Pesticide dissipation curves in peach,pear and tomato crops in Uruguay*

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r²=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r²=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Comparative abiotic or biotic degradation of carboxin by two Entisols with different surface properties or Pseudomonas aeruginosa strain: A toxicity study using the crustacean Thamnocephalus platyurus

The microcrustacean Thamnocephalus platyurus was used to detect the toxicity reduction of carboxin in abiotic degradation compared to biotic degradation. The abiotic degradation was obtained using two sterilized Entisols with different surface properties while the biotic degradation by Pseudomonas aeruginosa was obtained using the fungicide as the only C source. The results showed that the highest toxicity reduction rates for the abiotic degradation were achieved in 20 days with 49.2% for the coarser soil, 60.7% for the soil with a finer texture, whereas for the biotic degradation, 60.6%. Analysis (¹H NMR) showed that the soils transformed carboxin to produce sulfoxide and enol in different concentrations depending on the soil properties, while P. aeruginosa metabolized the fungicide to produce inorganic compounds such as ammonium and nitrite, minor degradation pathways were oxidized to sulfoxide and hydrolytic ring-opening to 2-[(2-hydroxyethyl)thio]acetoacetanilide enol. These results indicated that the degradation of carboxin occurred via abiotic catalytic processes as well as via biotic transformation leading to less toxic derivatives and such phenomena are caused by exchange/surface features of soils, rather than by the mere content of clay or organic matter fractions.     

Arsenic exposure in Hungary, Romania and Slovakia

Inorganic arsenic is a potent human carcinogen and toxicant which people are exposed to mainly via drinking water and food. The objective of the present study was to assess current exposure to arsenic via drinking water in three European countries. For this purpose, 520 individuals from four Hungarian, two Slovakian and two Romanian countries were investigated by measuring inorganic arsenic and methylated arsenic metabolites in urine by high performance liquid chromatography with hydride generation and inductively coupled plasma mass spectrometry. Arsenic in drinking water was determined by atomic absorption spectrometry. Significantly higher concentrations of arsenic were found in both the water and the urine samples from the Hungarian counties (median: 11 and 15 microg dm(-3), respectively; p < 0.001) than from the Slovakian (median: 0.94 and 4.5 microg dm(-3), respectively) and Romanian (median: 0.70 and 2.1 microg dm(-3), respectively) counties. A significant correlation was seen between arsenic in water and arsenic in urine (R(2)= 0.46). At low water arsenic concentrations, the relative amount of dimethylarsinic acid (DMA) in urine was increased, indicating exposure via food. Also, high body mass index was associated with higher concentrations of arsenic in urine (p= 0.03), mostly in the form of DMA. Smokers had significantly higher urinary arsenic concentrations than non-smokers (p= 0.03). In conclusion, elevated arsenic exposure via drinking water was prevalent in some of the counties. Exposure to arsenic from food, mainly as DMA, and cigarette smoke, mainly as inorganic arsenic, are major determinants of arsenic exposure at very low concentrations of arsenic in drinking water.     

Chemical and spectroscopic characterization of organic matter during the anaerobic digestion and successive composting of pig slurry

In this work, anaerobic digestion of pig slurry and successive composting of the digestate after centrifugation were studied by means of chemical analysis, FTIR and fluorescence spectroscopy as excitation–emission matrix (EEM). Chemical analysis highlighted the organic matter transformation occurring during the processes. A decrease of volatile solids and total organic carbon were observed in the digestate with respect to the fresh pig slurry as a consequence of the consumption of sugars, proteins, amino acids and fatty acids used by microorganisms as a C source. Water Extractable Organic Matter (WEOM) was obtained for all samples and fractionated into a hydrophilic and a hydrophobic fraction. The highest WEOM value was found in the pig slurry indicating a high content of labile organic C. The digestate centrifuged and the digestate composted showed lower hydrophilic and higher hydrophobic contents because of the decrease of labile C. Total phenolic content was lower in the digestate with respect to fresh pig slurry sample (36.7%) as a consequence of phenolic compounds degradation. The strong decrease of total reducing sugars in the digestate (76.6%) as compared to pig slurry confirmed that anaerobic process proceed mainly through consumption of sugars which represent a readily available energy source for microbial activity. FTIR spectra of pig slurry showed bands indicative of proteins and carbohydrates. A drop of aliphatic structures and a decrease of polysaccharides was observed after the anaerobic process along with the increase of the peak in the aromatic region. The composted substrate showed an increase of aromatic and a relative decrease of polysaccharides. EEM spectra provided tryptophan:fulvic-like fluorescence ratios which increased from fresh substrate to digestate because of the OM decompostion. Composted substrate presented the lowest ratio due to the humification process.     

Co-treatment of fruit and vegetable waste in sludge digesters. An analysis of the relationship among bio-methane generation,process stability and digestate phytotoxicity

The co-digestion of a variable amount of fruit and vegetable waste in a waste mixed sludge digester was investigated using a pilot scale apparatus. The organic loading rate (OLR) was increased from 1.46 kg VS/m³ day to 2.8 kg VS/m³ day. The hydraulic retention time was reduced from 14 days to about 10 days. Specific bio-methane production increased from about 90 NL/kg VS to the maximum value of about 430 NL/kg VS when OLR was increased from 1.46 kg VS/m³ day to 2.1 kg VS/m³ day. A higher OLR caused an excessive reduction in the hydraulic retention time, enhancing microorganism wash out. Process stability evaluated by the total volatile fatty acids concentration (mg/l) to the alkalinity buffer capacity (eq. mg/l CaCO₃) ratio (i.e. FOS/TAC) criterion was <0.1 indicating high stability for OLR <2.46 kg VS/m³ day. For higher OLR, FOS/TAC increased rapidly. Residual phytotoxicty of the digestate evaluated by the germination index (GI) (%) was quite constant for OLR < 2.46 kg VS/m³ day, which is lower than the 60% limit, indicating an acceptable toxicity level for crops. For OLR > 2.46 kg VS/m³ day, GI decreased rapidly. This corresponding trend between FOS/TAC and GI was further investigated by the definition of the GI ratio (GIR) parameter. Comparison between GIR and FOS/TAC suggests that GI could be a suitable criterion for evaluating process stability.     

Biopotentiality as an index of environmental compensation for composting plants

The Biopotentiality Index is a landscape ecology indicator, which can be used to estimate the latent energy of a given land and to assess the environmental impacts due to the loss of naturalness on a landscape scale. This indicator has been applied to estimate the effectiveness of the measures put in place to provide an environmental compensation for the revamping of a composting plant. These compensation measures are represented by a green belt with a minimum width of 25 m all around the plant, representing both a windbreak and a buffer zone, and by two wide wooded zones acting as core natural areas.This case-study shows that the compensation index could be used as a key tool in order to negotiate the acceptance of waste treatment plant with the population.     

A statistical methodology for the evaluation of long-range dispersion models: an application to the ETEX exercise

This paper describes the statistical methodology applied to evaluate the performance of the long-range dispersion models that were used in the modelling activities of ETEX (European Tracer EXperiment). The availability of a large number of models makes this exercise rather unique. These models are used for the practical purpose to quantify the contamination effects over a vast area, following a hypothetical accidental release of harmful material. This makes the quality judgement that could be attributed to the results of each model particularly important.The statistical indicators considered to be the most effective for the evaluation of long-range dispersion models are introduced and commented, with specific examples in the frame of ETEX simulations. The importance of using several indices and critically interpreting the results is discussed.