moraine (clay, 8-10%; silt, 22-37%; sand, 37-55%; gravel, 15-18%), moraine (unspecified), 6-mm bentonite (kaolin clay) fabric, lime and clay, Cefyll (mixture of pulverized coal fly ash, cement and water) and a mixture containing biosludge (30-35%) and bioashes (65-70%), was investigated. In the field, roots were studied by digging trenches alongside vegetation growing in 3- and 10-year-old mine sites. In the greenhouse root growth of Betula pendula, Pinus sylvestris, Poa pratensis and Salix viminalis were studied in compartments where the plants had been growing for 22 months. The results from the field experiment indicated that roots are able to penetrate both deep down in the cover layer (1.7 m) and also into the sealing layers of various materials, and even to penetrate hard Cefyll. The addition of nutrients in the top cover reduced deep root growth and thereby also penetration through the sealing layer. Low hydraulic conductivity of the sealing layer or a thick cover layer had less effect on root penetration. In the greenhouse experiment roots did not penetrate the thin bentonite fabric, due to low pH (2.1-2.7) that was created from the underlying weathered mine tailings. The clayey moraine was penetrated by all species used in the greenhouse experiment; Pinus sylvestris had the greatest ability to penetrate. To prevent root penetration of the other sealing layer, a suitable condition for the plants should be created in the upper part of the cover layer, namely a sufficient amount of plant nutrients. However, to define such a condition is difficult since different plant species have different requirements.     

Trace Organic Matter in the Ria Formosa,Portugal

The Ria Formosa lagoon, Portugal, receives organic matter from many natural and anthropogenic sources. This paper presents an overview of the contribution these sources made through the use of lipid biomarkers. Sixty-one surface sediment samples were collected and analysed for a range of lipids. Sewage materials were confined to regions within 2 km of discharge points; phytoplankton biomarkers (sterols and fatty acids) suggest production was greatest in the inner parts of the lagoon that also have greatest inorganic nutrient enrichment; terrestrial organic matter was present in relatively low concentrations as shown by both sterol and fatty alcohols; bacteria were widespread although the Sulphate Reducing Bacteria (SRBs, shown by the presence of 3-OH fatty acids) were located near but not adjacent to sewage discharge points.     

Distribution of pesticides and heavy metals in trophic chain

Determination of triazines herbicides (atrazine and simazine) by high performance liquid chromatography (HPLC) in samples of trophic chain were worked out. Determination limits of 0.5 μg g⁻¹ for atrazine, 0.8 μg g⁻¹ for simazine with pesticides recovery of 70–77% in trophic chain samples were obtained. The content of simazine in soils was in range 1.72–57.89 μg g⁻¹, in grass 5–88 μg g⁻¹, in milk 2.32–15.29 μg g⁻¹, in cereals 10.98–387 μg g⁻¹, in eggs 30.14–59.48 μg g⁻¹, for fruits: 2.45–6.19 μg g⁻¹. The content of atrazine in soils was in range 0.69–19.59 μg g⁻¹, in grass 7.85–23.85 μg g⁻¹, in cereals 1.88–43.08 μg g⁻¹. Cadmium, lead and zinc were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) in the same samples as atrazine and simazine. Determination limits for cadmium 5 × 10⁻³ μg g⁻¹, for lead 1 × 10⁻² μg g⁻¹, and for zinc 0.2 × 10⁻³ μg g⁻¹, were obtained. The content of cadmium in soil was in range 0.13–5.89 μg g⁻¹, in grass 114–627.72 × 10⁻³ μg g⁻¹, in milk 8.88–61.88 × 10⁻³ μg g⁻¹, in cereals 0.20–0.31 μg g⁻¹, in eggs 0.11–0.15 μg g⁻¹, in fruits 0.23–0.59 μg g⁻¹. The content of lead in soils was in range 0.57–151.50 μg g⁻¹, in grass 0.16–136.57 μg g⁻¹, in milk 1.16–3.74 μg g⁻¹, in cereals 1.05–5.47 μg g⁻¹, in eggs 5.79–55.87 μg g⁻¹, in fruits 21.00–87.36 μg g⁻¹. Zinc content in soil was in range 9.15–424.5 μg g⁻¹, in grass 35.20–55.87 μg g⁻¹, in milk 20.00–34.38 μg g⁻¹, in cereals 14.94–28.78 μg g⁻¹, in eggs 15.67–32.01 μg g⁻¹, in fruits 14.94–18.88 μg g⁻¹.

Described below extraction and mineralization methods for particular trophic chains allowed to determine of atrazine, simazine, cadmium, lead and zinc with good repeatability and precision. Emphasis was focused on liquid–liquid extraction and solid-phase extraction of atrazine and simazine from analysed materials, as well as, on monitoring the content of herbicides and metals in soil and along trophic chain. Higher concentration of pesticides in samples from west region of Poland in comparison to that of east region is likely related to common applying them in Western Europe in relation to East Europe. The content of metals strongly depends on samples origin (industry area, vicinity of motorways).     

Effects of concentrated drinking water injection on glutathione and glutathione-dependent enzymes in liver of Cyprinus carpio L

Two drinking water production plants located in North Italy, collecting water from the River Po (Plants 1 and 2) were chosen for this study. Water samples were collected before and after the disinfection process and at two points along the piping system. Water samples were concentrated by the solid-phase extraction system and injected intraperitoneally into specimens of Cyprinus carpio. The concentration of water samples was 3 l/equiv. In order to assess the effects of the water samples on carp liver, total glutathione and glutathione-dependent enzymes, such as glutathione S-transferase, glutathione peroxidase, glutathione reductase and glyoxalase I, were measured following this treatment for 6 days at two experimental times (3 and 6 days). Both water plant-treated carp showed a general increase of the enzymatic activities of glutathione S-transferase, and glutathione reductase which might be employed as potential biomarkers of oxidative stress induced by disinfected river water. Plant 1-treated carp showed higher glyoxalase I and glutathione levels and lower glutathione peroxidase activity. A depleted level of total glutathione and of glyoxalase I for specimens of water plant 2 (for both experimental times), without correlation with the distances in the pipeline, suggests that river plant water can also lead to potentially adverse effects on selected biochemical parameters in C. carpio.     

Contribution of precursor compounds to the release of per- and polyfluoroalkyl substances (PFASs) from waste water treatment plants (WWTPs)

Per-and polyfluoroalkyl substances(PFASs) are ubiquitous in sludge and water from waste water treatment plants, as a result of their incorporation in everyday products and industrial processes. In this study, we measured several classes of persistent PFASs,precursors, transformation intermediates, and newly identified PFASs in influent and effluent sewage water and sludge from three municipal waste water treatment plants in Sweden, sampled in 2015. For sludge, samples from 2012 and 2014 were analyzed as well.Levels of precursors in sludge exceeded those of perfluoroalkyl acids and sulfonic acids(PFCAs and PFSAs), in 2015 the sum of polyfluoroalkyl phosphoric acid esters(PAPs) were 15–20 ng/g dry weight, the sum of fluorotelomer sulfonic acids(FTSAs) was 0.8–1.3 ng/g,and the sum of perfluorooctane sulfonamides and ethanols ranged from non-detected to 3.2 ng/g. Persistent PFSAs and PFCAs were detected at 1.9–3.9 ng/g and 2.4–7.3 ng/g dry weight, respectively. The influence of precursor compounds was further demonstrated by an observed substantial increase for a majority of the persistent PFCAs and PFSAs in water after waste water treatment. Perfluorohexanoic acid(PFHxA), perfluorooctanoic acid(PFOA), perfluorohexane sulfonic acid(PFHxS), and perfluorooctane sulfonic acid(PFOS)had a net mass increase in all WWTPs, with mean values of 83%, 28%, 37% and 58%,respectively. The load of precursors and intermediates in influent water and sludge combined with net mass increase support the hypothesis that degradation of precursor compounds is a significant contributor to PFAS contamination in the environment.     

Spatiotemporal evolution of soil pH and zinc after the Aznalcollar mine spill

The residual pollution after the Aznalcóllar (southwestern Spain) pyrite mine spill is still a threat due to the continuing oxidation of sulfuric minerals. The objective of this paper was to analyze the combined effect of pyrite oxidation, sugar beet foam applications, and meteorological conditions on the spatiotemporal evolution of the pH and EDTA-extractable Zn concentration, using non co-located data from 11 sampling dates between June 1999 and March 2002. Median pH values ranged from 4.4 at the beginning of the monitoring period to 7.6 at the end, although values near 2.5 were observed throughout the entire period, despite of two sugar beet foam (SBF) applications. Zinc distributions were positively skewed and median concentrations ranged from 17 to 94 mg kg(-1). The inverse relationship between pH and Zn became weaker toward the end of the monitoring period as a consequence of the precipitation and posterior dissolution of newly formed minerals from the reaction products of the pyrite oxidation. Normal score maps showed that after the SBF applications only 0.5% of the monitored area was below the pH = 4 threshold, while on other dates up to one-third of the area remained below this value. The better performance of the second SBF application could be explained in terms of pyrite oxidation pathways and environmental conditions. From this analysis, with data obtained under uncontrolled field conditions, it is concluded that SBF should be applied before or during the wet and cold season to alleviate acidification, caused by the oxidation of pyrite or other sulfuric minerals.