Determination of acidic herbicides in cereals by QuEChERS extraction and LC/MS/MS

A simple and rapid method has been studied for the determination of acidic herbicides (2,4-D, Dichlorprop, Dichlorprop-p, Fluazifop, Fluroxypyr, MCPA, Mecoprop and Mecoprop-p) on cereals (rye). The method involves an alkaline hydrolysis with sodium hydroxide in order to release covalently bound compounds, prior to QuEChERS extraction, followed by neutralization and analysis via liquid chromatography-double mass spectrometry LC/MS/MS. The performance of the method either with or without alkaline hydrolysis was studied in terms of recovery rates and limit of quantification (LOQ). In either case, recoveries were determined at four spiking levels (0.02 mg/kg, 0.05 mg/kg, 0.1 mg/kg and 0.5 mg/kg) with 5 replicates for each level. Mean recoveries ranged from 90 to 120 %, whereas relative standard deviations (RSD %) proved to be less than 20 %. Quantitative analysis was carried out by the internal standard (Nicarbazin) and the LC/MS/MS analysis was performed in electrospray ionisation (ESI) negative mode using a Zorbax XCB Eclipse column. The developed method was applied to the analysis of several cereals commercially available like as rye flour, oat meal, oat flakes and dehusked oat. Residue levels were found below the limit of quantification (LOQ) of the method. The method has been tested in EU Proficiency Tests for cereals with good results.     

An overview of commercially used brominated flame retardants,their applications,their use patterns in different countries/regions and possible modes of release

Brominated flame retardants (BFRs) are used in a variety of consumer products and several of those are produced in large quantities. These compounds have been detected in environmental samples, which can be attributed to the anthropogenic uses of these compounds. Brominated flame retardants are produced via direct bromination of organic molecules or via addition of bromine to alkenes; hence, an overview of the production and usage of bromine over the past three decades is covered. Production, application, and environmental occurrence of high production brominated flame retardants including Tetrabromobisphenol A, polybrominated biphenyls, Penta-, Octa-, Deca-brominated diphenyl ether (oxide) formulation and hexabromocyclododecane are discussed.     

Sediment Quality Assessment in the Gulf of Gdańsk (Baltic Sea) Using Complementary Lines of Evidence

Sediments from Polish coastal environments were classified by a quality assessment approach that took into account trace metal and organic micropollutant concentrations, grain-size distribution, and organic carbon content. Generally, no benthic organisms were found at sites where sediments were classified as heavily polluted. However, areas characterized by a moderate contamination showed a variable composition of the benthic community and changing bioaccumulation patterns; therefore, no single species found in the Gulf of Gdańsk could be considered representative of the whole benthic environment. Although sediment monitoring must be considered a suitable tool to detect hot-spot pollution areas in coastal and inland waters, it should be complemented by bioaccumulation measurements to evaluate the actual risk posed by contaminants to benthic organisms. This “biological information” allows a better appreciation of the real benthic infaunal community exposure to chemicals and can usefully complement the existing sediment quality guidelines.     

Ca-Mg kutnahorite and struvite production by Idiomarina strains at modern seawater salinities

The production of Mg-rich carbonates by Idiomarina bacteria at modern seawater salinities has been investigated. With this objective, four strains: Idiomarina abyssalis (strain ATCC BAA-312), Idiomarina baltica (strain DSM 15154), Idiomarina loihiensis (strains DSM 15497 and MAH1) were used. The strain I. loihiensis MAH1 is a new isolate, identified in the scope of this work. The four moderately halophilic strains precipitated struvite (NH4MgPO4 x 6H2O) crystals that appear encased by small Ca-Mg kutnahorite [CaMg(CO3)2] spheres and dumbbells, which are also regularly distributed in the bacterial colonies. The proportion of Ca-Mg kutnahorite produced by the bacteria assayed ranged from 50% to 20%, and I. abyssalis also produced monohydrocalcite. All precipitated minerals appeared to be related to the bacterial metabolism and, consequently, can be considered biologically induced. Amino acid metabolism resulted in a release of ammonia and CO2 that increase the pH and CO(3)(2-) concentration of the culture medium, creating an alkaline environment that favoured carbonate and struvite precipitation. This precipitation may be also related to heterogeneous nucleation on negatively charged points of biological structures. Because the nature of the organic matrix determines which ion is preferentially adsorbed and, consequently, which mineral phase is formed, the uniquely high content in odd-iso-branched fatty acids of the Idiomarina suggests that their particular membrane characteristics could induce Ca-Mg kutnahorite production. The Ca-Mg kutnahorite, a mineral with a dolomite-ordered structure, production at seawater salinities is noticeable. To date, such precipitation in laboratory cultures, has only been described in hypersaline conditions. It has also been the first time that biomineralization processes have been related to Idiomarina bacteria.     

Influence of angular exposure and proximity to vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements

This study investigated the influence of angular exposure and distance from vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements in a town of central Italy. An Index of Lichen Diversity (ILD) was calculated on the street-facing and the opposite side of road-lining trees and in a urban park 250 m away, and the content of selected trace elements (Al, Ba, Ce, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, and Zn) was determined in samples of the lichen Punctelia borreri (Sm.) Krog growing on tree bark, both on the exposed and opposite sides. ILD increases with distance from traffic emissions. However, at the site with vehicle traffic, non-nitrophilous lichens decreased while nitrophilous ones increased. The concentration of the traffic-related elements Ba, Cr, Cu, Mn, Sb, and Zn accumulated in thalli of P. borreri was higher on roadside trees than in trees from the urban park. ILD was not affected by the angular exposure to the road and the bioaccumulation of traffic-related elements was similar in lichens from the side of the bole exposed to traffic emissions and particulate resuspension and from the opposite side. The angular exposure in respect to the traffic source does not influence trace element accumulation. These results are important when using lichens for biomonitoring purposes, both for planning future studies and for the reliability of the interpretation of past surveys that do not report information about the angular exposure of the collected lichen material.     

Palm oil biodiesel: An assessment of PAH emissions, oxidative potential and ecotoxicity of particulate matter

This work assessed the impact of fuelling an automotive engine with palm biodiesel (pure, and two blends of 10% and 20% with diesel, B100, B10 and B20, respectively) operating under representative urban driving conditions on 17 priority polycyclic aromatic hydrocarbon (PAH) compounds, oxidative potential of ascorbic acid (OP^AA), and ecotoxicity through Daphnia pulex mortality test. PM diluted with filtered fresh air (WD) gathered in a minitunel, and particulate matter (PM) collected directly from the exhaust gas stream (W/oD) were used for comparison. Results showed that PM collecting method significantly impact PAH concentration. Although all PAH appeared in both, WD and W/oD, higher concentrations were obtained in the last case. Increasing biodiesel concentration in the fuel blend decreased all PAH compounds, and those with 3 and 5 aromatic rings were the most abundant. Palm biodiesel affected both OP^AA and ecotoxicity. While B10 and B20 exhibited the same rate of ascorbic acid (AA) depletion, B100 showed significant faster oxidation rate during the first four minutes and oxidized 10% more AA at the end of the test. B100 and B20 were significantly more ecotoxic than B10. The lethal concentration LC50 for B10 was 6.13 mg/L. It was concluded that palm biodiesel decreased PAH compounds, but increased the oxidative potential and ecotoxicity.     

Enhancement of copper and cadmium adsorption on kaolin by the presence of humic acids

The competitive adsorption equilibrium isotherms of Cu²⁺ and Cd²⁺ on kaolin have been measured at 298 K, in the presence and the absence of humic acids (HAs). HAs were found to enhance the metal adsorption capacity of mineral surfaces, in particular kaolin. This enhancement was also observed in the competitive adsorption of copper and cadmium on kaolin and kaolin–HA complex. This competitive adsorption shows that the presence of Cd²⁺ has not an important effect on Cu²⁺ adsorption, whereas a dramatic decrease is observed on the adsorption of Cd²⁺ in the presence of Cu²⁺. The Freundlich isotherm equation was found to provide an excellent fit to the experimental data. These results were compared with the independent adsorption of both heavy metals.     

Lanthanum fixation by Myxococcus xanthus: cellular location and extracellular polysaccharide observation

Myxococcus xanthus is a soil bacterium of the myxobacteria group and is abundant in almost all soils. Its role in soil ecology is considered significant. One noteworthy characteristic of the bacterium is that it produces large quantities of extracellular polymeric substances (EPS). It is also known that its biomass has the capacity to fix heavy metals. Here it is reported that M. xanthus was able to accumulate 0.6 mmol of La per g of wet biomass and/or 0.99 mmol per g of dry biomass. Transmission Electron Microscopy (TEM) observation of M. xanthus cells treated with La showed that a substantial amount of this cation was fixed in the EPS and in the cell wall. Smaller amounts were also observed in the cytoplasm. Fixed La appeared as phosphate in all cellular locations. The results given here also show that the use of La enables TEM observation of the M. xanthus EPS as a dense fibrillar net surrounding the cells. This technique is relatively easy and prevents EPS collapse, which occurs frequently during the fixation and dehydration procedures commonly used in preparations for TEM observations. Since antibodies are no longer required, the La stain can be carried out without delaying bacterial cell cultivation or isolation. In addition, the presence of La in cell cytoplasm without cell degeneration suggests that this microorganism could be used as a model in the study of bacteria-lanthanide interactions.     

Myxococcus xanthus'' killed cells as inducers of struvite crystallization. Its possible role in the biomineralization processes

We studied the possibility of struvite formation using killed cells of Myxococcus xanthus. Cells were killed by heat, UV light and sonication. In all cases, we show that struvite crystallization occurs and we propose that the dead cells or cell debris can act by themselves as heterogeneous crystallization nuclei. We also show that the slime, produced by Myxococcus in a large quantities, is not involved in this process.