Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs)     

Pesticide dissipation curves in peach,pear and tomato crops in Uruguay*

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r²=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r²=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Bioaccumulation and effects of perfluorinated compounds (PFCs) in zebra mussels (Dreissena polymorpha)

Perfluorinated chemicals (PFCs) have been used for many years in numerous industrial products and are known to accumulate in organisms. A recent survey showed that tissue levels of PFCs in aquatic organisms varied among compounds and species being undetected in freshwater zebra mussels Dreissena polymorpha. Here we studied the bioaccumulation kinetics and effects of two major PFCs, perfluorooctane sulfonic acid compound (PFOS) and perfluorooctanoic acid (PFOA), in multixenobiotic transporter activity (MXR) and filtration and oxygen consumption rates in zebra mussel exposed to a range of concentrations of a PCF mixture (1–1,000 μg/L) during 10 days. Results indicate a low potential of the studied PFCs to bioaccumulate in zebra mussel tissues. PFCs altered mussel MXR transporter activity being inhibited at day 1 but not at day 10. Bioaccumulation kinetics of PFCs were inversely related with MXR transporter activity above 9 ng/g wet weight and unrelated at tissue concentration lower than 2 ng/g wet weight suggesting that at high tissue concentrations, these type of compounds may be effluxed out by MXR transporters and as a result have a low potential to be bioaccumulated in zebra mussels. Oxygen consumption rates but not filtering rates were increased in all exposure levels and periods indicating that at environmental relevant concentrations of 1 μg/L, the studied PFCs enhanced oxidative metabolism of mussels. Overall, the results obtained in this study confirm previous findings in the field indicating that an important fraction of PFC accumulated in mussel tissues is eliminated actively by MXR transporters or other processes that are metabolically costly.     

Relation between management's behavioural intentions toward the environment and environmental actions

Drawing on Ajzen's Theory of Planned Behaviour, this paper analyses whether there is a relation between management's behavioural intentions toward an environmental problem and the company's specific actions in this area, and also considers the impact of the company size on these actions. For the data, a questionnaire was sent to 184 managers employed in industrial companies located in Spain which belonged to the automobile industry. The empirical analysis produces positive and significant regression coefficients and provides support for the hypotheses proposed. Specifically, the results show that the environmental actions carried out in the company respond at least in part to management's behavioural intentions toward these issues and the size of the firm.     

Assessing water use and quality through youth participatory research in a rural Andean watershed

Water availability, use and quality in a rural watershed of the Colombian Andes were investigated through participatory research involving local youth. Research included the quantification of disaggregated water use at the household level; comparison of water use with availability; monitoring water quality of streams, community water intakes and household faucets; and the determination of land use – water quality interactions. Youth were involved in all aspects of the research from design to implementation, dissemination of results and remediation options. Quantification of domestic and on-farm water use, and water availability indicated that water availability was sufficient during the study period, but that only an 8% decrease in dry season supply would result in shortages. Elevated conductivity levels in the headwaters were related to “natural” bank erosion, while downstream high conductivity and coliform levels were associated with discharges from livestock stalls and poorly maintained septic tanks in the stream buffer zone. Through the involvement of youth as co-investigators, the knowledge generated by the research was appropriated at the local level. Community workshops led by local youth promoted water conservation and water quality protection practices based on research, and resulted in broader community participation in water management. The approach involving youth in research stimulated improved management of both land and water resources, and could be applied in small rural watersheds in developed or developing countries.     

Pluri-annual study of the reproduction of two Mediterranean Oscarella species (Porifera, Homoscleromorpha): cycle, sex-ratio, reproductive effort and phenology

This study presents the phenology of two common Mediterranean sponges belonging to the genus Oscarella (Porifera, Homoscleromorpha). Oscarella tuberculata and Oscarella lobularis are two sibling species, dwellers of shallow benthic communities which tend to have distinct ecological behavior, respectively, euryecious and rather stenoecious. The comparative study of their reproductive cycle showed that both Oscarella species have a seasonal reproductive cycle with a successive phase duration differing from one species to another. In both species, there is a continuous oogenesis, with new oocytes appearing in spring, whereas the spermatogenesis generally starts later with the early warming of the sea. The embryonic development and the larval release are restricted to the warmest months of the year. We also observed a shift in the period of gametogenesis and larval emission depending on species and differences in their sensitivity to changes in thermal regime. It appears that an increase in seawater temperature can affect sex determination, with mainly a shift toward males in both species. Their reproductive efforts are variable in time, and can be in some cases influenced by the temperature regime. This is especially the case of O. lobularis which seems to be the most thermosensitive, its phenology responding significantly to changes in thermal regime, whereas O. tuberculata seems to be less sensitive and/or reactive. By detecting phenological changes among sponges, this study demonstrated the relevance of such monitoring to assess the possible biological response to climate change.     

Long-term effect of temperature on bioaccumulation of dietary metals and metallothionein induction in Sparus aurata

Previous studies have demonstrated that the commercial feed of aquacultured fish contains trace amounts of toxic and essential metals which can accumulate in tissues and finally be ingested by consumers. Recently rising temperatures, associated to the global warming phenomenon, have been reported as a factor to be taken into consideration in ecotoxicology, since temperature-dependent alterations in bioavailability, toxicokinetics and biotransformation rates can be expected. Sparus aurata were kept at 22 °C, 27 °C and 30 °C for 3 months in order to determine the temperature effect on metallothionein induction and metal bioaccumulation from a non-experimentally contaminated commercial feed. A significant temperature-dependent accumulation of cadmium (Cd), copper (Cu), mercury (Hg), zinc (Zn), lead (Pb) and iron (Fe) was found in liver, together with that of manganese (Mn), Fe and Zn in muscle. Hg presented the highest bioaccumulation factor, and essential metal homeostasis was disturbed in both tissues at warm temperatures. An enhancement of hepatic metallothionein induction was found in fish exposed to the highest temperature.     

Bioindication of volatile elements emission by the Puyehue-Cordón Caulle (North Patagonia) volcanic event in 2011

The emission of volatile pollutants from the volcanic eruption of the Puyehue-Cordón Caulle complex (North Patagonia Andean Range) that started in June 4th, 2011, was investigated by bioindication means with the epyphytic fruticose lichen Usnea sp. The elemental composition of pooled samples made up with 10 lichen thalli were analysed by Instrumental Neutron Activation Analysis. Eleven sampling sites were selected within the impacted region at different distance from the volcanic source. Five sites were selected as they were already sampled in a previous study prior to the eruption. Two other new sampling sites were selected from outside the impacted zone to provide non-impacted baseline sites.The elements associated with the lichen incorporation of particulate matter (PM) of geological origin were identified by linear correlation with a geochemical tracer (Sm concentrations). The elements associated with PM uptake were Ce, Eu, Fe, Hf, La, Lu, Na, Nd, Sb, Sc, Se, Ta, Tb, Th, U, and Yb. Arsenic and Cs concentrations showed contributions exceeding the PM fraction in sites near the volcanic centre, also higher than the baseline concentrations, which could be associated with permanent emissions from the geothermal system of the Puyehue-Cordón Caulle complex. The lichen concentrations of Ba, Ca, Co, Hg, K, Rb, Sr, and Zn were not associated with the PM, not showing higher concentrations in the sites nearby the volcanic source or respect to the baseline values either. Therefore, there is no indication of the emission of volatile forms of these elements in the lichen records. The lichen records only identified Br volatile emissions associated with the Puyehue-Cordón Caulle complex eruption in 2011.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs).