An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (K_D) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg^?1) and carbaryl (3.1 and 4.2 L kg^?1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Herbicide toxicity,selectivity and hormesis of nicosulfuron on 10 Trichogrammatidae (Hymenoptera) species parasitizing Anagasta ( = Ephestia) kuehniella (Lepidoptera: Pyralidae) eggs

Selective agrochemicals including herbicides that do not affect non-target organisms such as natural enemies are important in the integrated pest management (IPM) programs. The aim of this study was to evaluate the herbicide toxicity, selectivity and hormesis of nicosulfuron, recommended for the corn Zea mays L. (Poaceae) crop, on 10 Trichogrammatidae (Hymenoptera) species. A female of each Trichogramma spp. or Trichogrammatoidea annulata De Santis, 1972 was individually placed in plastic test tubes (no choice) with a cardboard containing 45 flour moth Anagasta ( = Ephestia) kuehniella Zeller, 1879 (Lepidoptera: Pyralidae) eggs. Parasitism by these natural enemies was allowed for 48 h and the cardboards were sprayed with the herbicide nicosulfuron at 1.50 L.ha^?1, along with the control (only distilled water). Nicosulfuron reduced the emergence rate of Trichogramma bruni Nagaraja, 1983 females, but increased that of Trichogramma pretiosum Riley, 1879, Trichogramma acacioi Brun, Moraes and Smith, 1984 and T. annulata females. Conversely, this herbicide increased the emergence rate of Trichogramma brasiliensis Ashmead, 1904, T. bruni, Trichogramma galloi Zucchi, 1988 and Trichogramma soaresi Nagaraja, 1983 males and decreased those of T. acacioi, Trichogramma atopovilia Oatman and Platner, 1983 and T. pretiosum males. In addition, nicosulfuron reduced the sex ratio of T. galloi, Trichogramma bennetti Nagaraja and Nagarkatti, 1973 and T. pretiosum and increased that of T. acacioi, T. bruni, T. annulata, Trichogramma demoraesi Nagaraja, 1983, T. soaresi and T. brasiliensis. The herbicide nicosulfuron was “harmless” (class 1, <30% reduction) for females and the sex ratio of all Trichogrammatidae species based on the International Organization for Biological Control (IOBC) classification. The possible hormesis effect of nicosulfuron on Trichogrammatidae species and on the bacterium Wolbachia sp. (Rickettsiales: Rickettsiaceae) was also discussed.     

Efficiency in heavy metal purge in crustaceans during the ecdysis

Environment, Development and Sustainability - An abundant population of Ucides cordatus swamp crabs is present at Lameirão Ecological Station (Brazil), a tropical ecosystem man-made with...     

Public opinion and awareness towards MSW and separate collection programmes: A sociological procedure for selecting areas and citizens with a low level of knowledge

The principal aim of this study was to define and apply a procedure based on a structured questionnaire survey useful to analyze the people’s environmental knowledge in order to select the areas and age groups with a low level of knowledge in a municipality (in Southern Italy) and, therefore, suggest a specific educational campaign for each. The detailed sampling procedure made it possible to carry out a meticulous statistical analysis of the results. The youngest and oldest people showed the lowest level of awareness for each district. A high level of education did not necessarily imply a high level of environmental awareness as well as a greater acceptance of MSW facilities. The satisfaction level of the recycling program was higher amongst the oldest age group. All the citizens in the several areas were unanimous in pointing out the presence of dirt in the street as the main shortcoming of the bring separate collection program. Only the youngest age group self-criticised, considering that they revealed a low level of participation to the separate collection program. While, the oldest people retaining them less influential, claimed that the citizens were not responsible for the failure of the separate collection program. The prevailing opinion of the sample was that people protested against the construction of waste facilities because they were not well-informed, with the most significant opinion of all the age subdivisions being that incineration is a hazardous treatment. The presence of criminal organizations was indicated as the main reason why the Campania Region suffers a serious solid waste emergency. While, the percentage of people pointing their finger at politicians increases with the average age of the respondents with there being a very strong correlation (r² = 0.9903).     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen

The photochemical behavior of oxyfluorfen [2-chloro-1-(3-etoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene] on two Greek soils was investigated. Soils were sampled from Nea Malgara and Preveza regions, characterized by a different organic matter content. Soils were spiked with the diphenyl-ether herbicide and irradiation experiments were performed either in the laboratory with a solar simulator (xenon lamp) or outside, under natural sunlight irradiation; other soil samples were kept in the dark to control the retention reaction. Kinetic parameters of both retention and photochemical reactions were calculated using zero-, first- and second- (Langmuir-Hinshelwood) order equations, and best fit was checked through statistical analysis. The soil behaviors were qualitatively similar but quantitatively different, with the soil sampled from the Nea Malgara region much more sorbent as compared with Preveza soil. All studied reactions followed second-order kinetics and photochemical reactions were influenced by retaining capability of the soils. The contributions of the photochemical processes to the global dissipation rates were also calculated. Two main metabolites were identified as 2-chloro-1-(3-ethoxy-4-hydroxyphenoxy)-4-(trifluoromethyl)benzene and 2-chloro-1- (3-hydroxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene.     

Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.