Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. A case study: Suquía River basin (Argentina)

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC–MS). The optimized methodology showed LOQs at ng L^?1 levels (ranging 0.2–3.5 ng L^?1) in addition to acceptable precision and robustness (recoveries ranged 63–104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants.This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max. = 433.9 ng L^?1), alpha-cypermetrine (max. = 121.7 ng L^?1) and endosulfan sulfate (max. = 106.7 ng L^?1) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.     

Assessment of the effects of urbanization on trace elements of toe bones

Amphibians, particularly frogs and toads, are increasingly used as bioindicators of contaminant accumulation in pollution studies. We developed an analytical technique to analyse their elemental contents based on a small amount of toe bone samples. This method is environment-friendly as, unlike traditional methods, it is not necessary to kill animals during sampling. Using this technique, we explored the effects of urbanization on the elemental contents of toe bones. Bufo bufo specimens were collected from an urban and two rural ponds. The ratios of Ca and P at the ponds were: 20.5% Ca and 14.6% P at the urban pond and 30.4% and 29.6% Ca, 22.4% and 21.7% P at the rural ponds, respectively. For the other elements, the following percentage ratios were found: 0.7% B, 0.3% Mg and 0.06% Zn at the urban pond and 1.1% and 0.4% B, 0.4% Mg and 0.05% Zn at the rural ponds, respectively. Canonical discriminant analysis indicated the separation of the urban and the rural ponds based on the elemental concentrations of toe bones. Significant differences were found between the concentrations of Ca, P, Mg, B and Zn at the urban and the rural ponds (p?相似文献   

Polar organic chemical integrative sampler (POCIS): application for monitoring organic micropollutants in wastewater effluent and surface water

In this paper, we discuss the advantages and drawbacks of POCIS (Polar Organic Chemical Integrative Sampler) for the evaluation of river water quality downstream of wastewater treatment plants. POCIS proved well adapted to sampling alkylphenols and several pharmaceuticals. Concentration factors and the decrease in limits of quantification, compared to grab water sample analyses, were significant except for hormones, β-blockers and bronchodilators. Promising preliminary results obtained in situ on deuterated atenolol used as a performance reference compound need to be confirmed in-lab. This work confirms that POCIS is a valuable tool for monitoring hydrophilic organic molecules in river and wastewaters.     

Agricultural practices in grasslands detected by spatial remote sensing

The major decrease in grassland surfaces associated with changes in their management that has been observed in many regions of the earth during the last half century has major impacts on environmental and socio-economic systems. This study focuses on the identification of grassland management practices in an intensive agricultural watershed located in Brittany, France, by analyzing the intra-annual dynamics of the surface condition of vegetation using remotely sensed and field data. We studied the relationship between one vegetation index (NDVI) and two biophysical variables (LAI and fCOVER) derived from a series of three SPOT images on one hand and measurements collected during field campaigns achieved on 120 grasslands on the other. The results show that the LAI appears as the best predictor for monitoring grassland mowing and grazing. Indeed, because of its ability to characterize vegetation status, LAI estimated from remote sensing data is a relevant variable to identify these practices. LAI values derived from the SPOT images were then classified based on the K-Nearest Neighbor (KNN) supervised algorithm. The results points out that the distribution of grassland management practices such as grazing and mowing can be mapped very accurately (Kappa index?=?0.82) at a field scale over large agricultural areas using a series of satellite images.     

Assessment of potential health risk for inhabitants living near a former lead smelter. Part 2: site-specific human health risk assessment of Cd and Pb contamination in kitchen gardens

Metal contamination of urban soils and homegrown products has caused major concern. In Part 1, we investigated the long-term effects of a former smelter on the degree of kitchen garden-soil contamination and the quality of the homegrown vegetables from these gardens. The results showed that the soils retained a high level of contamination and that a large proportion of the vegetables produced did not comply with the legislation on the levels of metals allowed for human consumption. The present study aims to assess the associated potential health risk to local inhabitants through consumption of homegrown vegetables and ingestion of soil particles using a land use-based approach. For lead (Pb), the standard hazard quotient (HQ)-based risk assessment method was used to determine the HQ. For cadmium (Cd), the approach consisted of calculating the HQs and then deriving site-specific assessment criteria (SSAC) using the SNIFFER method. The results suggested that the exposure pathways considered should not engender any form of deleterious health effects for adults. For children, Pb was the main concern and induced a relatively high health risk through soil particle ingestion, and most total soil Cd concentrations exceeded the derived SSAC, in particular, through consumption of vegetables. The metal bioaccessibility in soils was incorporated into the methods to establish more realistic risk assessment measures. This study proposes an approach to integrate different human health risk assessment methods. Further investigations should complete the assessment to improve risk determination, e.g., the determination of metal bioaccessibility in vegetables.     

Blood lead levels, δ-ALAD inhibition, and hemoglobin content in blood of giant toad (Rhinella marina) to asses lead exposure in three areas surrounding an industrial complex in Coatzacoalcos, Veracruz, Mexico

The Coatzacoalcos Region in Veracruz, Mexico houses one of the most important industrial complexes in Mexico and Latin America. Lead is an ubiquitous environmental pollutant which represents a great risk to human health and ecosystems. Amphibian populations have been recognized as biomonitors of changes in environmental conditions. The purpose of this research is to measure exposure to lead and evaluate hematological and biochemical effects in specimens of giant toads (Rhinella marina) taken from three areas surrounding an industrial complex in the Coatzacoalcos River downstream. Lead levels in toads' blood are between 10.8 and 70.6 μg/dL and are significantly higher in industrial sites. We have found a significant decrease in the delta-aminolevulinic acid dehydratase (δ-ALAD) activity in blood from 35.3 to 78 % for the urban–industrial and industrial sites, respectively. In addition, we have identified a strong inverse relationship between the δ-ALAD activity and the blood lead levels (r?=??0.84, p?<?0.001). Hemoglobin and mean corpuscular hemoglobin levels, as well as the condition factor, are found to be lower at industrial sites compared with the reference sites. Our results suggest that the R. marina can be considered a good biomonitor of the δ-ALAD activity inhibition and hematological alterations at low lead concentrations.     

Dynamic extreme values modeling and monitoring by means of sea shores water quality biomarkers and valvometry

Water quality can be evaluated using biomarkers such as tissular enzymatic activities of endemic species. Measurement of molluscs bivalves activity at high frequency (e.g., valvometry) during a long time period is another way to record the animal behavior and to evaluate perturbations of the water quality in real time. As the pollution affects the activity of oysters, we consider the valves opening and closing velocities to monitor the water quality assessment. We propose to model the huge volume of velocity data collected in the framework of valvometry using a new nonparametric extreme values statistical model. The objective is to estimate the tail probabilities and the extreme quantiles of the distribution of valve closing velocity. The tail of the distribution function of valve closing velocity is modeled by a Pareto distribution with parameter ??_t,τ, beyond a threshold τ according to the time t of the experiment. Our modeling approach reveals the dependence between the specific activity of two enzymatic biomarkers (Glutathione-S-transferase and acetylcholinesterase) and the continuous recording of oyster valve velocity, proving the suitability of this tool for water quality assessment. Thus, valvometry allows in real-time in situ analysis of the bivalves behavior and appears as an effective early warning tool in ecological risk assessment and marine environment monitoring.     

Simultaneous Determination of O- and P- Nitrophenol by First Derivative Spectrophotometry

A simple method by first derivative spectrophotometry is proposed for the simultaneous determination of o-nitrophenol and p-nitrophenol. The analytes were separated from samples by liquid-liquid extraction (pH = 7.4) as tetrabutylammonium ion pairs into the 1,2-dichloroethane organic phase and subsequently the extracts were evaluated directly by derivative spectrophotometry. Simultaneous determination of both analytes could be carried out using the zero-crossing and the graphical methods for o-nitrophenol and p-nitrophenol, respectively. The determination ranges were found to be between 0.115 to 3.00 ppm and 0.130 to 3.00 ppm for o-nitrophenol and p-nitrophenol, respectively. The relative standard deviations were in all instances less than 2.0%. The proposed method was applied to the determination of these compounds in fruit juices.