Development and validation of LC-MS/MS method for the determination of Ochratoxin A and its metabolite Ochratoxin α in poultry tissues and eggs

The objective of this study was to develop a liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the determination of Ochratoxin A (OTA) and Ochratoxin α (OTα) in poultry tissues and eggs. The two toxins were extracted by a mixture of acetonitrile/water, purified with a reversed phase C18 solid phase extraction column (SPE) and determined by LC-MS/MS. The LC-MS/MS method performances were evaluated in terms of linearity in solvent and in matrix (ranged from 0.5 to 15.10 µg L^?1 for OTA and from 0.60 to 17.85 µg L^?1 for OTα), limit of detection (LOD), limit of quantitation (LOQ), specificity, accuracy and precision in repeatability conditions. Recovery experiments were performed by spiking poultry liver, kidney, muscle and eggs around 1 µg kg^?1 and 10 µg kg^?1. LODs were 0.27 and 0.26 µg kg^?1 while LOQs were fixed at 1.0 and 1.2 µg kg^?1 for OTA and OTα, respectively. Main recoveries for OTA ranged from 82 to 109% and for OTα ranged from 55 to 89%. The values of within-laboratory relative standard deviation (RSD_r) were equal to or below 20%. Considering the results obtained and that all analytical performance criteria were fulfilled, the new extraction and purification method developed for OTA and OTα determination in animal tissues and eggs was found appropriate for control laboratories and research activities designed to ensure food safety.     

Retention of arsenic on hydrous ferric oxides generated by electrochemical peroxidation

Electrochemical peroxidation (ECP), an emerging remediation technology, with direct electric current applied to steel electrode and small addition of H2O2, was used to remove As(III) from contaminated aqueous solutions. Bench scale experiments were conducted to evaluate the sorption and distribution of arsenic between the soluble and solid state hydrous ferric oxides (HFO) formed as part of the ECP process. ECP was effective in removing arsenic from the aqueous solution, with >98% of the applied As(III) adsorbed on HFO. Removal was complete within 3 min of ECP treatment and apparently independent of the initial pH of the water (3.5-9.5). In the absence of H2O2 more As(III) was adsorbed by solid state iron at pH 9.5 than at 3.5 (2600 vs. 1750 microg l(-1)). Thus H2O2 was crucial to oxidize As(III) to As(V) which is more strongly retained by HFO. Removal of As was not significantly affected by the concentration of H2O2 or by current processing time. The optimal operating conditions were pH < 6.5, H2O2 concentration of 10 mg l(-1) and current process time not exceeding 3 min. X-ray diffraction (XRD), diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy and transmission electron microscopy (TEM) were applied to study the HFO deposits. The XRD data indicated the prevalence of poorly ordered Fe minerals in the suspended ECP solids with a dominance of 5 line ferrihydrite in the absence of H2O2. At pH 3.5 and with 100 mg H2O2 l(-1), akaganeite was formed, whereas an incipient hematitic phase, reflection at 0.39 nm, occurred at pH 6.5. DRIFT data indicate that both As(III) and As(V) were specifically adsorbed onto HFO at acid and neutral pH. TEM observations indicated the presence of spherical shape ferrihydrite and provided evidence for possible formation of subrounded hematite and acicular shape goethite.     

Fate and degradation of triasulfuron in soil and water under laboratory conditions

The behavior and fate of triasulfuron (TRS) in water and soil systems were examined in laboratory studies. The degradation of TRS in both buffer solution and soil was highly pH-sensitive. The rate of degradation could be described with a pseudo first-order kinetic and was much faster at pH 4 than at pH 7 and 9. Aqueous hydrolysis occurred by cleavage of the sulfonylurea bridge to form 2-(2-chloroethoxy) benzenesulfonamide (CBSA) and [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] (AMMT). AMMT was unstable in aqueous solutions in any pH condition but it degraded more quickly at pH 4 and 9. CBSA did not degrade in aqueous solutions or in enriched cultures but it underwent a quick degradation in the soil. The rates of TRS degradation in sterile and non-sterile soils were similar, suggesting that microorganisms played a minimal role in the breakdown process. This hypothesis is supported by the results of studies on the degradation of TRS by enriched cultures during which the molecule underwent a prevalently chemical degradation.     

The adaptive response of lichens to mercury exposure involves changes in the photosynthetic machinery

Lichens are an excellent model to study the bioaccumulation of heavy metals but limited information is available on the molecular mechanisms occurring during bioaccumulation. We investigated the changes of the lichen proteome during exposure to constant concentrations of mercury. We found that most of changes involves proteins of the photosynthetic pathway, such as the chloroplastic photosystem I reaction center subunit II, the oxygen-evolving protein and the chloroplastic ATP synthase β-subunit. This suggests that photosynthesis is a target of the toxic effects of mercury. These findings are also supported by changes in the content of photosynthetic pigments (chlorophyll a and b, and β-carotene). Alterations to the photosynthetic machinery also reflect on the structure of thylakoid membranes of algal cells. Response of lichens to mercury also involves stress-related proteins (such as Hsp70) but not cytoskeletal proteins. Results suggest that lichens adapt to mercury exposure by changing the metabolic production of energy.     

Spatial variability of precipitation in Spain

The spatial variability of annual and seasonal precipitation in the conterminous land of Spain has been evaluated by using correlation decay distance analysis (CDD). The CDD analysis essentially explores how the correlation between neighbouring stations varies according to distance. We analysed CDD independently for the decades 1956–1965, 1966–1975, 1976–1985, 1986–1995, and 1996–2005 using only those stations with no missing values for each decade. To this end, 972, 1,174, 1,242, 773 and 695 complete series were used for each decade, respectively. In particular, for each station and decade, we calculated the threshold distance at which the common variance between target (i) and neighbour series is higher than 50 % (r ²  = 0.5) to evaluate whether current density of the climate data set captures the spatial variability of precipitation within the study area. Results indicate that, at an annual scale, neighbouring stations with 50 % of common variance are restricted on average to about 105 km, but this distance can vary from 28 to 251 km within the study area. The lowest variability is located to the SW and in winter, while the higher spatial variability is found to the north, in the Cantabrian area, and to the east, in the Mediterranean and Pyrenees, during summer. Our results suggest that current density of climate stations (those operating in 2005) is good enough to study precipitation variability at an annual scale for winter, spring and autumn, but not enough for summer.     

Voluntary GHG management using a life cycle approach. A case study

Voluntary GHG management is a primary issue for many organizations. To support organizations with this activity, authoritative bodies have published many different guidelines. Nevertheless, these guidelines show limitations in identification of the direct and indirect processes that have a major impact on climate change, which should be considered in GHG management.In this paper, a life cycle approach is used to identify the processes of an organization and its supply chain that have major impacts on climate change. The results show that this approach is compatible with the current ISO standards and that in the case study the greatest emissions come from the organization’s indirect processes.     

Implications of a changing climate on food security and smallholders’ livelihoods in Bogotá, Colombia

Small farmers who supply the city of Bogotá with food are facing many challenges that are jeopardizing their livelihoods and by extension, the food security of Colombia’s capital. We expect future changes in climatic conditions to exacerbate the plight of the small farmers and this is expected to compromise Bogota’s food security even further. This paper specifically seeks to assess the impact of climate change (CC) on the livelihoods of smallholders who supply Bogota with most of its food. In our multidisciplinary methodology, we translated the exposure to CC into direct impact on crops and assessed sensitivity and adaptive capacity using the sustainable rural livelihoods framework. The results show that rainfall (by average of 100 mm) and temperature (by average of 2.1 °C) will increase over the study area, while the future climate suitability of the most important crops such as mango (Mangifera indica), papaya (Carica papaya), corn (Zea mays) and plantain (Musa balbisiana) shows a decrease of 19 % to 47 % climate suitability by the year 2050. The assessment of sensitivity and adaptive capacity demonstrates that farmers participating in a farmers’ market, initiated by several local and international non-governmental organizations (NGOs), are less vulnerable to CC than farmers who sell through intermediaries. Those farmers selling directly to consumers in the farmers’ market have a higher adaptive capacity (3 on a scale of 3) in social and financial capital than those selling to intermediaries with less adaptive capacity (1 on a scale of 3). In light of the reduction in overall climatic suitability of some of the major crops and the change of geographic location of suitability for others, there are likely to be serious threats for Bogotá’s food security, the ecological landscape around the city, and farmers’ livelihoods. We further conclude that unless proper adaptation measures are implemented, the geographical shift in climate suitability may also force farmers to shift their crops to higher elevations including remaining forests and páramos (the Colombian alpine tundra ecosystems), which may be threatened in the near future.     

Quantification of Human Adenoviruses in European Recreational Waters

The presence of human adenoviruses (HAdV) in recreational water might cause disease in the population upon exposure. HAdV detected by PCR could also serve as indicators of the virological water quality. In order to assess the applicability of HAdV to the evaluation of the faecal contamination in European bathing waters, a real-time quantitative PCR assay was used for the quantification of HAdV in 132 samples collected from 24 different recreational marine and freshwater sites in nine European countries. Selected samples presenting positive nested PCR results for HAdV were analyzed using quantitative PCR and 80 samples from a total of 132 produced quantitative results with mean values of 3.2 × 10² per 100 ml of water, being human adenovirus 41 the most prevalent serotype between the samples where adenovirus was typified. HAdV were quantified in samples from all 15 surveillance laboratories. Statistical analysis showed no homogeneous linear relation between HAdV and E. coli, intestinal enterococci or somatic coliphages concentrations in the tested samples when considering all the data together. Significant correlations between HAdV and at least one of the other indicators were observed only when data from individual laboratories were considered. The quantification of HAdV may provide complementary information in relation to the use of bacterial standards in the control of water quality in bathing water.     

Interactive effects of personality and organizational politics on contextual performance

The authors explored the process of evaluating contextual performance in the context of a politically charged atmosphere. They hypothesized that the negative relationship between perceptions of organizational politics and contextual performance is weaker among workers high in three of the Big Five model of personality dimensions—agreeableness, extraversion, and conscientiousness. Data were collected from a matched sample of 540 supervisors and subordinates employed in the private sector. Results indicated that the interaction of politics and the personality dimension of agreeableness explained a significant incremental amount of variance in the interpersonal facilitation facet of contextual performance. These findings demonstrate the need to consider both the situation and the person as antecedents of contextual performance. Copyright © 2002 John Wiley & Sons, Ltd.     

Predicting dioxin-like PCBs soil contamination levels using milk of grazing animal as indicator

Dioxin-like PCBs (dl-PCBs) are ubiquitous persistent organic pollutants of recognized negative effects on human health. Assessing highly polluted areas should be an important public health issue. This study proposes to use the milk of grazing animals as a bioindicator of dl-PCB contamination in the environment. The hypothesis is that milk concentration of dl-PCBs are related to soil concentrations of these compounds, and that soils are generally reflective of a larger environmental issue of dl-PCB contamination. In this study, we evaluate the possibility of predicting soil concentrations using milk of sheep, cows and buffalos in a spatial model. For this purpose, samples of soil and milk collected in Campania (Italy) were introduced in a GIS platform to perform geostatistical analysis for building a simple predictive model. The ordinary least squares regressions (OLS) showed a statistically significant correlation (p < 0.05) between soil and milk contamination. However, this relationship was spatially variable. Thus, a geographically weighted regression (GWR) was performed, obtaining R² values of 0.91, 0.77 and 0.66 for sheep’s, buffalo’s and cow’s milk respectively. Assessed the mathematical relationships between the variables, new data was introduced to evaluate the performance of the model. Predictions of soil contamination with dl-PCBs using sheep’s, cow’s and buffalo’s milk showed a mean error of 23%, 25% and 36% respectively. According to these results the sheep’s milk can be considered the best bioindicator of dl-PCBs contamination among the three species. The results of this project evidence the potentialities of the proposed approach to assess bioindicator performance in a spatial predictive model.