Dissipation of racemic mecoprop and dichlorprop and their pure R-enantiomers in three calcareous soils with and without peat addition

Two racemic herbicides, mecoprop (R,S-MCPP) and dichlorprop (R,S-DCPP), as well as their enantiopure R-forms, were incubated in three calcareous soils at 15 degrees C and 80% of their field capacity to try to elucidate their behaviour in soil and compare the dissipation rates when racemic and enantiopure compounds are used. Quantitation of pesticides is made by HPLC and the R/S ratio by GC-MS. The inactive S-enantiomer from the racemic forms persists longer than the R-forms in silt and sandy loam soils, but for shorter time in the clay loam soil. The pure R-enantiomers, both for MCPP and DCPP, after incubation in soil, are partially converted into their S-forms. In all cases, the dissipation of racemic and pure enatiomeric forms is lower in the clay loam soil than in the silt and sandy loam soils. The R-forms' peristence, in the three soils, is approximately two times lower when they are incubated alone than when they are incubated as racemic compounds. When peat is added, the persistence of these herbicides in the silt and sandy loam soils increases, while in the clay loam soil it decreases. Besides, in the clay loam soil, the enantiomeric ratio (ER) changes from its S-preferential degradation to a preferential degradation of its R-form, so an increase in the persistence of the inactive S-form occurs.     

Toxicity of acid aluminium-rich water to seven freshwater fish species: a comparative laboratory study

The present study focuses on the relative sensitivity among freshwater fish species to aqueous aluminium. Seven common Scandinavian fish species were exposed to acidic Al-rich water, acidic Al-poor water, and approximately neutral water as a control. The relative sensitivity among the species to an acute aluminium challenge was documented, and was in the following order: Atlantic salmon, Salmo salar, as the most sensitive; then roach, Rutilus rutilus; minnow, Phoxinus phoxinus; perch, Perca fluviatilis; grayling, Thymallus thymallus; brown trout, Salmo trutta; and Arctic char, Salvelinus alpinus. Substantial mortality was observed in all species when exposed to the Al-rich medium. Some mortality was also observed in minnow, roach, and brown trout exposed to the acidic Al-poor medium and the control medium. A high resistance to aluminium was observed in Arctic char, while perch was found to be more sensitive to aluminium than expected and, for the first time, a toxic response to aqueous aluminium in grayling was documented. Through controlled experimental studies, the results confirm that aluminium is an important factor in the toxicity of acidified waters to freshwater fish species.     

Identification of some plasticizers compounds in landfill leachate

In this work it was described a simple method for extraction of plasticizer compounds (mainly phthalate esters and bisphenol A (BPA)) from landfill leachate samples. The samples were submitted to an extraction procedures based on precipitation, solid phase extraction (SPE) and ionic exchange chromatography (IEC). Firstly the landfill leachate sample was acidified by addition of HCl concentrated, in order to precipitate the organic compounds that are less soluble in water. The precipitate was washed with several solvents. The aqueous phase was then submitted to SPE with XAD-4 resin and IEC with Amberlyst A-27 resin. The instrumental analysis was performed by gas chromatography with mass spectrometer detector (GC/MSD) and the compounds were identified by the GC/MSD library (Wiley) and by using some standard substances. These methodologies allow the isolation and identification of the following compounds: dioctylphthalate, diisobutilphthalate, BPA, benzoic acid, palmitic acid and diisopentylphthalate. The methods are very simple, rapid and selective, for plasticizers extraction from landfill leachate matrices.     

The significance of water ionic strength on aluminium toxicity in brown trout (Salmo trutta L.)

The toxicity of aluminium to fish is related to interactions between aluminium and the gill surface. We investigated the possible effect of water ionic strength on this interaction. The mortality of brown trout (Salmo trutta L.) exposed to three different degrees of Al polymerisation was compared in water with increased ionic strength (mean 7.31 x 10(-4) M) after additions of the base cations Ca2+, Mg2+, Na+ or K+, and in water with no such addition (mean ionic strength 5.58 x 10(-4) M). Only a very slight ameliorating effect of increased ionic strength was observed, while the degree of Al polymerisation was of major importance in fish mortality. In addition, it was observed that smaller fish survived the Al exposures for a longer time than larger fish. We hypothesise that this is because larger fish are more susceptible to hypoxia than smaller fish.     

Stochastic model to forecast ground-level ozone concentration at urban and rural areas

Stochastic models that estimate the ground-level ozone concentrations in air at an urban and rural sampling points in South-eastern Spain have been developed. Studies of temporal series of data, spectral analyses of temporal series and ARIMA models have been used. The ARIMA model (1,0,0) x (1,0,1)24 satisfactorily predicts hourly ozone concentrations in the urban area. The ARIMA (2,1,1) x (0,1,1)24 has been developed for the rural area. In both sampling points, predictions of hourly ozone concentrations agree reasonably well with measured values. However, the prediction of hourly ozone concentrations in the rural point appears to be better than that of the urban point. The performance of ARIMA models suggests that this kind of modelling can be suitable for ozone concentrations forecasting.     

Adsorption of atrazine from aqueous solution on heat treated kerolites

The adsorption of 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on heat treated kerolite samples at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400) and 600 degrees C (K-600) from aqueous solution at 25 degrees C has been studied. The evolution of surface properties of kerolite samples such as specific surface area and porosity after heat treatment was analysed. The clays were characterised by using usual techniques: FTIR spectroscopy, XRD diffraction, TG and DTG analysis, surface analysis and Hg porosimetry. The adsorption experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values range from 468 mgkg(-1) for the K-110 sample up to 2291 mgkg(-1) for the K-600 sample. The values obtained for the removal efficiency (R), (percentage of pesticide removed), ranged from 48% for K-110 up to 78% for K-600. The adsorption experiments showed that the stronger heat treatment, the most effective adsorption of atrazine, so, as this type of clay is relatively plentiful, these activated samples might be used in order to remove this pesticide from water.     

Alternative herbicides to manage Italian ryegrass (Lolium multiflorum lam) resistant to glyphosate at different phenological stages

During the growing season of 2002--2003, field and greenhouse experiments were conducted with the objective of evaluating the influence of Italian ryegrass phenological stages and management alternatives on the control of resistant biotypes to glyphosate. Three field experiments were conducted in Lagoa Vermelha, RS, Brazil and glyphosate was applied alone and in combinations with alternative herbicides. Two greenhouse experiments were also conducted at the Department of Crop Science, ESALQ/USP, Piracicaba, SP, Brazil. The Italian ryegrass resistant population was collected from Lagoa Vermelha, RS, Brazil. From the results it was possible to conclude that: (i) the more advanced the phenological stage of application, the more difficult the control of resistant Italian ryegrass by glyphosate, mainly by the rate of 960 g a.i. ha(-1); however, this rate applied at earlier phenological stage (five tillers), the control was higher than 90%; (ii) with the increment of glyphosate rate, it significant response was observed on the control at all stages of application; (iii) the mixture of glyphosate + clethodim (1440 + 72 g a.i. ha(-1)), paraquat + diuron (500 + 250 g a.i. ha(-1)), at all stages of application and clethodim (96 g a.i. ha(-1)) and paraquat + diuron (300 + 150 g a.i. ha(-1)) at the initial stages until pre-flowering were excellent alternatives for management of these populations; and (iv) the response of control was much faster for the mixture of glyphosate + clethodim, independently of growth stage.     

Photocatalytic degradation of formaldehyde containing wastewater from veterinarian laboratories

The photocatalytic destruction of methanol, formaline (mixture of formaldehyde, methanol and water) and formaline wastes from the preservation of vertinarian physiologic samples has been attempted by two different processes, at high concentrations of reagents and by dossification of reagents, varying pH in both. Experiment evolution has been monitored by measuring the organic matter such as TOC and formaldehyde concentrations [H2CO]. Also, methanol and methanol-formaldehyde interactions with the TiO2 surface have been analysed by FTIR spectroscopy. Results indicate that at high concentrations the catalyst surfacial alterations given by methoxy, formates or carbonates, according to the pH of the sample can profoundly affect catalyst behaviour. It has been established that reagent dossification is advantageous for enhancing photonic efficiency as it minimizes the adsorbate presence that hampers the photocatalytic process.     

Effects of herbicide and insecticide interaction on soil entomofauna under maize crop

The aim of this study was to evaluate the impact of the herbicide mixture nicosulfuron + atrazine, with or without the insecticide chlorpyrifos, onto soil entomofauna under maize crop. The treatments, applied 25 days after maize emergence, were represented by a weeded control without insecticide and herbicide, a weeded control with chlorpyrifos, and mixtures of nicosulfuron + atrazine, with or without chlorpyrifos. Arthropods populations, on the soil surface, as well as inside the soil under maize, were principally represented by mites (Arachnida: Acari), decomposer collembolans (Hexapoda:Parainsecta:Collembola) and predator ants (Hymenoptera:Formicidae). The nicosulfuron + atrazine mixture with chlorpyrifos and the isolated chlorpyrifos reduced the population dynamics of all insect groups on the soil surface compared to the weeded control. In the soil, mite and ant populations were reduced after application of the herbicide mixture with chlorpyrifos and of the isolated chlorpyrifos.     

Distribution coefficients (Kd) and desorption rates of 137Cs and 241Am in Black Sea sediments

The distribution coefficients (K_d) and desorption rates of ¹³⁷Cs and ²⁴¹Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The K_d values were found to be 500 for ¹³⁷Cs and 3800 for ²⁴¹Am at the steady state and described exponential curves. Rapid uptake of the radionuclides occurred during the initial period and little accumulation happened after four days. The desorption rates for ¹³⁷Cs in different bottom sediments were best described by a three-component exponential model. The desorption half-times of ¹³⁷Cs ranged from 26 to 50 d at the slow components. However, the desorption rate of ²⁴¹Am described one component for all sediment samples and desorption half-time was found to be 75 d. In general, the results showed that the ²⁴¹Am radionuclide is more effectively transferred to bottom sediment and has longer turnover time than ¹³⁷Cs under Black Sea conditions.