Limitations in the determination of maximum residue limits and highest residues of pesticides: Part I

The pesticide usages are controlled by comparing residue concentrations in treated commodities to legally permitted maximum levels (MRLs) determined based on supervised trials designed to reflect likely maximum residues occurring in practice following authorised use. The number of trials available may significantly affect the accuracy of estimated maximum residues. We conducted a study with synthetic lognormal distributions with mean of 1 and standard deviations of 0.8 and 1.0, which reflect the residue distributions observed in practice. The likely residues in samples were modelled by drawing random samples of size 3, 5, 10 and 25 from the synthetic populations. The results indicate that the estimations of highest residues (HR), used for calculation of short-term intake, and the MRLs, serving as legal limits, are very uncertain based on 3–5 trials indicated by the calculated HR_0.975/HR_0.025 and MRL_0.975/MRL_0.025 ratios of 12 and 9, and 13 and 10, respectively, which question the suitability of such trials for the intended purpose. As the 95% range of HR and MRL rapidly decreases with number of trials, ideally ≥15 but minimum 6–8 trials should be used for estimation of HR and MRL according to the current typical practice of Codex Alimentarius.     

Effect of feeding strategy and COD/sulfate ratio on the removal of sulfate in an AnSBBR with recirculation of the liquid phase

The objective of this work was to analyze the effect of the interaction between feeding strategy and COD/sulfate ratio on the removal efficiency of sulfate and organic matter from a synthetic wastewater. An anaerobic sequencing batch reactor with recirculation of the liquid phase and containing immobilized biomass on polyurethane foam (AnSBBR) was used. The AnSBBR with a total volume of 3.7 L, treated 2.0 L synthetic wastewater in 8-h cycles at 30 ± 1 °C and was inoculated with anaerobic biomass from a UASB. Two feeding strategies were assessed: (a) batch and (b) batch followed by fed-batch. In strategy (a) the reactor was fed in 10 min with 2 L wastewater containing sulfate and carbon sources. In strategy (b) 1.2 L wastewater (containing only the sulfate source) was fed during the first 10 min of the cycle and the remaining 0.8 L (containing only the carbon source) in 240 min. The COD/sulfate ratios assessed were 1 and 3. Based on these values and on the concentrations of organic matter (0.5–11.25 gCOD/L) and sulfate (0.5 and 2.5 gSO₄^2?/L), the sulfate and organic matter loading rates applied equaled 1.5 and 4.5 gSO₄^2?/L d for sulfate and 1.5, 4.5 and 13.5 gCOD/L d for organic matter. After stabilization of the system time profiles were run of monitored parameters (COD, sulfate, sulfide and sulfite). In general, the reactor showed to be robust for use in the anaerobic treatment of wastewaters containing sulfate. Gradual feeding (strategy b) of the carbon source favored sulfate reduction, resulting in sulfate removal efficiencies of 84–98% and organic matter removal efficiencies of 48–95%. The best results were observed under COD/sulfate ratio equal to 1 (loading rates of 1.5 and 4.5 gSO₄^2?/L d for sulfate, and 1.5 and 4.5 gCOD/L d for organic matter). When COD/sulfate ratio was 3 (loading rates of 1.5 and 4.5 gSO₄^2?/L d for sulfate, and 4.5 and 13.5 gCOD/L d for organic matter) the effect of feed mode became less significant. These results show that the strategy batch followed by fed-batch is more advantageous for COD/sulfate ratios near the stoichiometric value (0.67) and higher organic matter and sulfate concentrations.     

Proposal for selective differentiating of nerve agent G and V type with utilisation of modified Ellman’s method

We studied issues of organophosphorus agents’ analysis. Immobilised enzyme–inhibitors complexes (e.g. acetylcholinesterase-organophosphate nerve agent) were studied with modified Ellman’s biochemical method utilised for assessment of acetylcholinesterase activity. Biochemical reactions are widespread and they are the most frequent used analytical methods for determination of nerve agents. This modified method is based on the nucleophilic reactions of mono- and bispyridinium aldoximes of a type 2-PAM, MMB-4 and HI-6, their homologues and isomers with enzyme–inhibitor complexes. The procedure for a gradual analysis of G and V type, Sarin, Cyclohexylsarin, Soman, Tabun, agent VX and R-33 was proposed in terms of studied nucleophilic substitution reactions quantification results. This method enables selective determination of these chemical warfare agents. A gradual analysis was evaluated by statistic method of probabilistic calculus. This type of analysis can be used for assessment of acetylcholinesterase inhibitors in very low concentrations close to hygienic limits.     

Comparison of environmental impacts related to municipal solid waste and construction and demolition waste management and recycling in a Latin American developing city

Environmental Science and Pollution Research - Construction and demolition waste (CDW) and municipal solid waste (MSW) are the waste flows mostly generated at a global level. In developing...     

Effects of deltamethrin on hepatic microsomal cytochrome p450‐dependent monooxygenases in carp

Abstract The in vivo effects of sublethal concentrations of deltamethrin (DM), a pyrethroid insecticide, on the hepatic microsomal cytochrome P450 (Cyt P450) content and the Cyt P450‐dependent monooxygenase activities (para‐nitrophenetole‐O‐deethylase, pNPOD; aminopyrene‐N‐demethylase, APND; ethylmorphine‐N‐demethylase, EMND; 7‐ethoxycoumarin‐O‐deethylase, ECOD; and ethoxyresorufin‐O‐deethylase, EROD) were examined in adult carp (Cyprinus carpió L.).

0.2 μg/1 DM treatment resulted in significant increases in APND, EMND and ECOD activities, whereas 2 μg/1 DM resulted in significant inhibitions of all studied isoenzyme activities with the exceptions of pNPOD and APND after 72 h. EROD was the only enzyme for which a slight increase in activity was observed. On repeated treatment, Cyt P450 could not be detected after 48 h, but the Cyt P420 level increased. All tested isoenzyme activities were inhibited, with the exception ofthat of EROD, which was enhanced.

All these changes in enzyme activities and Cyt P450 content demonstrate the effects of DM on fish. DM treatment at low concentration is presumed to cause induction of the Cyt P450‐dependent monooxygenases which may lead to faster metabolization of the insecticide. In contrast, DM at higher concentration strongly inhibited the activities of the studied enzymes. This finding may be due to the damaging effect of DM on the xenobiotic metabolizing enzyme systems offish.     

Determination of gaseous polycyclic aromatic hydrocarbons by a simple direct method using thermal desorption–gas chromatography–mass spectrometry

In the last decade, the development of novel analytical methodologies enabled the identification of several environmental pollutants responsible for health problems associated with indoor exposure. Polycyclic aromatic hydrocarbons (PAHs) are among the potential hazardous chemicals present in ambient air. Due to their bioaccumulation potential and carcinogenic/mutagenic effects, 16 PAHs are currently listed as priority air pollutants. The main goal of this work was to implement a new and simple method for sampling and determination of PAHs in air by using a thermal desorption (TD) technique followed by gas chromatography coupled with mass spectrometry analysis. A detailed study was carried out to optimise the experimental method in each of its phases, including (active) sampling, TD and chromatographic analysis. The results demonstrate that this approach allowed the detection and quantification of the six more volatile PAHs, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. Acceptable precision and good linearity over the explored range were obtained. No carry-over was observed during experimental tests and the method provided a reproducible answer. The applicability of the novel methodology was tested in real environment, namely, on the roof of a building in an urban area, in a domestic kitchen and in a collective car garage. The method enabled the identification of two PAHs in the field samples, specifically, naphthalene (two rings) and phenanthrene (three rings). With regard to PAHs sample composition, the most abundant PAH found, in the three different locations, was naphthalene, accounting for about 84–100 % of the total PAH mass detected.     

Brassica napus hairy roots and rhizobacteria for phenolic compounds removal

Phenolic compounds are contaminants frequently found in water and soils. In the last years, some technologies such as phytoremediation have emerged to remediate contaminated sites. Plants alone are unable to completely degrade some pollutants; therefore, their association with rhizospheric bacteria has been proposed to increase phytoremediation potential, an approach called rhizoremediation. In this work, the ability of two rhizobacteria, Burkholderia kururiensis KP 23 and Agrobacterium rhizogenes LBA 9402, to tolerate and degrade phenolic compounds was evaluated. Both microorganisms were capable of tolerating high concentrations of phenol, 2,4-dichlorophenol (2,4-DCP), guaiacol, or pentachlorophenol (PCP), and degrading different concentrations of phenol and 2,4-DCP. Association of these bacterial strains with B. napus hairy roots, as model plant system, showed that the presence of both rhizospheric microorganisms, along with B. napus hairy roots, enhanced phenol degradation compared to B. napus hairy roots alone. These findings are interesting for future applications of these strains in phenol rhizoremediation processes, with whole plants, providing an efficient, economic, and sustainable remediation technology.     

Remediation procedure used for contaminated soil and underground water: A case study from the chemical industry

This is a case study of contamination by a non-aqueous phase liquid (NAPL) that leaked from a chemical plant. The remediation procedure adopted for the initial phase of the plume migration was a plastic diaphragm wall coupled with a series of water extraction wells designed to avoid environmental impact on the surrounding ecosystems. Monitoring has shown that the containment is successful, and additional measures that contribute to accelerating remediation have been adopted. The authors wished to investigate how remediation might be further enhanced. The use of in situ aeration coupled with a system of soil vapor extraction (AS/SVE) has been chosen, since the remediation of sites with characteristics similar to those in this study, if based exclusively on dissolved-phase control, would take several decades to be completed. The transport of contaminant plumes has been simulated by using an analytical model to evaluate the effectiveness of the natural attenuation of the contaminant. The results of the simulation have confirmed the limited effectiveness of the natural attenuation of the contaminant, as well as the effective increase of remediation that would occur if the AS/SVE system is applied. A sensitivity analysis that included several combinations of increments of parameters that correspond to the decay rate of the source and the dissolved plume has simulated what might happen if the AS/SVE system is implemented.     

Are either sod and catalase or the polyamines involved in the paraquat resistance of Conyza canadensis ?

Abstract

Paraquat/atrazine coresistant (PqAR) and paraquat resistant (PqR) horseweed (Conyza canadensis /L./ Cronq.) plants showed ‐ in the first hour after 0.5 mM paraquat spraying ‐ a decreased catalase activity followed by a slight increase. However, the enzyme activity remained always below the initial value. Sensitive plants showed a significant increase of catalase activity in the first 4 hour after spraying. The transient character of paraquat inhibition, the recovery of photosyn‐thetic activity of the PqAR Conyza plants (characterized by variable fluorescence) after spraying remained unaffected by the Superoxide dismutase (SOD) inhibitor, diethyldithiocarbamate. This indicates that SOD is not involved in the resistance mechanism. Untreated resistant biotypes showed about 2.5 times higher total polyamine and putrescine level than the sensitive one. 100 μM of exogenously added putrescine was observed as having a protecting effect against paraquat in floated leaves of the sensitive biotype only. The resistant leaves were unaffected probably on account of their higher endogenous polyamine level. It is concluded that polyamines may play a role in the paraquat resistance of Conyza canadensis.     

Heavy metal concentrations in Squilla mantis (L.) (Crustacea,Stomatopoda) from the gulf of cadiz evaluation of the impact of the Aznalcollar mining spill

After the Aznalcóllar mining spill (25th April 1998), considerable social concern arose amongst the inhabitants of the SW Iberian Peninsula concerning the consumption of local seafood. Squilla mantis was collected in four regions of the Gulf of Cádiz with a dual objective: to analyze the heavy metal levels for human consumption and as part of biomonitoring program. Heavy metal concentrations (Fe, Mn, Zn, Cu, Cd and Pb) were analyzed in soft tissues and cuticle. The highest values were found in the soft tissues for zinc, copper and cadmium and in the cuticle for iron, manganese and lead. The mean copper concentration in the soft tissue, corresponding to the edible part, was 27.1 microg x g(-1) wet weight. Approximately 80% of stations showed values higher than 20 microg x g(-1) wet weight of copper, the Spanish legal limit for the concentration of this metal in the crustacean for human consumption. For Zn and Cu no significant differences were found between regions, probably related with the capacity for regulation of S. mantis. The highest values found for copper in the Gulf of Cádiz compared to other areas is likely to be related with contamination from terrestrial mining activities (copper and pyrites) in the region, dating back to the times of Tartessians and Romans, rather than the effects of mining spill which was shown not to create any significant increases in heavy metal concentrations of organisms of the Guadalquivir River or the adjacent coastal area.