Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Trametes sp.LS-10C漆酶对直接类偶氮染料的脱色作用

利用栓菌（Trametes sp.LS-10C）漆酶在单酶和漆酶-介体体系2种情况下对3种直接类偶氮染料进行脱色。结果表明,在给酶量为10 U·mL-1、染料浓度为100 mg·mL-1条件下反应24 h后,直接蓝86在非介体体系中脱色率达到71.2%,其最适脱色温度和pH范围分别为45~60℃和3.5~5.0;直接橙26在介体体系（10 μmol·L-1 ABTS）中脱色率达到78.7%,其最适脱色温度和pH范围分别为35~45℃和4.5~6.5;直接红31在介体体系（10 μmol·L-1 ABTS）中脱色率达到90.7%,其最适脱色温度和pH范围分别为35~45℃和3.5~5.0。     

Chemical characterization of fine aerosols in respect to water-soluble ions at the eastern Middle Adriatic coast

Fine particulate matter (PM2.5) concentrations at the Middle Adriatic coastal site of Croatia were affected by different air-mass inflows and/or local sources and meteorological conditions, and peaked in summer. More polluted continental air-mass inflows mostly affected the area in the winter period, while southern marine pathways had higher impact in spring and summer. Chemical characterization of the water-soluble inorganic and organic ionic constituents is discussed with respect to seasonal trends, possible sources, and air-mass inputs. The largest contributors to the PM2.5 mass were sea salts modified by the presence of secondary sulfate-rich aerosols indicated also by principal component analysis. SO42− was the prevailing anion, while the anthropogenic SO42− (anth-nssSO42−) dominantly constituted the major non-sea-salt SO42− (nssSO42−) fraction. Being influenced by the marine origin, its biogenic fraction (bio-nssSO42−) increased particularly in the spring. During the investigated period, aerosols were generally acidic. High Cl− deficit was observed at Middle Adriatic location for which the acid displacement is primarily responsible. With nssSO42− being dominant in Cl− depletion, sulfur-containing species from anthropogenic pollution emissions may have profound impact on atmospheric composition through altering chlorine chemistry in this region. However, when accounting for the neutralization of H2SO4 by NH3, the potential of HNO3 and organic acids to considerably influence Cl− depletion is shown to increase. Intensive open-fire events substantially increased the PM2.5 concentrations and changed the water-soluble ion composition and aerosol acidity in summer of 2015. To our knowledge, this work presents the first time-resolved data evaluating the seasonal composition of water-soluble ions and their possible sources in PM2.5 at the Middle Adriatic area. This study contributes towards a better understanding of atmospheric composition in the coastal Adriatic area and serves as a basis for the comparison with future studies related to the air quality at the coastal Adriatic and/or Mediterranean regions.     

Effects of permethrin exposure on antioxidant enzymes and protein status in Mediterranean clams Ruditapes decussatus

The effects of permethrin (PER) on a panel of antoxidant enzymes; superoxide dismutase (SOD), catalase (CAT) and glutathione S-transferase (GST) and indices of protein oxidation status (carbonylation and free thiols) were determined in digestive gland and gills of the clam Ruditapes decussatus. Animals were exposed to 100 ppb PER for 2 days. These enzyme activities increased significantly in digestive gland (p?<?0.05) after PER treatment and oxidative modification of proteins was detected in both gill and digestive gland extracts using redox proteomics. PER exposure significantly reduced the amount of protein free thiol groups in digestive gland rather than in gill, when compared to controls. Conversely, digestive gland showed significantly higher levels of carbonylated proteins than gill after PER exposure. Some proteins were successfully identified by mass spectrometry of tryptic peptides. Our data suggest that digestive gland of R. decussatus can be used as a model tissue for investigating environmental risk of PER contamination.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

Distribution of PCDD/Fs and dioxin-like PCBs in sediment and plants from a contaminated salt marsh (Tejo estuary,Portugal)

Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g^?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g^?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Soil moisture determines the effectiveness of two urease inhibitors to decrease N<Subscript>2</Subscript>O emission

Among the mitigation strategies to prevent nitrogen (N) losses from ureic fertilizers, urease inhibitors (UIs) have been demonstrated to promote high N use efficiency by reducing ammonia (NH₃) volatilization. In the last few years, some field experiments have also shown its effectiveness in reducing nitrous oxide (N₂O) losses from fertilized soils under conditions of low soil moisture. An incubation experiment was carried out with the aim of assessing the main biotic mechanisms behind N₂O emissions once that the UIs N-(n-butyl) thiophosphoric triamid (NBPT) and phenil phosphorodiamidate (PPDA) were applied with Urea (U) under different soil moisture conditions (40, 60 and 80 % water-filled pore space, WFPS). In the same study we tried to analyze to what extent soil WFPS regulates the effect of these inhibitors on N₂O emissions. The use of PPDA in our study allowed us to compare the effect of NBPT with that of another commercially available urease inhibitor, aiming to see if the results were inhibitor-specific or not. Based on the results from this experiment, a WFPS (i.e. 60 %) was chosen for a second study (i.e. mesocosm experiment) aiming to assess the efficiency of the UIs to indirectly affect N₂O emissions through influencing the pool of soil mineral N. The N₂O emissions at 40 % WFPS were almost negligible, being significantly lower from all fertilized treatments than that produced at 60 and 80 % WFPS. When compared to U alone, NBPT+U reduced the N₂O emissions at 60 % WFPS but had no effect at 80 % WFPS. The application of PPDA significantly increased the emissions with respect to U at 80 % WFPS whereas no significant effect was found at 60 %. At 80 % WFPS, denitrification was the main source of N₂O emissions for all treatments. In the mesocosm study, the application of NBPT+U was an effective strategy to reduce N₂O emissions (75 % reduction compared to U alone), due to a lower soil ammonium (NH₄ ⁺) content induced by the inhibitor. These results suggest that adequate management of the UI NBPT could provide, under certain soil conditions, an opportunity for mitigation of N₂O emissions from fertilized soils.     

Presence of Torque Teno Virus (TTV) in Tap Water in Public Schools from Southern Brazil

Torque teno virus (TTV) was surveyed in tap water collected in schools from three municipalities located in the south of Brazil. TTV genomes were found in 11.7 % (4/34) of the samples. TTV DNA was detected in 10.5 % (2/19) of the samples collected at the city of Caxias do Sul and in 25 % (2/8) of the samples from Pelotas. Those cities have a low rate of sewage treatment. All samples from Santa Cruz do Sul, which has nearly 92 % of its sewage treated, were negative. These results suggest that the amount of sewage treated may have an effect on the detection rates of TTV DNA in drinking water in a given urban area, showing a mild negative correlation (r = ?0.76), when comparing the percentage of sewage treatment to the detection of TTV genomes. The detection rate of TTV was also compared with Escherichia coli, showing a strong correlation (r = 0.97), indicating that TTV may be a suitable marker of fecal contamination.     

Ecological restoration as a strategy for mitigating and adapting to climate change: lessons and challenges from Brazil

Climate change is a global phenomenon that affects biophysical systems and human well-being. The Paris Agreement of the United Nations Framework Convention on Climate Change entered into force in 2016 with the objective of strengthening the global response to climate change by keeping global temperature rise this century well below 2 °C above pre-industrial levels and to pursue efforts to limit the temperature increase even further to 1.5 °C. The agreement requires all Parties to submit their “nationally determined contributions” (NDCs) and to strengthen these efforts in the years ahead. Reducing carbon emissions from deforestation and forest degradation is an important strategy for mitigating climate change, particularly in developing countries with large forests. Extensive tropical forest loss and degradation have increased awareness at the international level of the need to undertake large-scale ecological restoration, highlighting the need to identify cases in which restoration strategies can contribute to mitigation and adaptation. Here we consider Brazil as a case study to evaluate the benefits and challenges of implementing large-scale restoration programs in developing countries. The Brazilian NDC included the target of restoring and reforesting 12 million hectares of forests for multiple uses by 2030. Restoration of native vegetation is one of the foundations of sustainable rural development in Brazil and should consider multiple purposes, from biodiversity and ecosystem services conservation to social and economic development. However, ecological restoration still presents substantial challenges for tropical and mega-diverse countries, including the need to develop plans that are technically and financially feasible, as well as public policies and monitoring instruments that can assess effectiveness. The planning, execution, and monitoring of restoration efforts strongly depend on the context and the diagnosis of the area with respect to reference ecosystems (e.g., forests, savannas, grasslands, wetlands). In addition, poor integration of climate change policies at the national and subnational levels and with other sectorial policies constrains the large-scale implementation of restoration programs. The case of Brazil shows that slowing deforestation is possible; however, this analysis highlights the need for increased national commitment and international support for actions that require large-scale transformations of the forest sector regarding ecosystem restoration efforts. Scaling up the ambitions and actions of the Paris Agreement implies the need for a global framework that recognizes landscape restoration as a cost-effective nature-based solution and that supports countries in addressing their remaining needs, challenges, and barriers.