The synthetic pyrethroid isomers II. Biological activity

Abstract

Pure optical isomers of phenothrin, permethin and cypermethrin were synthesised and tested on a wide spectrum of insects (Blattella germanica, Leptinotarsa decemlineata, Tribolium confusum, Oncopeltus fasciatus, Musca domestica, Aedes aegypti). Our results suggest that in the structurally related series phenothrin, permethrin and cypermethrin the chemical modifications had only a small influence on intrinsic activity of the compounds at the target site. The activity of piperonylbutoxide synergised 1Rtrans phenothrin and 1Rcis permethrin (LD₅₀=1.2 ng/fly in both cases) is in a similar range to the most active 1RcisS cypermethrin isomer alone or with PB (LD₅₀=0.9 and 0.4 ng/fly, respectively). Some cypermethrin isomers considered previously to be totally inactive show significant activity depending on the tested insect species. The 1ReisR and 1RtransR isomers proved to be as active as the most potent isomers on mosquito. A similarly unexpected result was that in the case of mosquito all four trans isomers were significantly more active than the corresponding eis isomers.

The superiority of the (S)‐α configuration over (R)‐α was found. It does not result from a higher intrinsic activity at the target site, but rather from the enhanced metabolic resistance of (S)‐α‐esters to ester cleavage as confirmed by Synergist studies. The activity of the two most potent stereoisomers, 1ReisS and 1RtransS, could not be elevated by quinalphos, while the inactive 1ScisR and 1StransR isomers showed significant activity with the esterase inhibitor quinalphos administered sublethally.

In contrast with the antagonism between (S)‐ and (R)‐α‐epimers of cypermethrin reported earlier a considerable synergism was observed between 1RtransS and 1StransR enantiomer pair on flour beetle and housefly in tarsal contact tests.

The results with stereoisomers and their mixtures were utilised in the development of two new products, Chinmix (beta‐cypermetrhin) and Transmix (theta‐cypermetrhin).     

Are pharmaceuticals more harmful than other pollutants to aquatic invertebrate species: a hypothesis tested using multi-biomarker and multi-species responses in field collected and transplanted organisms

The aim of this study was to test if pharmaceuticals could explain observed responses of field collected and transplanted invertebrate species (Hydropsyche exocellata, Echinogammarus longisetosus, and Daphnia magna). The study was performed in the middle and lower course of Llobregat river basin, which is affected by pharmaceuticals and other pollutants coming from sewage treated effluents. Up to 10 different endpoints including enzyme activities related with detoxication mechanisms (i.e. glutathione S transferase, catalase, esterases), the oxidative stress damage marker (lipid peroxidation), and individual responses (mortality, post-exposure feeding rates) were assessed. Biological responses were complemented with a detailed chemical analysis of metals, detergents, pesticides, pharmaceuticals and other general water quality variables to allow identifying causal abiotic factors. Estimated hazard indexes of measured pollutants indicated that pesticides and metals accounted for most of the predicted toxicity (>95%) in the most contaminated site and that the predicted toxicity of pharmaceuticals was marginal (<5%). The three species showed a clear impact across the studied gradient indicated by higher levels of feeding inhibition and of mortality towards lower reaches. Specific responses such as inhibition of cholinesterase activities were closely related to high and presumable toxic levels of diazinon, whereas unspecific responses such as enhanced levels of antioxidant defensive mechanism and of lipid peroxidation levels were associated with most pollutant classes as well as with high and presumable toxic levels of salt and ammonia. These results indicate that pesticides, salinity, ammonia probably had greater effects on the studied species than pharmaceuticals.     

Estimation of hydrogen sulfide emission rates at several wastewater treatment plants through experimental concentration measurements and dispersion modeling

The management and operation of wastewater treatment plants (WWTP) usually involve the release into the atmosphere of malodorous substances with the potential to reduce the quality of life of people living nearby. In this type of facility, anaerobic degradation processes contribute to the generation of hydrogen sulfide (H2S), often at quite high concentrations; thus, the presence of this chemical compound in the atmosphere can be a good indicator of the occurrence and intensity of the olfactory impact in a specific area. The present paper describes the experimental and modelling work being carried out by CEAM-UMH in the surroundings of several wastewater treatment plants located in the Valencia Autonomous Community (Spain). This work has permitted the estimation of H2S emission rates at different WWTPs under different environmental and operating conditions. Our methodological approach for analyzing and describing the most relevant aspects of the olfactory impact consisted of several experimental campaigns involving intensive field measurements using passive samplers in the vicinity of several WWTPs, in combination with numerical simulation results from a diagnostic dispersion model. A meteorological tower at each WWTP provided the input values for the dispersion code, ensuring a good fit of the advective component and therefore more confidence in the modelled concentration field in response to environmental conditions. Then, comparisons between simulated and experimental H2S concentrations yielded estimates of the global emission rate for this substance at several WWTPs at different time periods. The results obtained show a certain degree of temporal and spatial (between-plant) variability (possibly due to both operational and environmental conditions). Nevertheless, and more importantly, the results show a high degree of uniformity in the estimates, which consistently stay within the same order of magnitude.     

Characterisation of cholinesterases and evaluation of the inhibitory potential of chlorpyrifos and dichlorvos to Artemia salina and Artemia parthenogenetica

In this study, the acute toxicity of the organophosphorous pesticides dichlorvos and chlorpyrifos to two different species of Artemia (A. salina and A. parthenogenetica) was evaluated. In addition, the in vivo effect of these two pesticides on cholinesterase (ChE) activity of both A. salina and A. parthenogenetica was also determined. The characterisation of the ChE, using different substrates and specific inhibitors, and the normal range of activity in non-exposed individuals were previously investigated for both species. The results obtained indicate that the ChE of A. salina is different from that of A. parthenogenetica and that both enzymes cannot be classified neither as acetylcholinesterase nor as butyrylcholinesterase since they show intermediary characteristics between the two vertebrate forms. The range of normal ChE activity was 2.65+/-0.15 U/mg protein for A. salina, and 3.69+/-0.17 U/mg protein for A. parthenogenetica. Significant in vivo effects of both pesticides on Artemia ChE activity were found, at concentrations between 5.38 and 9.30 mg/l for dichlorvos and between 1.85 and 3.19 mg/l for chlorpyrifos. Both Artemia species are resistant to these pesticides and they are able to survive with more than 80% ChE inhibition. However, A. parthenogenetica is more resistant than A. salina, with about a 95% reduction in its ChE activity respect to the control for nauplii exposed to the median lethal concentrations (LC50), without lethal effects after 24 h of exposure.     

Spatial scales and probability based sampling in determining levels of benthic community degradation in the Chesapeake Bay

The extent of degradation of benthic communities of the Chesapeake Bay was determined by applying a previously developed benthic index of biotic integrity at three spatial scales. Allocation of sampling was probability-based allowing areal estimates of degradation with known confidence intervals. The three spatial scales were: (1) the tidal Chesapeake Bay; (2) the Elizabeth River watershed; and (3) two small tidal creeks within the Southern Branch of the Elizabeth River that are part of a sediment contaminant remediation effort. The areas covered varied from 10^–1 to 10⁴ km² and all were sampled in 1999. The Chesapeake Bay was divided into ten strata, the Elizabeth River into five strata and each of the two tidal creeks was a single stratum. The determination of the number and size of strata was based upon consideration of both managerially useful units for restoration and limitations of funding. Within each stratum 25 random locations were sampled for benthic community condition. In 1999 the percent of the benthos with poor benthic community condition for the entire Chesapeake Bay was 47% and varied from 20% at the mouth of the Bay to 72% in the Potomac River. The estimated area of benthos with poor benthic community condition for the Elizabeth River was 64% and varied from 52–92%. Both small tidal creeks had estimates of 76% of poor benthic community condition. These kinds of estimates allow environmental managers to better direct restoration efforts and evaluate progress towards restoration. Patterns of benthic community condition at smaller spatial scales may not be correctly inferred from larger spatial scales. Comparisons of patterns in benthic community condition across spatial scales, and between combinations of strata, must be cautiously interpreted.     

Rapid quantitative monitoring method for the fish spoilage bacteria Pseudomonas

Pseudomonas spp. is a group of microorganisms commonly found in fish and other fresh foods and is involved in their spoilage process. The aim of this study was to develop a rapid and accurate quantitative assay for Pseudomonas spp. in fish using real-time PCR. The assay targets the carbamoyl phosphate synthase gene (carA) with SYBR green based real-time PCR. The selectivity of the assay was confirmed using 24 Pseudomonas strains and 55 non-pseudomonad strains. A linear quantification was established over seven orders of magnitude, from 40 - 4(7) copies reaction(-1). The assay was validated on cod samples collected during two shelf life trials and showed a high degree of correlation to the plate count method (rP = 0.891) where the difference between the methods was 0.04 log(10) CFU g(-1) on average. The study shows that it is possible to quantify accurately the specific spoilage organisms belonging to the genus Pseudomonas in fish using real-time PCR. The method takes less than 5 h from sampling to results. The short detection time of the method can provide the fish industry with an important tool for quality control and processing management.     

Methods,fluxes and sources of gas phase alkyl nitrates in the coastal air

The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3–C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO₂ levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor.     

Modelling the spatio-temporal evolution of 3H in the waters of the River Tagus

Measurements of tritium specific activity levels and of temperatures in waters of the Torrejón-Tagus reservoir (Spain) showed that their radioactive characteristics were basically influenced by the radioactive liquid effluent from the Almaraz Nuclear Power Plant. This enters the Torrejón-Tagus reservoir via the Arrocampo cooling reservoir, which exchanges water with the first. We studied the temporal and spatial (in two dimensions) evolution of the mentioned parameters for years 1997 and 1998. The tritium levels were found to be significantly correlated with temperature. Two numerical models were constructed for a quantitative study of the tritium levels along Torrejón reservoir: a 1D model was used for the dispersion of tritium along the whole length of the reservoir, and a 2D depth-averaged model was used for a detailed study of the area where tritium is released into the reservoir. Both models solve the hydrodynamic equations, to obtain the currents induced by the exchanges of water between the reservoirs in the River Tagus and Arrocampo, and the advection/diffusion equation to calculate the dispersion of tritium. In general, the model results were in agreement with the experimental observations.     

Monitoring concentrations of persistent organic pollutants in the general population: the international experience

Assessing the adverse effects on human health of persistent organic pollutants (POPs) and the impact of policies aiming to reduce human exposure to POPs warrants monitoring body concentrations of POPs in representative samples of subjects. While numerous ad hoc studies are being conducted to understand POPs effects, only a few countries are conducting nationwide surveillance programs of human concentrations of POPs, and even less countries do so in representative samples of the general population. We tried to identify all studies worldwide that analyzed the distribution of concentrations of POPs in a representative sample of the general population, and we synthesized the studies' main characteristics, as design, population, and chemicals analyzed. The most comprehensive studies are the National Reports on Human Exposure to Environmental Chemicals (USA), the German Environmental Survey, and the Arctic Monitoring and Assessment Programme. Population-wide studies exist as well in New Zealand, Australia, Japan, Flanders (Belgium) and the Canary Islands (Spain). Most such studies are linked with health surveys, which is a highly-relevant additional strength. Only the German and Flemish studies analyzed POPs by educational level, while studies in the USA offer results by ethnic group. The full distribution of POPs concentrations is unknown in many countries. Knowledge gaps include also the interplay of age, gender, period and cohort effects on the prevalence of exposures observed by cross-sectional surveys. Local and global efforts to minimize POPs contamination, like the Stockholm convention, warrant nationwide monitoring of concentrations of POPs in representative samples of the general population. Results of this review show how such studies may be developed and used.     

Concentrations of PCDD/PCDFs and PCBs in fish and seafood from the Catalan (Spain) market: estimated human intake

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) in samples from 14 fish and seafood species widely consumed by the population of Catalonia, Spain, were measured. These samples were randomly purchased independently of their geographical origin. The intake of PCDD/Fs and PCBs through consumption of these species was also estimated for various age and sex groups of this population. The highest and lowest levels of PCDD/Fs and dioxin-like PCBs (DL-PCBs) were found in red mullet and shrimp, respectively. For a standard adult man (70 kg body weight), the intake of PCDD/Fs plus DL-PCBs through consumption of fish and other seafood was estimated to be 38.0 pg WHO-TEQ/day. Tuna, hake, and sardine were the species with the highest contribution to this intake. The results of this study indicate that, in general terms, the dietary habits of the population of Catalonia (Spain) regarding fish and seafood consumption do not contribute remarkably to increase PCDD/F and DL-PCB intake.