Mass Spectrometric Detection and Identification of Polar Pesticides and their Degradation Products - A Comparison of Different Ionization Methods

Due to increasing use of polar pesticides, they are found together with their degradation products in ground- and surface waters serving for drinking water treatment. The triazine derivatives acetamido-atrazine, ametryne, atrazine, cyanazine, deethylatrazine, deethyldeisopropyl-hydroxyatrazine, deethyl-hydroxyatrazine, deisopropyl-atrazin, deisopropyl-hydroxyatrazine, desmetryn, hydroxyatrazine, prometryne, propazine, simazine, terbumeton, terbutryne and terbutylazine, and the pesticides 2,4-D, dichlorprop, isoproturon, diuron, metolachlor, glyphosate, metsulfuronmethyl and dalapon, all of them belonging to this type of pesticides, have been studied. For determination of triazine derivatives UV detection by means of diode array detector (DAD) as well as mass spectrometric (MS) detection coupled by thermospray interface (TSP) have been used successfully after liquid chromatoraphic (LC) separation. Interfaces like thermospray (TSP), electrospray (ESP) and atmospheric pressure chemical ionisation (APCI) were examined with regard to their suitability for substance-specific detection of polar pesticides by flow injection analysis (FIA) with MS- and tandem mass spectroscopic detection (MS/MS) without preceding LC separation. Optimised detection conditions for these pesticides using FIA are presented, and solutions for occurring problems are offered.     

Toxicological responses in Laeonereis acuta (annelida, polychaeta) after arsenic exposure

Several environmental pollutants, including metals, can induce oxidative stress. So, the objective of this study was to evaluate the effects of arsenic (As(III), as As(2)O(3)) on the antioxidant responses in the polychaete Laeonereis acuta. Worms were exposed to two environmentally relevant concentrations of As, including the highest previously allowed by Brazilian legislation (50 microg As/l). A control group was kept in saline water (10 per thousand) without added metal. It was observed that: (1) a peak concentration of lipid peroxide was registered after 2 days of exposure to 50 microg As/l (61+/-3.2 nmol CHP/g wet weight) compared to the control group (43+/-4.5 nmol CHP/g wet weight), together with a lowering of the activity of the antioxidant enzyme catalase (-47 and -48%, at 50 or 500 microg As/l respectively) and a higher superoxide dismutase activity (+305% at 50 microg As/l with respect to the control group); (2) a lower conjugation capacity through glutathione-S-transferase activity was observed after 7 days of exposure to 50 microg As/l (-48% compared to the control group); (3) a significant increase in As concentration was verified after 1 week of exposure to both As concentrations (50 and 500 microg/l); (4) worms exposed to As showed a limited accumulation of related methylated As species and the levels of non-toxic As species like arsenobetaine (AsB) and arsenocholine (AsC) remained unchanged during the exposure period when compared with the controls. Overall, it can be concluded that As interfered in the antioxidant defense system of L. acuta, even at low concentrations (50 microg/l) that Brazilian legislation previously considered safe. The fact that worms exposed to As showed high levels of methylated As species indicates the methylation capability of L. acuta, although the high levels of inorganic As suggest that not all the administered As(III) (as As(2)O(3)) is completely removed or biotransformed after 7 days of exposure.     

Antioxidant responses and reactive oxygen species generation in different body regions of the estuarine polychaeta Laeonereis acuta (Nereididae)

The aim of this study was to analyze the total antioxidant capacity (TOSC), generation of reactive oxygen species (ROS) and lipid peroxidation (LPO) in the different body regions of the estuarine polychaeta Laeonereis acuta (Nereididae) sampled at non-polluted (NOPOL) and polluted (POL) sites from Lagoa dos Patos (Southern Brazil). Organisms collected at POL during summer showed similar (p>0.05) TOSC values along the body, but worms collected at NOPOL presented higher (p<0.05) TOSC values in the posterior (P) region in respect of anterior (A) region and middle (M) region. TOSC in the P region at NOPOL was higher (p<0.05) compared with the same body region of worms at POL. In summer, ROS concentration was higher in A and M regions of worms at POL in respect of the organisms at NOPOL. During winter all the regions showed higher ROS in worms sampled at POL. It was registered absence of season influence on LPO content, but in the P region at NOPOL in summer there were lower LPO levels compared with the others regions (p<0.05). In vitro assays showed that P region, despite a higher basal ROS, presented a higher competence to cope with pro-oxidants compared with A and M regions (p<0.05), corroborating the field results. A lower proteic sulfhydril content was observed in P in respect of the other regions (p<0.05) supporting the idea of a highest oxidant condition in this region. The results indicate that worms collected at the POL site are confronted to higher ROS concentrations, affecting its antioxidant capacity, a result that depends of body regions.     

Predicted Climate‐Driven Bird Distribution Changes and Forecasted Conservation Conflicts in a Neotropical Savanna

Abstract: Climate‐change scenarios project significant temperature changes for most of South America. We studied the potential impacts of predicted climate‐driven change on the distribution and conservation of 26 broad‐range birds from South America Cerrado biome (a savanna that also encompass tracts of grasslands and forests). We used 12 temperature or precipitation‐related bioclimatic variables, nine niche modeling techniques, three general circulation models, and two climate scenarios (for 2030, 2065, 2099) for each species to model distribution ranges. To reach a consensus scenario, we used an ensemble‐forecasting approach to obtain an average distribution for each species at each time interval. We estimated the range extent and shift of each species. Changes in range size varied across species and according to habitat dependency; future predicted range extent was negatively correlated with current predicted range extent in all scenarios. Evolution of range size under full or null dispersal scenarios varied among species from a 5% increase to an 80% decrease. The mean expected range shifts under null and full‐dispersal scenarios were 175 and 200 km, respectively (range 15–399 km), and the shift was usually toward southeastern Brazil. We predicted larger range contractions and longer range shifts for forest‐ and grassland‐dependent species than for savanna‐dependent birds. A negative correlation between current range extent and predicted range loss revealed that geographically restricted species may face stronger threat and become even rarer. The predicted southeasterly direction of range changes is cause for concern because ranges are predicted to shift to the most developed and populated region of Brazil. Also, southeastern Brazil is the least likely region to contain significant dispersal corridors, to allow expansion of Cerrado vegetation types, or to accommodate creation of new reserves.     

Residential Water Consumption,Motivation for Conserving Water and the Continuing Tragedy of the Commons

This paper explores the effect of the perception of externalities (PE) on residential water consumption. Externalities occur when individuals make decisions that harm others, without concern for the impact or feeling a need to compensate for the harm. The aim of this study was to investigate whether PE affects people's motivation to conserve water, and, consequently, the practice of residential water consumption. Two hundred eighty Mexican citizens responded to a questionnaire investigating how they perceived that other individuals in their community wasted water. Respondents were also asked about their motives to conserve water, and direct observations of individual water consumption were recorded. Results were processed within a structural equations model, which revealed that motives to conserve water significantly inhibit water consumption. Since the perception of externalities also inhibits conservation motives, the resulting effect of PE on water consumption is positive. This result means that the more people perceive that others waste water, the less their conservation motives, and, therefore, the more their own water consumption.