Qualitative aspects and validation of a screening method for pesticides in vegetables and fruits based on liquid chromatography coupled to full scan high resolution (Orbitrap) mass spectrometry

The analytical capabilities of liquid chromatography with single-stage high-resolution mass spectrometry have been investigated with emphasis on qualitative aspects related to selective detection during screening and to identification. The study involved 21 different vegetable and fruit commodities, a screening database of 556 pesticides for evaluation of false positives, and a test set of 130 pesticides spiked to the commodities at 0.01, 0.05, and 0.20 mg/kg for evaluation of false negatives. The final method involved a QuEChERS-based sample preparation (without dSPE clean up) and full scan acquisition using alternating scan events without/with fragmentation, at a resolving power of 50,000. Analyte detection was based on extraction of the exact mass (±5 ppm) of the major adduct ion at the database retention time ±30 s and the presence of a second diagnostic ion. Various options for the additional ion were investigated and compared (other adduct ions, M + 1 or M + 2 isotopes, fragments). The two-ion approach for selective detection of the pesticides in the full scan data was compared with two alternative approaches based on response thresholds. Using the two-ion approach, the number of false positives out of 11,676 pesticide/commodity combinations targeted was 36 (0.3 %). The percentage of false negatives, assessed for 2,730 pesticide/commodity combinations, was 13 %, 3 %, and 1 % at the 0.01-, 0.05-, and 0.20-mg/kg level, respectively (slightly higher with fully automated detection). Following the SANCO/12495/2011 protocol for validation of screening methods, the screening detection limit was determined for 130 pesticides and found to be 0.01, 0.05, and ≥0.20 mg/kg for 86, 30, and 14 pesticides, respectively. For the detected pesticides in the spiked samples, the ability for unambiguous identification according to EU criteria was evaluated. A proposal for adaption of the criteria was made

Cysts of potentially harmful dinoflagellates, with emphasis on the genus Alexandrium, in Sepetiba Bay (Brazil) during a port survey of GloBallast

Sepetiba Bay in south-eastern Brazil has been selected as a pilot demonstration site within the Global Ballast Water Management Programme (GloBallast; IMO/PNUD/ GEF). As part of the port baseline survey, a series of 43 sediment cores was taken in triplicate in the bay in November 2001, by SCUBA divers, using PVC tubes. The top 60mm of each core was processed for dinoflagellate cyst analysis. Cysts of the potentially toxic Alexandriumcf. minutum were identified in 41% of the samples, but the highest density (22 cysts cm–3) was found in the port area, at the Iron Ore Terminal. Other Alexandrium-type cysts were observed in 37% of the samples and theirhighest density (26 cysts cm–3) was also associated with the port area. These results indicate that the northern area of the bay is unsuitable for the intake by ships of ballast water. This investigation highlights the importanceof cyst surveys to the management of ballasting and deballasting in port areas

Molecular detection of bioluminescent dinoflagellates in surface waters of the Patagonian Shelf during early austral summer 2008

We investigated the distribution of bioluminescent dinoflagellates in the Patagonian Shelf region using “universal” PCR primers for the dinoflagellate luciferase gene. Luciferase gene sequences and single cell PCR tests, in conjunction with taxonomic identification by microscopy, allowed us to identify and quantify bioluminescent dinoflagellates. We compared these data to coincidental discrete optical measurements of stimulable bioluminescence intensity. Molecular detection of the luciferase gene showed that bioluminescent dinoflagellates were widespread across the majority of the Patagonian Shelf region. Their presence was comparatively underestimated by optical bioluminescence measurements, whose magnitude was affected by interspecific differences in bioluminescence intensity and by the presence of other bioluminescent organisms. Molecular and microscopy data showed that the complex hydrography of the area played an important role in determining the distribution and composition of dinoflagellate populations. Dinoflagellates were absent south of the Falkland Islands where the cold, nutrient-rich, and well-mixed waters of the Falklands Current favoured diatoms instead. Diverse populations of dinoflagellates were present in the warmer, more stratified waters of the Patagonian Shelf and Falklands Current as it warmed northwards. Here, the dinoflagellate population composition could be related to distinct water masses. Our results provide new insight into the prevalence of bioluminescent dinoflagellates in Patagonian Shelf waters and demonstrate that a molecular approach to the detection of bioluminescent dinoflagellates in natural waters is a promising tool for ecological studies of these organisms

Phytoplankton interannual variability at Cassino beach, southern Brazil (1992 2007), with emphasis on the surf zone diatom Asterionellopsis glacialis

A long-term study (monthly sampling, 1992 to 2007) was conducted in the surf zone of Cassino Beach, Southern Brazil, in order to detect possible natural and/or anthropogenic disturbances. Surface water temperature (6– 29°C) was the only parameter with predictable seasonal variation; salinity (14–38) was inversely related to rainfall (3.1–485.2 mm month−1) and low values followed extreme precipitation periods in 1997/1998 and 2002/2003 (El Niño years). Asterionellopsis glacialis and chlorophyll a presented high concentrations and peak frequency until 1998, when an intense mud deposition occurred with concomitant extreme rainfall. It affected the surf zone and beach, changing the hydrology and dissolved inorganic nutrient availability. Six phytoplankton species groups were recognized with distinct responses to this mud deposition. We conclude that large-scale climatic changes, like El Niño Southern Oscillation, in conjunction with human activities significantly altered the phytoplankton ecology of the highly dynamic Cassino Beach surf zone

A review on macrobenthic trophic relationships along subtropical sandy shores in southernmost Brazil

Main trophic relationships that occur along the exposed sandy shores in southernmost Brazil (,336 S) are established taking into account several biological compartments operating at morphodynamically distinct environments. Beaches are predominantly of the intermediate type but some stretches of coastline are truly dissipative (Cassino Beach) or tending-to-reflective (Concheiros Beach), presenting thus diverse biological compartments and inhabitant macrobenthic assemblages. Dense concentrations of the surf-zone diatom Asterionellopsis glacialis are responsible - at least for the intermediate shorelines - for the most year-round primary production, sustaining several consumers up to tertiary level. Among them, bivalves Amarilladesma mactroides, Donax hanleyanus and the hippid crab Emerita brasiliensis can account for more than 95% of all the surf-zone secondary production, in addition to the elevated biomass of the suspension-feeder polychaete Spio gaucha and the scavenger isopod Excirolana armata. Crabs, whelks, carnivorous polychaetes, seabirds and surf-zone fishes may also be present and occupy superior trophic levels depending on the beach morphodynamics. Based on the high species richness, abundance and the role of macrobenthic fauna in transferring matter and energy to seabirds and the surf-zone fish assemblages, we address this important issue on the Southwestern Atlantic ecology. Conservation efforts should be implemented for the southernmost Brazilian sandy shores, at least for those non urbanized areas.As principais relac¸o˜ es tro´ ficas observadas ao longo da costa arenosa exposta do extremo sul do Brasil (,336 S) sa˜o estabelecidas levando-se em considerac¸a˜o os va´ rios compartimentos biolo´ gicos que operam em ambientes morfodinamicamente distintos. Estas praias sa˜o predominantemente do tipo intermedia´ rio, embora alguns trechos sejam dissipativos (Praia do Cassino) ou apresentem tendeˆncias reflectivas (Praia dos Concheiros), possuindo compartimentos biolo´ gicos diversificados e associac¸o˜es macrobentoˆnicas residentes. Densas concentrac¸o˜ es da diatoma´cea Asterionellopsis glacialis sa˜o responsa´ veis - pelo menos para as praias intermedia´ rias - por grande parte da produtividade prima´ ria anual, sustentando va´ rios consumidores ate´ o nı´vel tercia´ rio. Entre estes, os bivalves Amarilladesma mactroides, Donax hanleyanus e o crusta´ceo Emerita brasiliensis sa˜o responsa´ veis por mais de 95% de toda a produc¸a˜o secunda´ ria da zona de surfe, em adic¸a˜o a` elevada biomassa do poliqueta suspensı´voro Spio gaucha e do iso´pode necro´fago Excirolana armata. Caranguejos, gastro´ podes, poliquetas carnı´voros, aves marinhas e peixes da zona de surfe tambe´m podem estar presentes, ocupando nı´veis tro´ ficos superiores dependendo da morfodinaˆmica praial. Baseado na alta riqueza de espe´cies, na abundaˆncia e no papel da macrofauna bentoˆ nica em transferir mate´ria e energia para as aves marinhas e as assemble´ias de peixes da zona de surfe, esta importante questa˜o ecolo´ gica do Atlaˆntico Sudoeste foi investigada. Esforc¸os de conservac¸a˜o devem ser implementados nas praias arenosas do extremo sul do Brasil, pelo menos naquelas a´ reas na˜o urbanizadas