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.     

Matrine and oxymatrine in corroborant plant extracts and fertilizers: HPLC/MS-MS method development and single-laboratory validation

A reversed phase high-performance liquid chromatographic method (HPLC/MS-MS) has been developed and validated for detection of alkaloids matrine and oxymatrine in fertilizer with labeled enhancer plant defense activities. The analytical method was validated statistically. The results show a strong matrix effect, requiring quantification by standard addition method. The regression lines showed r² > 0.994. Recoveries ranging from 97 to 104% were obtained for the fortification level of 0.01% wt wt^?1 and the relative standard deviations ranged from 3 to 4% (n = 10). The limits of detection were below 0.0001% wt wt^?1, while the limits of quantification did not exceed 0.0004% wt wt^?1. The method is currently applied in ICQRF Laboratory of Catania on fertilized and corroborant plant extract collected in the Italian market in the frame of MIPAAF institutional quality control activity, with the aim to dectect these unpermitted active substances.     

The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

Age-dating Diesel Fuel Spills: Using the European Empirical Time-based Model in the U.S.A.

In 1993, a paper was published by Christensen and Larsen that offered a method for determining the age of diesel oil spills in soil (Christensen and Larsen, 1993 Ground Water Mount. R . Fall , 142-149). It presented an empirical time-based model of the degradation of diesel fuel in soils using chemical data gathered at petroleum release sites in Denmark and the Netherlands. Now, evaluation of the validity of the application of this work to subsurface petroleum releases in other countries remains. In the U.S.A., investigations assessing date(s) of release of diesel fuel in soils, e.g. age dating of subsurface petroleum contamination, have considerable interest. Litigation-driven scientific investigations with accompanying expert testimony in a court of law are underway. The number of instances where application of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties is growing in the U.S.A. This paper presents two case studies which evaluate the applicability of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties in general. It illustrates the approach using gas chromatographic data from two recently-completed projects evaluating the applicability of the Christensen and Larsen model to a No. 2 fuel oil/diesel fuel surface spill in the U.S.A. Results showed that the application of the model to petroleum-contaminated soils was scientifically valid, provided its applicability was evaluated using hypothesis testing for specific changes in the characteristics of the petroleum hydrocarbon distribution in a number of soil samples collected over time at one site. The paper offers observations on the application of the Christensen and Larsen model to petroleum found in the light non-aqueous phase liquid (LNAPL) phase and groundwater.     

氨/硫铵法烟气脱硫技术特点及市场前景分析

通过对我国二氧化硫污染现状及控制要求的分析,提出了氨/硫铵法作为一种资源回收型脱硫方法,具有反应速度快、工艺流程简单、吸收剂利用率高、适用范围广及可实现资源回收利用的特点;以工程案例的形式分析了氨/硫铵法的技术经济指标,并对氨/硫铵法的应用前景和市场需求进行了预测。     

高加速应力试验装置技术参数的测量

气锤驱动的高加速应力试验装置,能产生温度和非高斯随机振动应力,其中振动应力是由多个气锤作六自由度运动产生的。一般用来进行高温步进、低温步进、快速温度变化、振动、快速温变和振动复合试验。目前国家标准和校准规程中均无关于该试验装置的技术参数的校准方法。本文结合试验装置的技术特点,提出了几个关于温度和振动技术参数的测量方法,如:温度偏差、温度波动度、温度均匀度、温度过冲量、温度变化速率、均方根加速度、横向振动比、功率谱密度等。     

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.     

System Dynamics to Sustainable Water Resources Management in the Eastern Snake Plain Aquifer Under Water Supply Uncertainty1

Abstract: Water supply uncertainty continues to threaten the reliability of regional water resources in the western United States. Climate variability and water dispute potentials induce water managers to develop proactive adaptive management strategies to mitigate future hydroclimate impacts. The Eastern Snake Plain Aquifer in the state of Idaho is also facing these challenges in the sense that population growth and economic development strongly depend on reliable water resources from underground storage. Drought and subsequent water conflict often drive scientific research and political agendas because water resources availability and aquifer management for a sustainable rural economy are of great interest. In this study, a system dynamics approach is applied to address dynamically complex problems with management of the aquifer and associated surface‐water and groundwater interactions. Recharge and discharge dynamics within the aquifer system are coded in an environmental modeling framework to identify long‐term behavior of aquifer responses to uncertain future hydrological variability. The research shows that the system dynamics approach is a promising modeling tool to develop sustainable water resources planning and management in a collaborative decision‐making framework and also to provide useful insights and alternative opportunities for operational management, policy support, and participatory strategic planning to mitigate future hydroclimate impacts in human dimensions.     

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.     

Laboratory studies on formation and minimisation of polychlorinated dibenzodioxins and -furans (PCDD/F) in secondary aluminium process

The objectives of this work were to study the formation mechanisms of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) in thermal aluminium recycling processes by use of laboratory experiments. The pattern of isomers of PCDD/F indicates that de novo synthesis is important in aluminium smeltery. The mechanisms of PCDD/F formation in aluminium smelting are similar to that of various incineration processes of waste material. The results of bioanalysis (EROD-test) confirms the existence of de novo synthesis of PCDD/F, but points out to the existence to some additional, toxic compounds of unknown structure. To reduce the amount of PCDD/F the input of carbon at the metal should be reduced; in addition the metal smeltery plants should be cleaned from fly ash particles. It is suggested to use good primary methods in the technical plants like constant feeding of the metal into the oven will minimise PCDD/F concentration. The biological EROD-bioassay is a good tool to estimate PCDD/F-TEQ values also for this technical process simulated in the laboratory.