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).     

Hybridization between wheat (Triticum aestivum) and the wild species Aegilops geniculata and A. biuncialis under experimental field conditions

Hybridization between Aegilops geniculata, A. biuncialis and bread wheat Triticum aestivum has been evaluated during two seasons under simulated field conditions to estimate the field hybridization rate under Central Spain conditions. The mean frequencies of hybridization between A. biuncialis and A. geniculata with wheat were 0.34% and 0.31%, respectively. Data from 10 hybrid plants for each combination showed that hybrids can be partially fertile by backcrossing with wheat parent, with percent averages of 3.17 grains/spikelets for A. biuncialis × wheat hybrids and 2.87 grains/spikelets for A. geniculata × wheat hybrids. Self-pollination, although at very low rates, was also possible in hybrids. The potential risks associated with natural hybridization in the context of transgenic wheat cultivation are discussed.     

Differences in phosphorus translocation contributes to differential arsenic tolerance between plants of Borreria verticillata (Rubiaceae) from mine and non-mine sites

We have identified new arsenic-tolerant plant species Borreria verticillata (Rubiaceae) that has mine and non-mine populations at a highly contaminated site (CS) and an uncontaminated site (UCS), respectively, in Brazil. Plants of B. verticillata from both sites were cultivated at different As and P concentrations. At low P concentration, CS plants showed reduced As uptake, higher P translocation to shoots, higher constitutive levels of phenolic compounds in roots, and higher tolerance to this metalloid. At the lowest P and highest As concentration, CS plants showed higher biomass. In addition, CS plants showed higher P uptake in the absence of As, suggesting that more efficient P translocation could contribute more to tolerance than decreased As uptake. In contrast, at low P concentration, UCS plants showed higher As content in shoot and root, increase in phenol levels in roots, reduction in dry biomass, and decrease of the effective efficiency of photochemical reactions and the electron transport rate. Under higher P concentrations, the decrease in As uptake was similar in both populations. The differences between the two populations with respect to As and P uptake suggest that altered kinetic properties or expression of P transporters contribute to higher As tolerance in B. verticillata from CS. As a ruderal and As-tolerant plant, B. verticillata could be successfully used for the revegetation of contaminated soils.     

Assessing single and joint effects of chemicals on the survival and reproduction of Folsomia candida (Collembola) in soil

Chemicals are often found in the environment as complex mixtures. There has been a large effort in the last decade to assess the combined effect of chemicals, using the conceptual models of Concentration Addition and Independent Action, but also including synergistic, antagonistic, dose-level and dose-ratio dependent deviations from these models. In the present study, single and mixture toxicity of atrazine, dimethoate, lindane, zinc and cadmium were studied in Folsomia candida, assessing survival and reproduction. Different response patterns were observed for the different endpoints and synergistic patterns were observed when pesticides were present. Compared with the previously tested Enchytraeus albidus and Porcellionides pruinosus, the mixture toxicity pattern for F. candida was species specific. The present study highlights the importance of studying toxicity of chemicals mixtures due to the observed potentiation of effects and confirms that for an adequate ecologically relevant risk assessment different organisms and endpoints should be included.     

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 μg L⁻¹. Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L⁻¹ of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 μg L⁻¹. This highly effective arsenic removal method is easy to use and inexpensive to implement.     

Water Remediation: PVA-Based Magnetic Gels as Efficient Devices to Heavy Metal Removal

Scientific and technological researches are devoted to obtain materials capable of retaining different kinds of pollutants, contributing to contamination solutions. In this context, hydrogels have emerged as great candidates because of their excellent absorption properties as well as good mechanical, thermal and chemical properties. More specifically, ferrogels (magnetic gels) present the extra advantage of being easily manipulated by a permanent magnet. Here, we present the results derived from the application of ferrogels as efficient tools to extract heavy metal pollutants from wastewater samples. The gels were prepared following the method of freezing and thawing of a polyvinyl alcohol aqueous solution with magnetic nanoparticles coated with polyacrylic acid. Ferrogels were fully characterized and their ability to retain Cu²⁺ and Cd²⁺, as model heavy metals, was studied. Thus kinetics and mechanisms of adsorption were evaluated and modeled. The concentration of MNPs on the PVA matrix was key to improve the adsorption capability (approximately the double of retention is improved by the MNPs addition). The adsorption kinetics was determined as pseudo-second order model, whereas the Langmuir model was the most appropriate to explain the behavior of the gels. Finally reuse ability was evaluated to determine the real potential of these materials, the ferrogels demonstrated high efficiency up to about five cycles, retaining about 80–90% of their initial adsorption capability. All the results indicated that the materials are promising candidates able to compete with the commercial technology regarding to water remediation.