Multivariate analysis applied to X-ray fluorescence to assess soil contamination pathways: case studies of mass magnetic susceptibility in soils near abandoned coal and W/Sn mines.

Determining the origin and pathways of contaminants in the natural environment is key to informing any mitigation process. The mass magnetic susceptibility of soils allows a rapid method to measure the concentration of magnetic minerals, derived from anthropogenic activities such as mining or industrial processes, i.e., smelting metals (technogenic origin), or from the local bedrock (of geogenic origin). This is especially effective when combined with rapid geochemical analyses of soils. The use of multivariate analysis (MVA) elucidates complex multiple-component relationships between soil geochemistry and magnetic susceptibility. In the case of soil mining sites, X-ray fluorescence (XRF) spectroscopic data of soils contaminated by mine waste shows statistically significant relationships between magnetic susceptibility and some base metal species (e.g., Fe, Pb, Zn, etc.). Here, we show how qualitative and quantitative MVA methodologies can be used to assess soil contamination pathways using mass magnetic susceptibility and XRF spectra of soils near abandoned coal and W/Sn mines (NW Portugal). Principal component analysis (PCA) showed how the first two primary components (PC-1 + PC-2) explained 94% of the sample variability, grouped them according to their geochemistry and magnetic susceptibility in to geogenic and technogenic groups. Regression analyses showed a strong positive correlation (R2 > 0.95) between soil geochemistry and magnetic properties at the local scale. These parameters provided an insight into the multi-element variables that control magnetic susceptibility and indicated the possibility of efficient assessment of potentially contaminated sites through mass-specific soil magnetism.

Alzheimer's Disease and Toxins Produced by Marine Dinoflagellates: An Issue to Explore.

This paper examined the toxins naturally produced by marine dinoflagellates and their effects on increases in ß-amyloid plaques along with tau protein hyperphosphorylation, both major drivers of Alzheimer's disease (AD). This approach is in line with the demand for certain natural compounds, namely those produced by marine invertebrates that have the potential to be used in the treatment of AD. Current advances in AD treatment are discussed as well as the main factors that potentially affect the puzzling global AD pattern. This study focused on yessotoxins (YTXs), gymnodimine (GYM), spirolides (SPXs), and gambierol, all toxins that have been shown to reduce ß-amyloid plaques and tau hyperphosphorylation, thus preventing the neuronal or synaptic dysfunction that ultimately causes the cell death associated with AD (or other neurodegenerative diseases). Another group of toxins described, okadaic acid (OA) and its derivatives, inhibit protein phosphatase activity, which facilitates the presence of phosphorylated tau proteins. A few studies have used OA to trigger AD in zebrafish, providing an opportunity to test in vivo the effectiveness of new drugs in treating or attenuating AD. Constraints on the production of marine toxins for use in these tests have been considered. Different lines of research are anticipated regarding the action of the two groups of toxins.

Selective incorporation of rare earth elements by seaweeds from Cape Mondego, western Portuguese coast.

This study examined the mechanism of incorporation of the rare earth elements (REEs), La, Ce, Nd, Eu, Gd, Tb, Yb, into green (Codium tomentosum, Ulva rigida), red (Gracilaria gracilis, Osmundea pinnatifida, Porphyra sp), and brown seaweeds (Saccorhiza polyschides, Undaria pinnatifida) collected from a single site near the coastline of the Cape Mondego, western Portugal. The concentrations of REEs, Mg, Ca, Al, Fe, Zn, and Cu in the biomasses were determined by inductively-coupled plasma mass spectrometry (ICP-MS). The species showed differences in their incorporation and fractionation of REEs from the same environment: the sum of REEs was higher in U. rigida, C. tomentosum, G. gracilis, and O. pinnatifida (0.7-1.7 µg g-1) than in Porphyra sp., S. polyschides, and U. pinnatifida (0.1-0.2 µg g-1). Ratios of Ce/Yb ranged from 13 (in S. polyschides) to 103 (in U. rigida), indicating different proportions of light and heavy REEs among species. Good correlations were found between Al and Fe (R2 = 0.98), and between these elements and La, Ce, Nd, Gd (R2 = 0.88-0.97) and Yb (R2 = 0.66-0.71) for all species except C. tomentosum and G. gracilis. Profiles of REE values normalised to average upper-continental crust composition indicated positive anomalies of Eu and Tb that reinforced the singularity of these elements in the REE group. Correlations between the REEs and Al or Fe suggest that detrital terrigenous particles, adhered to seaweed walls, may be an important mechanism for the incorporation of REEs by seaweeds. Different patterns for C. tomentosum and G. gracilis may also be indicative of the higher influence of cell wall composition on REE incorporation.

Sorption of perfluoroalkyl substances in sewage sludge.

The sorption behaviour of three perfluoroalkyl substances (PFASs) (perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonic acid (PFBS)) was studied in sewage sludge samples. Sorption isotherms were obtained by varying initial concentrations of PFOS, PFOA and PFBS. The maximum values of the sorption solid-liquid distribution coefficients (Kd,max) varied by almost two orders of magnitude among the target PFASs: 140-281 mL g(-1) for PFOS, 30-54 mL g(-1) for PFOA and 9-18 mL g(-1) for PFBS. Freundlich and linear fittings were appropriate for describing the sorption behaviour of PFASs in the sludge samples, and the derived KF and Kd,linear parameters correlated well. The hydrophobicity of the PFASs was the key parameter that influenced their sorption in sewage sludge. Sorption parameters and log(KOW) were correlated, and for PFOS (the most hydrophobic compound), pH and Ca + Mg status of the sludge controlled the variation in the sorption parameter values. Sorption reversibility was also tested from desorption isotherms, which were also linear. Desorption parameters were systematically higher than the corresponding sorption parameters (up to sixfold higher), thus indicating a significant degree of irreversible sorption, which decreased in the sequence PFOS > PFOA > PFBS.

Sorption behaviour of perfluoroalkyl substances in soils.

The sorption behaviour of three perfluoroalkyl substances (PFASs), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS), was studied in six soils with contrasting characteristics, especially in the organic carbon content. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions spiked with increasing concentrations of the target PFAS. The sorption reversibility of PFASs was also tested for some of the samples. Liquid chromatography coupled to tandem mass spectrometry was used to quantify the target PFASs in the solutions. Both the Freundlich and linear models were appropriate to describe the sorption behaviour of PFASs in soils, and enabled us to derive solid-liquid distribution coefficients (Kd) for each compound in each soil. Kd values increased from 19 to 295 mL g(-1) for PFOS, from 2.2 to 38 mL g(-1) for PFOA and from 0.4 to 6.8 mL g(-1) for PFBS, and were positively correlated with the organic carbon content of the soil. KOC values obtained from the correlations were 710, 96 and 17 mL g(-1) for PFOS, PFOA and PFBS, respectively. Whereas Kd values decreased in the sequence PFOS>PFOA>PFBS, desorption yields were lower than 13% for PFOS, from 24 to 58% for PFOA, and from 32 to 60% for PFBS. This shows that the physicochemical characteristics of PFASs, basically their hydrophobicity, controlled their sorption behaviour in soils, with PFOS being the most irreversibly sorbed PFAS.

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge.

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP1EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP1EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.

Assessment of heavy metal and pesticide levels in soil and plant products from agricultural area of Belgrade, Serbia.

This study was aimed to assess the levels of selected heavy metals and pesticides in soil and plant products from an agricultural area of Belgrade, Serbia and to indicate possible sources and risks of contamination. Soil, vegetable, and fruit samples from the most important agricultural city areas were collected from July to November of 2006. Metal contents were determined by atomic absorption spectrometry, whereas pesticide residues were analyzed by gas chromatography-mass spectrometry after extraction performed using solid-phase microextraction technique. Soil characterization based on the determination of selected physical and chemical properties revealed heterogeneous soils belonging to different soil groups. The concentrations of lead, cadmium, copper, and zinc in soil samples do not exceed the limits established by national and international regulations. Residues of the herbicide atrazine were detected in three soil samples, with levels lower than the relevant limit. The presence of other herbicides, namely prometryn, chloridazon, acetochlor, flurochloridone, and napropamide, was registered in some soil samples as well. Among the insecticides investigated in the soil, fenitrothion and chlorpyrifos were the only ones detected. In most of the investigated vegetable samples from the Obrenovac area, Pb and Cd contents are higher in comparison with the maximum levels, indicating the emission of coal combustion products from local thermal power plants as a possible source of contamination. Residue levels of some herbicides and insecticides (metribuzin, trifluralin, pendimethalin, bifenthrin, chlorpyrifos, and cypermethrin) determined in tomato, pepper, potato, and onion samples from Slanci, Ovca, and Obrenovac areas are even several times higher than the maximum residue levels. Inappropriate use of these plant protection products is considered to be the most probable reason of contamination. Because increased levels of heavy metals and pesticide residues found in plant products could pose a risk to consumers' health, their continual monitoring before product distribution to city markets is indispensable.