Application of a LC–MS/MS method for multi-mycotoxin analysis in infant formula and milk-based products for young children commercialized in Southern Brazil

ABSTRACT

An analytical method based on liquid chromatography–tandem mass spectrometry (LC–MS/MS) was validated and applied for the analysis of aflatoxin M₁ (AFM₁), ochratoxin A (OTA) and deoxynivalenol (DON) in infant formula and milk-based products for young children commercialized in Brazil. A total of 38 samples were evaluated, including 12 infant formula, 14 follow-on formula and 12 samples of milk-based products. AFM₁ was detected in 12 (32%) samples, and seven (18%) samples contained AFM₁ levels above the method limit of quantification in a concentration range between 0.013 and 0.067 ng mL^?1 (0.026 ± 0.019). Two samples of milk-based products exceeded the maximum level (ML) fixed by the European Union for AFM₁ in baby foods, however, all samples were in agreement with the levels established by the Brazilian regulation. OTA and DON were not detected in any of the analyzed samples.     

Occurrence and source characterization of perfluorochemicals in an urban watershed

Perfluorochemicals (PFCs) are used in numerous applications, mainly as surfactants, and occur ubiquitously in the environment as complex mixtures. This study was undertaken to characterize the occurrence and sources of commonly detected PFC compounds in surface waters of the Marina catchment, a watershed that drains an urbanized section of Singapore. Of the 19 target PFCs, 13 were detected with perfluorooctanoic acid (PFOA) (5-31 ng L⁻¹) and perfluorooctane sulfonate (PFOS) (1-156 ng L⁻¹) being the dominant components. Other compounds detected included perfluoroalkyl carboxylates (C7-C12) and perfluoroalkyl sulfonates (C6 and C8). Sulfonamide compounds detected 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA), 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA), perfluorooctanesulfonamido acetic acid (FOSAA) and perfluorooctanesulfonamide (FOSA) were putative transformation products of N-EtFOSE and N-MeFOSE, the N-ethylated and N-methylated ethyl alcohol derivatives, respectively. Surface water concentrations were generally higher during dry weather than during storm water flow: the median concentrations of total PFCs in dry and wet weather were 57 and 138 ng L⁻¹ compared to 42 and 79 ng L⁻¹, respectively, at Stamford and Alexandra canal, suggesting the presence of a continuous source(s) which is subject to dilution during storm events. In rain water, median concentrations were 6.4 ng L⁻¹, suggesting rain contributed from 12-25% to the total PFC load for non-point source sites. The longitudinal concentration profile along one of the canals revealed a point source of sulfonated PFCs (PFOS), believed to originate from aqueous film-forming foam (AFFF). Sources were characterized using principal component analysis (PCA) and by plotting PFHxS/PFOA against PFOS/PFOA. Typical surface waters exhibit PFOS/PFOA and PFHxS/PFOA ratios below 0.9 and 0.5, respectively. PCA plots reveal waters impacted by “non-typical” PFC sources in Alexandra canal.     

Induced responses to competition and herbivory: natural selection on multi-trait phenotypic plasticity

Herbivory and competition are two of the most common biotic stressors for plants. When occurring simultaneously, responses to one interaction can constrain the induction of responses to the other interaction due to resource limitation and other interactive effects. Thus, to maximize fitness when interacting with competitors and herbivores, plants are likely to express particular combinations of plastic responses. This study reports the interactive effects of herbivory and competition on responses induced in Tithonia tubaeformis plants and describes how natural selection acts on particular plastic responses and on their different combinations. Competition induced a stem elongation response, expressed through an increase in height and mean internode length, together with a decrease in basal diameter. Interestingly, realized resistance increased in both competition and herbivory treatments, suggesting a plastic response in both constitutive and induced resistance traits. Particular combinations of plastic responses defined three plant phenotypes: vigorous, elongated, and resistant plants. The ecological context in which plants grew modified the traits and the particular combinations of plastic responses that were favored by selection. Vigorous plants were favored by selection in all environments, except when they were damaged by herbivores in the absence of neighbors. The combination of responses defining an elongated plant phenotype was favored by selection in crowded conditions. Resistance was negatively selected in the absence of competition and herbivory but favored in the presence of both interactions. In addition, contextual analyses detected that population structure in heterogeneous environments can also influence the outcomes of selection. These findings suggest that natural selection can act on particular combinations of plastic responses, which may allow plants to adjust their phenotypes to those that promote greater fitness under particular ecological conditions.     

Direction of CRT waste glass processing: electronics recycling industry communication

Cathode Ray Tube, CRT, waste glass recycling has plagued glass manufacturers, electronics recyclers and electronics waste policy makers for decades because the total supply of waste glass exceeds demand, and the formulations of CRT glass are ill suited for most reuse options. The solutions are to separate the undesirable components (e.g. lead oxide) in the waste and create demand for new products. Achieving this is no simple feat, however, as there are many obstacles: limited knowledge of waste glass composition; limited automation in the recycling process; transportation of recycled material; and a weak and underdeveloped market. Thus one of the main goals of this paper is to advise electronic glass recyclers on how to best manage a diverse supply of glass waste and successfully market to end users. Further, this paper offers future directions for academic and industry research. To develop the recommendations offered here, a combination of approaches were used: (1) a thorough study of historic trends in CRT glass chemistry; (2) bulk glass collection and analysis of cullet from a large-scale glass recycler; (3) conversations with industry members and a review of potential applications; and (4) evaluation of the economic viability of specific uses for recycled CRT glass. If academia and industry can solve these problems (for example by creating a database of composition organized by manufacturer and glass source) then the reuse of CRT glass can be increased.     

Determination of the applicability of CERCLA's petroleum exclusion at contaminated sites – focus on metals

Areas impacted by petroleum refining and handling operations may become subject to CERCLA enforcement. Because of CERCLA's petroleum exclusion clause, determining whether contamination in a CERCLA Site originated from petroleum products or hazardous wastes becomes important. Because certain metals are typically enriched in wastes relative to petroleum products and background soils, knowledge of metal contents in these potential end member metal sources is an important step towards contaminant source identification in soils and sediments. In LNAPL plumes, metal content, particularly lead, may be claimed to be the result of wastes mishandling and not due only to the presence of leaded gasoline in the plume. Analysis of the percent gasoline in the plume and accounting for weathering are steps to determining whether the lead content in an LNAPL plume is within the historical lead concentration ranges in gasolines. In addition to metals analyses, understanding of operational parameters such as the history of petroleum refining and handling operations, leaks, spills, and cleanup activities are needed for successful conclusion of the applicability of the petroleum exclusion.     

Distribution of polycyclic aromatic hydrocarbons in marine sediments and their potential toxic effects

The presence of polycyclic aromatic hydrocarbons (PAHs) in samples of marine sediments from Paranagua Bay on the southern coast of Brazil was investigated. Paranagua Bay is the location of a major port, one of the busiest in Brazil. The region has a great potential for tourism and port-related industries and activities. Due to its characteristics as a venue for tourism, two major campaigns were planned: one 3 months before the summer (between December and February) and a second after the vacation season. Total concentration of PAHs in sediments ranged from 26.33 to 406.76 ng/g (in both campaigns). The highest values were found in sediments with higher organic carbon content. We found no substantial differences between the two campaigns, and the values are quite similar. Ternary diagrams show that points P5 and P6 were considered polluted, while others were classified as non-polluted. Molecular ratios indicate that the main sources of PAHs are petrogenic and the burning of fossil fuels. Sediment toxicity was assessed by the presence of PAHs in terms of benzo(a)pyrene (BaP) concentration. The toxicity of PAHs mixtures can be characterized more accurately by developing and establishing toxic equivalency factors (TEFs) for PAHs. Considering TEFs, the BaP_eq concentrations vary between 0.264 and 5.922 ng/g (considering both campaigns). Thus, two points are above the maximum level recommended (3 ng/g) by the Netherlands sediment quality guidelines. In fact, sites P5 and P6 apparently are exposed to a greater number of pollution sources, thus reflecting the higher concentration of PAHs compounds in sediments.     

Guiding principles for rewilding

There has been much recent interest in the concept of rewilding as a tool for nature conservation, but also confusion over the idea, which has limited its utility. We developed a unifying definition and 10 guiding principles for rewilding through a survey of 59 rewilding experts, a summary of key organizations’ rewilding visions, and workshops involving over 100 participants from around the world. The guiding principles convey that rewilding exits on a continuum of scale, connectivity, and level of human influence and aims to restore ecosystem structure and functions to achieve a self-sustaining autonomous nature. These principles clarify the concept of rewilding and improve its effectiveness as a tool to achieve global conservation targets, including those of the UN Decade on Ecosystem Restoration and post-2020 Global Biodiversity Framework. Finally, we suggest differences in rewilding perspectives lie largely in the extent to which it is seen as achievable and in specific interventions. An understanding of the context of rewilding projects is the key to success, and careful site-specific interpretations will help achieve the aims of rewilding.     

Occurrence of emerging organic contaminants in a tropical urban catchment in Singapore

The aim of this study was to test in a short term laboratory experiment the accumulation and physiological effects of As in the epiphytic lichen Xanthoria parietina. Arsenic content in treated samples increased progressively with increasing concentration in treatment solutions. Treatment of X. parietina thalli with 0.1, 1, 10 ppm As solutions caused significant decrease of viability, measured as intensity of respiratory activity, and damages to cell membranes, assessed by increase of electric conductivity of rinsing water and lipid peroxidation products. Soluble proteins content decreased and H₂O₂ content increased already at the lowest As concentration tested (0.01 ppm). Photosynthetic efficiency, measured in terms of F_V/F_M ratio, decreased significantly only at the highest As concentration (10 ppm). It was concluded that As exposure causes physiological stress both on the mycobiont and the photobiont and that cell membrane damage, expressed in terms of electric conductivity of rinsing water, is the parameter most affected by As treatment.     

Inhomogeneity of methane emissions from a dairy waste lagoon

Methane (CH₄) is the dominant greenhouse gas emitted by animal agriculture manure. Since the gas is relatively insoluble in water, it is concentrated in discrete bubbles that rise through waste lagoons and burst at the surface. This results in lagoon emissions that are inhomogeneous in both space and time. Emissions from a midwestern dairy waste lagoon were measured over 2 weeks to evaluate the spatial homogeneity of the source emissions and to compare two methods for measuring this inhomogeneous emission. Emissions were determined using an inverse dispersion model based on CH₄ concentrations measured both by a single scanning tunable diode laser (TDL) aimed at a series of reflectors and by flame ionization detection (FID) gas chromatography on line-sampled air. Emissions were best estimated using scanned TDL concentrations over relatively short optical paths that collectively span the entire cross-wind width of the source, so as to provide both the best capture of discrete plumes from the bursting bubbles on the lagoon surface and the best detection of CH₄ background concentrations. The lagoon emissions during the study were spatially inhomogeneous at hourly time scales. Partitioning the inhomogeneous source into two source regions reduced the estimated emissions of the overall lagoon by 57% but increased the variability. Consequently, it is important to assess the homogeneity of a source prior to measurements and final emissions calculation.

Implications: Plans for measuring methane emissions from waste lagoons must take into account the spatial inhomogeneity of the source strength. The assumption of emission source homogeneity for a low-solubility gas such as CH₄ emitted from an animal waste lagoon can result in significant emission overestimates. The entire breadth and length of the area source must be measured, preferably with multiple optical paths, for the detection of discrete plumes from the different emitting regions and for determining the background concentration. Other gases with similarly poor solubility in water may also require partitioning of the lagoon source area.