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.     

Evaluating Environmental Parameters for Minimum Ammonium Losses during Composting of Trimming Residues

Abstract

A neural fuzzy system was used to investigate the influence of environmental variables (time, aeration, moisture, and particle size) on composting parameters (pH, organic matter [OM], nitrogen [N], ammonium nitrogen [NH₄ ⁺-N] and nitrate nitrogen [NO₃ ^--N]). This was to determine the best composting conditions to ensure the maximum quality on the composts obtained with the minimum ammonium losses. A central composite experimental design was used to obtain the neural fuzzy model for each dependent variable. These models, consisting of the four independent process variables, were found to accurately describe the composting process (the differences between the experimental values and those estimated by using the equations never exceeded 5–10% of the former). Results of the modeling showed that creating a product with acceptable chemical properties (pH, NH₄ ⁺-N and NO₃ ^--N) entails operating at medium moisture content (55%) and medium to high particle size (3–5 cm). Moderate to low aeration (0.2 L air/min · kg) would be the best compromise to compost this residue because of the scant statistical influence of this independent variable.     

Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System1

Stoeckel, James A., Jade Morris, Elizabeth Ames, David C. Glover, Michael J. Vanni, William Renwick, and María J. González, 2012. Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System. Journal of the American Water Resources Association (JAWRA) 48(3): 616-634. DOI: 10.1111/j.1752-1688.2011.00633.x Abstract: We used enzyme-linked immunosorbent assay to examine reservoir-mediated shifts in spring to fall exposure of aquatic organisms to the spring atrazine pulse over four years in a Midwestern stream-reservoir system. Peak atrazine concentrations in the major inflowing stream exceeded 10 μg/l in all four years. The reservoir had a beneficial effect in two of four years by diluting atrazine below the 10 μg/l threshold. However, during the other two years, exposure times above 10 μg/l were approximately doubled in the reservoir compared to the major inflowing stream. Thresholds of 3 and 5 μg/l were exceeded during all four years in the reservoir. The uplake and downlake reservoir sites were four to five times more likely to exceed these thresholds and aquatic organisms were subjected to longer exposure times above these thresholds compared to the inflowing stream. Release of elevated atrazine concentrations from the reservoir extended exposure times in the outflowing stream. This effect was most pronounced just below the dam. Aquatic organisms upstream of the reservoir were most likely to experience acute exposures whereas organisms within and immediately downstream of the reservoir were more likely to experience chronic exposures. The ubiquity of reservoirs and the annual spring herbicide flush highlight the importance of considering the presence and relative location of reservoirs when assessing risk to aquatic communities as well as locations of drinking water intakes.     

Is Urban Stream Restoration Worth It?1

Kenney, Melissa A., Peter R. Wilcock, Benjamin F. Hobbs, Nicholas E. Flores, and Daniela C. Martínez, 2012. Is Urban Stream Restoration Worth It? Journal of the American Water Resources Association (JAWRA) 48(3): 603-615. DOI: 10.1111/j.1752-1688.2011.00635.x Abstract: Public investment in urban stream restoration is growing, yet little has been done to quantify whether its benefits outweigh its cost. The most common drivers of urban stream projects are water quality improvement and infrastructure protection, although recreational and aesthetic benefits are often important community goals. We use standard economic methods to show that these contributions of restoration can be quantified and compared to costs. The approach is demonstrated with a case study in Baltimore, Maryland, a city with a legal mandate to reduce its pollutant load. Typical urban stream restoration costs of US$500-1,200 per foot are larger than the cost of the least expensive alternatives for management of nitrogen loads from stormwater (here, detention ponds, equivalent to $30-120 per foot of restored stream) and for protecting infrastructure (rip-rap armoring of streambanks, at $0-120 per foot). However, the higher costs of stream restoration can in some cases be justified by its aesthetic and recreational benefits, valued using a contingent valuation survey at $560-1,100 per foot. We do not intend to provide a definitive answer regarding the worth of stream restoration, but demonstrate that questions of worth can be asked and answered. Broader application of economic analysis would provide a defensible basis for understanding restoration benefits and for making restoration decisions.     

Concentrations of organochlorine pesticides and 2,4,6-trichloroanisole in cork bark

Organochlorine pesticides are persistent lipophilic organic pollutants and tend to accumulate in growing plants. During growth, cork is in contact with the open air for long periods (9-12 years). Owing to the previous widespread use of organochlorine pesticides and their high persistence in the environment, there is a risk that residues of such pesticides may be present in cork.In this study, the concentrations of 14 organochlorine pesticides—all of which are indicators of environmental pollution—were analyzed in cork bark samples from three regions in Spain and one in Portugal. In addition, the concentrations of 2,4,6-trichlorophenol (TCP) and 2,4,6-trichloroanisole (TCA) were also analyzed.Our results show only very low concentrations of lindane, γ-HCH (<2.6 ng g⁻¹) and its byproducts α-HCH (<3.5 ng g⁻¹) and β-HCH (<0.6 ng g⁻¹).Among the DDT and its metabolites, only two were found: p,p′-DDT was found in a cork sample from Extremadura (0.1 ng g⁻¹) and p,p′-DDE was present at a maximum concentration of 2.9 ng g⁻¹ in a cork sample from Castile-La Mancha. However, all concentrations were well below the legal limit established by Regulation (EC) No. 396/2005 (10 ng g⁻¹ in foodstuffs). We can conclude, therefore, that the cork samples we studied complied with food safety standards.     

Levels of organochlorine pesticides and polychlorinated biphenyls in the critically endangered Iberian lynx and other sympatric carnivores in Spain

Accumulation of organochlorine compounds is well studied in aquatic food chains whereas little information is available from terrestrial food chains. This study presents data of organochlorine levels in tissue and plasma samples of 15 critically endangered Iberian lynx (Lynx pardinus) and other 55 wild carnivores belonging to five species from three natural areas of Spain (Doñana National Park, Sierra Morena and Lozoya River) and explores their relationship with species diet. The Iberian lynx, with a diet based on the consumption of rabbit, had lower PCB levels (geometric means, plasma: <0.01 ng mL⁻¹, liver: 0.4 ng g⁻¹ wet weight, fat: 87 ng g⁻¹ lipid weight) than other carnivores with more anthropic and opportunistic foraging behavior, such as the red fox (Vulpes vulpes; plasma: 1.11 ng mL⁻¹, liver: 459 ng g⁻¹, fat: 1984 ng g⁻¹), or with diets including reptiles at higher proportion, such as the Egyptian mongoose (Herpestes ichneumon; plasma: 7.15 ng mL⁻¹, liver: 216 ng g⁻¹, fat: 540 ng g⁻¹), or the common genet (Genetta genetta; liver: 466 ng g⁻¹, fat: 3854 ng g⁻¹). Chlorinated pesticides showed interspecific variations similar to PCBs. Organochlorine levels have declined since the 80s in carnivores from Doñana National Park, but PCB levels are still of concern in Eurasian otters (Lutra lutra; liver: 3873-5426 ng g⁻¹) from the industrialized region of Madrid.     

Phenol and nitrophenols in the air and dew waters of Santiago de Chile

Phenol, nitrophenols and dinitrophenols were measured in air and dews in downtown Santiago de Chile. In both systems, phenol, 2-nitrophenol (2-NP), and 4-nitrophenol (4-NP) were the compounds found in higher concentrations and with major frequency. Temporal profiles in air were compatible with a significant direct incorporation from mobile sources. The data can be explained in terms of a faster removal of 2-NP than 4-NP, with the former predominating in fresh air masses and 4-NP in more aged samples. All these compounds, as well as dinitrophenols, were found in dew waters. Simultaneous measurements in air and dew indicate that phenol present in dew exceeds that expected in equilibrated samples, while the opposite occurs with 4-NP. This last result is associated to mass transfer limitations for the highly water soluble nitroderivative.     

Photocatalytic degradation of five sulfonylurea herbicides in aqueous semiconductor suspensions under natural sunlight

In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO₃), tin (IV) oxide (SnO₂) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na₂S₂O₈) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t_½) ranged from 8 to 27 min (t_30W = 0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na₂S₂O₈ system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L⁻¹).     

Long-term effect of temperature on bioaccumulation of dietary metals and metallothionein induction in Sparus aurata

Previous studies have demonstrated that the commercial feed of aquacultured fish contains trace amounts of toxic and essential metals which can accumulate in tissues and finally be ingested by consumers. Recently rising temperatures, associated to the global warming phenomenon, have been reported as a factor to be taken into consideration in ecotoxicology, since temperature-dependent alterations in bioavailability, toxicokinetics and biotransformation rates can be expected. Sparus aurata were kept at 22 °C, 27 °C and 30 °C for 3 months in order to determine the temperature effect on metallothionein induction and metal bioaccumulation from a non-experimentally contaminated commercial feed. A significant temperature-dependent accumulation of cadmium (Cd), copper (Cu), mercury (Hg), zinc (Zn), lead (Pb) and iron (Fe) was found in liver, together with that of manganese (Mn), Fe and Zn in muscle. Hg presented the highest bioaccumulation factor, and essential metal homeostasis was disturbed in both tissues at warm temperatures. An enhancement of hepatic metallothionein induction was found in fish exposed to the highest temperature.     

Lindane removal by pure and mixed cultures of immobilized actinobacteria

Stereoselective dissipation of epoxiconazole had been studied in grape and soil during plant growing under field conditions in this paper. A sensitive and rapid chiral method was developed and validated for the determination of epoxiconazole stereoisomers in grape and soil based on liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS). Phenomenex Lux Cellulose-1 column was used for enantioseparation with a mixture of acetonitrile/water (90/10, v/v) as mobile phase at flow rate of 0.3 mL min⁻¹. Fortified recoveries in grape and soil samples ranged from 76.0% to 91.9% and relative standard deviations were less than 11.4% with fortified levels of 0.025-1.0 mg kg⁻¹. The limits of detection and quantification were 0.005 mg kg⁻¹ and 0.025 mg kg⁻¹, respectively, with linear calibration curves extending up to 5.0 mg kg⁻¹. The field experimental results showed that dissipations of epoxiconazole stereoisomers in grape followed first-order kinetics (R² > 0.92) and stereoselectivity occurred in 2 h after spraying. The (−)-stereoisomer with half-life of 9.3 d degraded faster than (+)-stereoisomer with that of 13.2 d, and resulted in relative enrichment of (+)-stereoisomer. However, the stereoisomeric dissipations in soil were triphasic (“increase-decrease-steady”) with lower dissipation rates, and also occurred with preferential degradation of (−)-stereoisomer under field condition. The results for stereoselective dissipations can be applied for food and environmental assessments of chiral pesticides.