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.     

Aqueous solubility, effects of salts on aqueous solubility, and partitioning behavior of hexafluorobenzene: experimental results and COSMO-RS predictions

The aqueous solubility of hexafluorobenzene has been determined, at 298.15 K, using a shake-flask method with a spectrophotometric quantification technique. Furthermore, the solubility of hexafluorobenzene in saline aqueous solutions, at distinct salt concentrations, has been measured. Both salting-in and salting-out effects were observed and found to be dependent on the nature of the cationic/anionic composition of the salt. COSMO-RS, the Conductor-like Screening Model for Real Solvents, has been used to predict the corresponding aqueous solubilities at conditions similar to those used experimentally. The prediction results showed that the COSMO-RS approach is suitable for the prediction of salting-in/-out effects. The salting-in/-out phenomena have been rationalized with the support of COSMO-RS σ-profiles. The prediction potential of COSMO-RS regarding aqueous solubilities and octanol-water partition coefficients has been compared with typically used QSPR-based methods. Up to now, the absence of accurate solubility data for hexafluorobenzene hampered the calculation of the respective partition coefficients. Combining available accurate vapor pressure data with the experimentally determined water solubility, a novel air-water partition coefficient has been derived.     

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.