Carbofuran degraded by iron-doped anatase: Weakening the cholinesterase inhibitory activity in the photoproducts mixture

Carbofuran is a toxic carbamate pesticide, and its use has increased in recent years. While marketing information indicates stability in different chemical media, carbofuran exhibits relative photolability. The aim of this research was to decompose carbofuran and to identify the photoproducts achieved when two different doped titania photocatalysts were employed under UV irradiation. The iron-doped TiO₂ materials were obtained (a) via a hydrothermal method and (b) by an ultrasound-assisted sol–gel method. The precursors were TiOSO₄?xH₂O and Fe₃(NO₃)·9H₂O. X-ray studies confirmed that the anatase phase of the iron-doped TiO₂ resulted from the two preparation methods. The photocatalytic performance of the prepared materials was monitored by LC/ESI-QTOF-MS, enabling the identification of photoproducts: oxo-carbamates, hydroxylated benzofuranes, a carboxamide, and one amine. By using the iron-doped TiO₂ materials, 2,2-dimethyl-2,3-dihydrobenzofuran-3,7-diol was the most abundant photoproduct, and N,2,2-trimethyl-2,3-dihydrobenzofuran-7-amine was the only compound that had not been previously reported in the photolysis and photocatalysis of carbofuran. The product 3-hydroxy carbofuran, a cholinesterase inhibitor, was quantified and was found to be transformed into compounds that lack this inhibitive property.     

Health risks of environmental exposure to metals and herbicides in the Pardo River,Brazil

Mixture of metals and herbicides in rivers may pose relevant risks for the health of surrounding communities. Humans may be exposed to river pollution through intake of contaminated water and fish, as well as irrigated agricultural products. The aim of this study was to assess the human health risks of environmental exposure to metals and herbicides through water and fish intake in the Pardo River. Metals (Al, As, Be, Cd, Cr, Cu, Pb, Mn, Hg, Ni, Tl, Sn, V, and Zn) were analyzed in river water and in edible fish. Herbicides (ametryn, atrazine, diuron, hexazinone, simazine, and tebuthiuron) were analyzed in river water. Seasonal variances were also studied. Aluminum, Cd, Cu, Mn, Pb, and Zn levels in river water were higher than the USEPA benchmarks. Non-carcinogenic risks due to pollutants mixture exposure were above the limit, and carcinogenic risks of As exposure were >10^?6 in the sampling points during the rainy season. Metal levels in fish were lower than the Brazilian legislation and do not pose a threat to public health. Herbicides were detected in four sampling points, with atrazine concentrations (range 0.16–0.32 μg/L) below the Brazilian standard (2.0 μg/L), but above the European Union standard (0.1 μg/L). Considering the water supply needs of cities located in the Pardo River Basin and the persistence of metals and herbicides, the present study indicated that there was a seasonal influence on non-carcinogenic and carcinogenic risks to human health, especially in the rainy season. Studies for water treatment plants implantation should consider the risks of exposure to persistent substances, in order to protect the population.     

Evaluation of the mobility of c14‐labelled pesticides in soils by thin layer chromatography using a linear analyser

Abstract

The mobility of seven pesticides in a chromic cambisol soil was studied by soil thin layer chromatography. Pesticide mobilities were determined by means of conventional autoradiographs of the chromatograms, as well as from sequential series of curves and images of the pesticide spots provided by a linear analyser. The R _f values obtained from the autoradiographs and those provided by the linear analyser were quite consistent. Based on such values, pesticide mobility decreased in the following order: acephate > fluometuron > atrazine > ethofumesate > metolachlor > diazinon > glyphosate. According to the mobility scale proposed by Helling and Turner (1968), acephate is highly mobile; atrazine, fluometuron, ethofumesate and metolachlor are moderately mobile; diazinon is slightly mobile; and glyphosate is immobile. The images provided by the linear analyser allow to determine the R _f values for the zones of maximum activity in the pesticide spots (R _f ^max), as well as the activities of different spot zones and those corresponding to R _f and R _f ^max. The results obtained show the image analyser to provide more expeditious R _f measurements from the chromatograms and open up new prospects for using soil TLC to investigate pesticide mobility.     

Novel approach for assessing heavy metal pollution and ecotoxicological status of rivers by means of passive sampling methods

In order to study the pollution of fluvial ecosystems, it is necessary to analyze not only the levels of chemical contaminants in water, but also those accumulated in the sediment matrix, as well as to assess its ecotoxicological status. Eleven Catalan (Spain) river sections (one sampling point per river) located near urban and industrial areas were sampled during winter of 2009. Water pollutants were collected by using passive samplers as Diffusive Gradient in Thin-Films (DGTs) and Semi-Permeable Membrane Devices (SPMDs). Point water samples were also collected. The concentrations of potentially toxic elements (PTE) in water, filtered water, DGTs and sediment samples were analyzed. Aqueous and organic solvent extracts of sediments samples and organic extracts of SPMDs were performed to assess acute toxicity to Vibrio fischeri by Microtox(?), and chronic toxicity to the green alga Pseudokirschneriella subcapitata. Microtox(?) test was also performed with DGT extracts. The results show that metals content of Catalan river waters are below the freshwater screening US EPA benchmarks, excepting some industrial areas (for Hg, Pb, and Zn). In contrast, sediments levels of some rivers were far above freshwater sediment screening US EPA benchmarks (for Zn, As, Cr, Pb, Ni, Hg, and Mn), particularly in the most industrialized areas. A good correlation was found between toxicity values of extracts (from sediments and DGTs) and PTE levels in sediments. The current results support the suitability of using combined point and passive sampling methods for assessing the chemical and ecotoxicological status of aqueous environments.     

Toxicity persistence in runoff and soil from experimental soybean plots following insecticide applications

Persistence of toxicity in runoff water and soil was investigated in experimental soybean plots subjected to successive runoff events following pesticide application. Runoff events were produced by irrigation using a sprinkler system. The pesticides applied were cypermethrin and endosulfan, which are widely used in soy production in Argentina. Toxicity tests were performed on two abundant components of the regional fauna, the amphipod Hyalella curvispina and the fish Cnesterodon decemmaculatus. Runoffs from two pesticide applications were assayed at different stages of the growing season: an early application when the soil was almost bare and a late one close to harvest, when the ground was covered by vegetation and just before soy leaves fell. Toxicity to H. curvispina in runoff ceased almost one month after the early application of the two pesticides, while it persisted for over three months after the late application. Soil toxicity to H. curvispina and runoff toxicity to C. decemmaculatus followed the same pattern. Higher temperatures and solar radiation are likely to have enhanced insecticide degradation after the early application. Lower temperatures and solar radiation in combination with increased organic matter from litter probably contributed to the longer persistence of toxicity recorded after the late application, as compared with the early application. Cypermethrin caused no mortality to C. decemmaculatus after the early application, while endosulfan toxicity persisted for almost four months after the late one.     

Polybrominated diphenyl ethers and their methoxylated and hydroxylated analogs in Brown Bullhead (Ameiurus nebulosus) plasma from Lake Ontario

Polybrominated diphenyl ethers (PBDEs), methoxylated PBDEs (MeO-PBDEs) and hydroxylated PBDEs (OH-PBDEs) were detected and quantified in Brown Bullhead (Ameiurus nebulosus) from Lake Ontario. Samples were collected in 2006 from three different locations near the city of Toronto: Frenchman’s Bay, Toronto Island, and Tommy Thompson Park. A total of 117 plasma samples were pooled into 19 samples, separating males and females by site of capture. Pooled samples were analyzed for 36 PBDEs, 20 MeO-PBDEs and 20 OH-PBDEs, but only six PBDEs, five MeO- and eight OH-compounds were confirmed against standards currently available. These peaks were quantified as “identified” peaks, while peaks matching ion ratios but not matching the retention time of the available standards were quantified as “unidentified” peaks. Both “identified” and “unidentified” concentrations were combined to obtain a total concentration. No significant variations were obtained for total PBDE concentrations, ranging from 3.33 to 9.02 ng g^?1 wet weight. However, OH- and MeO-PBDE totals ranged over 1 order of magnitude among the samples (not detected – 3.57 ng g^?1 wet weight for OH-PBDEs and not detected ?0.10 ng/g wet weight for MeO-PBDE). The results of this study suggested that these compounds are ubiquitous in biota. Source estimation of MeO- and OH-PBDEs in freshwater fish were discussed. Considering that up to date no freshwater sources for MeO- or OH-PBDEs have been reported, concentrations found should be mainly related to bioaccumulation from anthropogenic sources, although other sources could not be dismissed.     

Exposure to chemical mixtures in Mexican children: high-risk scenarios

In developing countries, the management of environmental toxicants is inadequate, thus, humans may be exposed to levels higher than normal levels (background levels). Therefore, the aim of this study was to evaluate the exposure level of Mexican children to dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethylene (DDE), lead, and polycyclic aromatic hydrocarbons [using 1-hydroxypyrene (1-OHP) as exposure biomarker] and to assess the percentage of children exposed to these four compounds at concentrations higher than normal in each community studied. We performed random sampling in eight communities in Mexico (five communities in Chiapas State and three communities in San Luis Potosi State). DDT and DDE were analyzed by gas chromatography/mass spectrometry, the quantification of lead in blood was performed using atomic absorption spectrophotometry, and 1-OHP analyses were performed using HPLC with a fluorescence detector. Elevated DDT, DDE, and 1-OHP levels were found in children living in the indigenous communities of Chiapas State, while higher blood lead levels were found in two communities in San Luis Potosí. Approximately 30 % of children living in Chiapas were exposed to all four compounds at concentrations above the guidelines for each compound, whereas 48 % of children studied were exposed to all four contaminants at concentrations higher than normal in a community in San Luis Potosí State. As expected, our results showed that in hot spots, children are exposed to levels higher than normal. Therefore, child environmental health programs are urgently needed.     

A Gis-Based Assessment of Groundwater Suitability for Irrigation Purposes in Flat Areas of the Wet Pampa Plain, Argentina

The Pampa in Argentina is a large plain with a quite obvious dependence on agriculture, water availability and its quality. It is a sensitive environment due to weather changes and slope variations. Supplementary irrigation is a useful practice for compensating the production in the zone. However, potential negative impacts of this type of irrigation in salinization and sodification of soils are evident. Most conventional methodologies for assessing water irrigation quality have difficulties in their application in the region because they do not adjust to the defined assumptions for them. Consequently, a new GIS-based methodology integrating multiparametric data was proposed for evaluating and delineating groundwater suitability zones for irrigation purposes in flat areas. Hydrogeological surveys including water level measurements, groundwater samples for chemical analysis and electrical conductivity (EC) measurements were performed. The combination of EC, sodium adsorption ratio, residual sodium carbonate, slopes and hydraulic gradient parameters generated an irrigation water index (IWI). With the integration of the IWI 1 to 3 classes (categories of suitable waters for irrigation) and the aquifer thickness the restricted irrigation water index (RIWI) was obtained. The IWI's index application showed that 61.3?% of the area has "Very high" to "Moderate" potential for irrigation, while the 31.4?% of it has unsuitable waters. Approximately, 46?% of the tested area has high suitability for irrigation and moderate groundwater availability. This proposed methodology has advantages over traditional methods because it allows for better discrimination in homogeneous areas.     

Agave salmiana Plant Communities in Central Mexico as Affected by Commercial Use

Agave salmiana is a native plant species harvested for the commercial production of mezcal (Agave spirits) in the highlands of central Mexico. The objective of this study was to identify vegetation changes in natural communities where A. salmiana has been differentially harvested for commercial purposes. Three plant community categories were identified in the state of Zacatecas based on their history of A. salmiana utilization: short (less than 10 years of use), moderate (about 25 years), and long (60 or more years). Species cover, composition, and density were evaluated in field surveys by use category. A gradient of vegetation structure of the communities parallels the duration of A. salmiana use. A. salmiana density was greatest (3,125 plants ha⁻¹) in the short-use areas and less (892 plants ha⁻¹) in the moderate-use areas, associated with markedly greater density of shrubs (200%) and Opuntia spp. (50%) in moderate-use areas. The main shrubs were Larrea tridentata, Mimosa biuncifera, Jatropha dioica and Buddleia scordioides while the main Opuntia species were Opuntia leucotricha and Opuntia robusta. A. salmiana density was least (652 plants ha⁻¹) in the long-use areas where shrubs were less abundant but Opuntia spp. density was 25% higher than in moderate-use areas. We suggest that shrubs may increase with moderate use creating an intermediate successional stage that facilitates the establishment of Opuntia spp. Long-term Agave use is generating new plant communities dominated by Opuntia spp. (nopaleras) as a replacement of the original communities dominated by A. salmiana (magueyeras).     

Influence of linear alkylbenzene sulfonate (LAS) on the structure of Alphaproteobacteria,Actinobacteria, and Acidobacteria communities in a soil microcosm

Background, aim, and scope  

Linear alkylbenzene sulfonate (LAS) is the most used anionic surfactant in a worldwide scale and is considered a high-priority pollutant. LAS is regarded as a readily biodegradable product under aerobic conditions in aqueous media and is mostly removed in wastewater treatment plants, but an important fraction (20–25%) is immobilized in sewage sludge and persists under anoxic conditions. Due to the application of the sludge as a fertilizer, LAS reaches agricultural soil, and therefore, microbial toxicity tests have been widely used to evaluate the influence of LAS on soil microbial ecology. However, molecular-based community-level analyses have been seldom applied in studies regarding the effects of LAS on natural or engineered systems, and, to our knowledge, there are no reports of their use for such appraisals in agricultural soil. In this study, a microcosm system is used to evaluate the effects of a commercial mixture of LAS on the community structure of Alphaproteobacteria, Actinobacteria, and Acidobacteria in an agricultural soil.