Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).     

Detection of Human Enteric Viruses in Freshwater from European Countries

The transmission of water-borne pathogens typically occurs by a faecal–oral route, through inhalation of aerosols, or by direct or indirect contact with contaminated water. Previous molecular-based studies have identified viral particles of zoonotic and human nature in surface waters. Contaminated water can lead to human health issues, and the development of rapid methods for the detection of pathogenic microorganisms is a valuable tool for the prevention of their spread. The aims of this work were to determine the presence and identity of representative human pathogenic enteric viruses in water samples from six European countries by quantitative polymerase chain reaction (q-PCR) and to develop two quantitative PCR methods for Adenovirus 41 and Mammalian Orthoreoviruses. A 2-year survey showed that Norovirus, Mammalian Orthoreovirus and Adenoviruses were the most frequently identified enteric viruses in the sampled surface waters. Although it was not possible to establish viability and infectivity of the viruses considered, the detectable presence of pathogenic viruses may represent a potential risk for human health. The methodology developed may aid in rapid detection of these pathogens for monitoring quality of surface waters.     

AMEG: the new SETAC advisory group on aquatic macrophyte ecotoxicology

Introduction and background

Primary producers play critical structural and functional roles in aquatic ecosystems; therefore, it is imperative that the potential risks of toxicants to aquatic plants are adequately assessed in the risk assessment of chemicals. The standard required macrophyte test species is the floating (non-sediment-rooted) duckweed Lemna spp. This macrophyte species might not be representative of all floating, rooted, emergent, and submerged macrophyte species because of differences in the duration and mode of exposure; sensitivity to the specific toxic mode of action of the chemical; and species-specific traits (e.g., duckweed's very short generation time).

Discussion and perspectives

These topics were addressed during the workshop entitled “Aquatic Macrophyte Risk Assessment for Pesticides” (AMRAP) where a risk assessment scheme for aquatic macrophytes was proposed. Four working groups evolved from this workshop and were charged with the task of developing Tier 1 and higher-tier aquatic macrophyte risk assessment procedures. Subsequently, a SETAC Advisory Group, the Macrophyte Ecotoxicology Group (AMEG) was formed as an umbrella organization for various macrophyte working groups. The purpose of AMEG is to provide scientifically based guidance in all aspects of aquatic macrophyte testing in the laboratory and field, including prospective as well as retrospective risk assessments for chemicals. As AMEG expands, it will begin to address new topics including bioremediation and sustainable management of aquatic macrophytes in the context of ecosystem services.     

Cell-programmed death induced by walnut husk washing waters in three horticultural crops

Walnut husk washing waters (WHWW), a by-product of walnut production, are indiscriminately used for irrigation without preliminary risk assessment. Basing on previous in vitro results on the toxicity of this by-product, we have followed the morphophysiological development of Zea mays, Lactuca sativa cv. Gentilina and L. sativa cv. Canasta under diluted and undiluted WHWW irrigation. Significant development alterations have been observed in root and shoot elongations for all crops as well as in total biomass and chlorophyll content. The genotoxic potential of WHWW has been concurrently verified; acridine orange/ethidium bromide staining evidenced chromatin modifications and DNA degradation and also was confirmed by DNA laddering. The DNA instability was also assessed through RAPD, thus suggesting the danger of the by-product of walnut processing and focusing the attention on the necessity of an efficient treatment of WHWWs. The findings obtained by PCA of agronomic and physiological traits suggested that establishing guidelines for the administration of WHWW for irrigation is of great importance, and it is necessary to supervise their use in agricultural soils.     

Cancer values of prevented fatalities (VPFs), one size does not fit all: the benefits of contaminated site cleanups in Italy

The authors conducted a survey based on conjoint choice experiments in Milan, Italy, about mortality risk reductions delivered by hypothetical private behaviors and public programs, and used it to estimate the value of a prevented fatality (VPF) when the cause of death is cancer. Their estimate of the VPF is 4.2 million Euros. The VPF is about C1 million larger when the risk reduction is delivered by a public program, but further analyses reveal that it is so only when the respondent believes that public programs are effective at reducing this particular type of mortality risk This estimate of the VPF is higher than generic European Union-wide figures recommended by the European Commission Directorate-General for Environment (DG Environment) for environmental policy analyses, and is comparable to other VPFs that are appropriate for Italy, hazardous waste regulations, and enforcement-based cleanup programs. The authors use their VPF to compute the benefits of addressing leaking landfills, illegal disposal of hazardous wastes, and poor hazardous waste management practices in the provinces of Naples and Caserta in southern Italy. The authors also examine the importance of the discount rates, since the mortality benefits of remediation begin in 20 yr and are assumed to continue over 30 yr.     

PCBs in the eggs of Eurasian kestrels indicate exposure to local pollution

Fail-to-hatch kestrel (Falco tinnunculus) eggs collected at the end of the 1999 and 2005 breeding seasons from nest boxes in and around the city of Rome, Italy, were analyzed by gas chromatography with electron capture detection for their PCB content and for the presence of DDT derivatives and other organochlorines. Among the various PCBs, congeners 153 and 180 were detected in all the eggs and showed the highest concentrations. Eggs collected from the same nest from a polluted location in Rome during 2 different years showed similar type and number of PCB congeners. These data and the fact that eggs from another nest near a sulphate mine had, atypically, low-chlorinated congeners support the conclusion that eggs of this species, whose adults in the Mediterranean and continental Europe perform only short or no migration movements, might be indicative of local pollution. When multiple eggs in the same clutch were analyzed, the PCBs were similar in type but their concentration decreased within clutch, likely in parallel to the laying order.     

Arbuscular mycorrhizal fungi differentially affect the response to high zinc concentrations of two registered poplar clones

The effects of a high concentration of zinc on two registered clones of poplar (Populus alba Villafranca and Populus nigra Jean Pourtet), inoculated or not with two arbuscular mycorrhizal fungi (Glomus mosseae or Glomus intraradices) before transplanting them into polluted soil, were investigated, with special regard to the extent of root colonization by the fungi, plant growth, metal accumulation in the different plant organs, and leaf polyamine concentration. Zinc accumulation was lower in Jean Pourtet than in Villafranca poplars, and it was mainly translocated to the leaves; the metal inhibited mycorrhizal colonization, compromised plant growth, and, in Villafranca, altered the putrescine profile in the leaves. Most of these effects were reversed or reduced in plants pre-inoculated with G. mosseae. Results indicate that poplars are suitable for phytoremediation purposes, confirming that mycorrhizal fungi can be useful for phytoremediation, and underscore the importance of appropriate combinations of plant genotypes and fungal symbionts.     

Monitoring agricultural burning in the Mississippi River Valley region from the moderate resolution imaging spectroradiometer (MODIS)

The 2003 active fire observations from the Moderate Resolution Imaging Spectroradiometer (MODIS), on board NASA's Terra and Aqua satellites, were analyzed to assess burning activity in the cropland areas of the Mississippi River Valley region. Agricultural burning was found to be an important contributor to fire activity in this region, accounting for approximately one-third of all burning. Agricultural fire activity showed two seasonal peaks: the first, smaller peak, occurring in June during the spring harvesting of wheat; and the second, bigger peak, in October during the fall harvesting of rice and soy. The seasonal signal in agricultural burning was predominantly evident in the early afternoon MODIS Aqua fire detections. A strong diurnal agricultural fire signal was prevalent during the fall harvesting months, as suggested by the substantially higher number (approximately 3.5 times) of fires detected by MODIS Aqua in the early afternoon, compared with those detected by MODIS Terra in the morning. No diurnal variations in agricultural fire activity were apparent during the springtime wheat-harvesting season. The seasonal and diurnal patterns in agricultural fire activity detected by MODIS are supported by known crop management practices in this region. MODIS data provide an important means to characterize and monitor agricultural fire dynamics and management practices.