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.     

Relative movement and soil fixation of soluble organic and inorganic phosphorus

There is considerable concern about pollution of surface waters with P. Although most of the research has focused on inorganic P in surface runoff, it has recently become possible to easily follow the fate of soluble organic P forms in soils and waters. Two experiments were performed to compare the relative mobility and soil fixation affinity of orthophosphate monoesters, orthophosphate diesters, and soluble inorganic P. We used three P substrates, 4-methylumbelliferyl phosphate (MUP), deoxyribonucleic acid (DNA), and KH(2)PO(4) in (i) a soil column experiment and (ii) a soil P adsorption test tube experiment. Shortly after columns were prepared, approximately two pore volumes of 0.005 M CaCl(2) were passed through 25 cm length columns containing 10 cm of loamy sand amended with approximately 10 mg P as MUP, DNA, or KH(2)PO(4) above 15 cm of nonamended loamy sand. The total net quantity of 757.8 microg P 2L(-1) of orthophosphate diesters in the leachate from the DNA columns exceeded the net quantity of orthophosphate monoesters in leachate from the MUP columns (4.6 microg P 2L(-1)) and soluble inorganic P from the KH(2)PO(4) columns (34.0 microg P 2L(-1)). Adsorption of soluble organic and inorganic P in the test tube experiment yielded similar results: DNA, containing orthophosphate diesters, had a relatively low affinity for soils. In both experiments, high concentrations of other P compounds were identified in samples treated with organic P substrates, suggesting enzymatic hydrolysis by native soil phosphatase enzymes. These findings indicate that repeated application of organic forms of P could lead to significant leaching of P to ground water.     

Autoclaving soil samples affects algal-available phosphorus

Unwanted microbial interference in samples used for biological assays of P availability has routinely been eliminated by autoclaving samples before inoculation with algae. Twenty-three soils were selected to evaluate the relationship between algal growth in P-deficient solutions containing small quantities of soil and the level of P determined by a variety of tests used to evaluate P availability in soils and sediments. Soils were either autoclaved or not before addition to flasks containing P-starved algae in a nutrient solution without P. Compared to non-autoclaved samples, autoclaving soil resulted in approximately 60% more available P as estimated by increased algal growth. However, algal growth in the presence of autoclaved soil was highly correlated with growth in the presence of non-autoclaved samples. There was no consistent change in the correlations (r) between autoclaving or non-autoclaving samples in the relationships of algal numbers with P extracted by a number of soil tests. The effect of autoclaving soil on soluble P was also evaluated for a subset of six soils. Autoclaved soils had significantly greater concentrations of soluble P than non-autoclaved soils, with 78% more orthophosphate monoesters, 60% more orthophosphate diesters, and 54% more soluble inorganic P. Inhibition of algal growth may have occurred with two high-Zn soils that produced relatively low numbers of algae despite being very high in estimated available P by all extraction methods. Removing those samples from the calculations dramatically improved correlations between soil P measured by various methods and algal growth. With these two soils removed from calculations, algal growth with autoclaved soil was most highly correlated with Olsen P (r = 0.95), with other correlations as follows: Fe-oxide strip (r = 0.80), Mehlich 3 (r = 0.75,), modified Morgan (r = 0.61), and Bray-Kurtz 1 (r = 0.57).     

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.