Water quality index for agricultural systems in Northwest Uruguay

Agricultural systems have experienced rapid expansion and intensification in the last several decades. In Uruguay, since the beginning of 2000, the most common cropping systems have included soybeans. Currently, this crop is expanding towards lowlands traditionally occupied by rice in rotation with pastures. However, the environmental effects of agricultural intensification and diversification are not well known. Thus, some indices have been proposed to quantify the changes in agricultural production systems and assess water quality. The main goal of this study was to develop a water quality index (WQI) to assess the impacts of the diversification of rice production systems in northwest Uruguay. The study was carried out in an agricultural basin where other summer crops have been incorporated in the rice-pasture sequence. Agriculture intensification and crop diversification indices were calculated using information provided by farmers. Water samples were collected downstream of the production area before crop sowing and after crop harvest (2008–2009 to 2010–2011 and 2016–2017 to 2017–2018). Biochemical oxygen demand, nitrates, total phosphorus, fecal coliforms, and total suspended solids were the variables that mainly explained the effects of the agricultural activities on water quality. The proposed water quality index included these unweighted variables, which allowed for the pre-sowing and post-harvest to be differentiated, as well as the degree of diversification. Therefore, the proposed WQI constitutes a tool that can be used to evaluate the water quality in an agricultural basin. Likewise, it can be used to select agricultural sequences that generate the least possible impacts on the associated water resources.     

Biodegradability of the anticancer drug etoposide and identification of the transformation products

Etoposide susceptibility to microbiological breakdown was studied in a batch biotransformation system, in the presence or absence of artificial wastewater containing nutrients, salts and activated sludge at two concentration levels. The primary focus of the present study was to study etoposide transformation products by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry (MS/MS). Data-dependent experiments combining full-scan MS data with product ion spectra were acquired to identify the molecular ions of etoposide transformation products, to propose the molecular formulae and to elucidate their chemical structures. Due to the complexity of the matrix, visual inspection of the chromatograms showed no clear differences between the controls and the treated samples. Therefore, the software package MZmine was used to facilitate the identification of the transformation products and speed up the data analysis. In total, we propose five transformation products; among them, four are described as etoposide transformation products for the first time. Even though the chemical structures of these new compounds cannot be confirmed due to the lack of standards, their molecular formulae can be used to target them in monitoring studies.     

First inter-laboratory comparison exercise for the determination of anticancer drugs in aqueous samples

The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jo?ef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV?≤?12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27–143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV?=?8 %). Random and total errors were identified by means of Youden plots.     

Pesticide dissipation curves in peach,pear and tomato crops in Uruguay*

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r²=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r²=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Pesticide dissipation curves in peach, pear and tomato crops in Uruguay

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r(2)=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r(2)=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Distribution and human health risk assessment of PAHs in four fish species from a SW Atlantic estuary

Environmental Science and Pollution Research - The aim of this study is to assess—for the first time—the concentration of the 16 polycyclic aromatic hydrocarbons (PAHs) in the muscle...     

Establishment Success of Coexisting Native and Exotic Trees Under an Experimental Gradient of Irradiance and Soil Moisture

The exotic trees Ailanthus altissima, Robinia pseudoacacia, Acer negundo and Elaeagnus angustifolia coexist with the native trees Fraxinus angustifolia and Ulmus minor in river banks of central Spain. Similarly, the exotic trees Acacia dealbata and Eucalyptus globulus co-occur with the natives Quercus pyrenaica and Pinus pinaster in Northwest Spain. We aimed to identify the environmental conditions that favour or hamper the establishment success of these species. In spring 2008, seeds of the studied species were sown under an experimental gradient of light (100, 65, 35, 7% of full sunlight) combined with three levels of soil moisture (mean soil water potential = −0.97, −1.52 and −1.77 MPa.). During the first growing season we monitored seed emergence and seedling survival. We found that the effect of light on the establishment success was stronger than the effect of soil moisture. Both exotic and native species of central Spain showed a good performance under high light, A. negundo being the most shade tolerant. Water shortage diminished E. angustifolia and A. altissima success. Among NW Spain species, A. dealbata and P. pinaster were found to be potential competitors for colonizing high-irradiance scenarios, while Q. pyrenaica and E. globulus were more successful under moderate shade. High soil moisture favoured E. globulus but not A. dealbata establishment. These results contribute to understand some of the factors controlling for spatial segregation between coexisting native and exotic tree species, and can help to take decisions orientated to the control and management of these exotic species.     

The natives are restless, but not often and mostly when disturbed

The argument that the threat posed by introduced species is overblown is often buttressed by the observation that native species sometimes also become invasive. An examination of the literature on plant invasions in the United States shows that six times more nonnative species have been termed invasive than native species, and that a member of the naturalized nonnative pool is 40 times more likely than a native species to be perceived as invasive. In the great majority of instances in which a native plant species is seen as invasive, the invasion is associated with an anthropogenic disturbance, especially changed fire or hydrological regime, livestock grazing, and changes wrought by an introduced species. These results suggest that natives are significantly less likely than nonnatives to be problematic for local ecosystems.     

Lichen microalgae are sensitive to environmental concentrations of atrazine

The identification of new organisms for environmental toxicology bioassays is currently a priority, since these tools are strongly limited by the ecological relevance of taxa used to study global change. Lichens are sensitive bioindicators of air quality and their microalgae are an untapped source for new low-cost miniaturized bioassays with ecological importance. In order to increase the availability of a wider range of taxa for bioassays, the sensitivity of two symbiotic lichen microalgae, Asterochloris erici and Trebouxia sp. TR9, to atrazine was evaluated. To achieve this goal, axenic cultures of these phycobionts in suspension were exposed to a range of environmental concentrations of the herbicide atrazine, a common water pollutant. Optical density and chlorophyll autofluorescence were used as endpoints of ecotoxicity and ecophysiology on cell suspensions. Results show that lichen microalgae show high sensitivity to very low doses of atrazine, being higher in Asterochloris erici than in Trebouxia sp. TR9. We conclude that environmental concentrations of atrazine could modify population dynamics probably through a shift in reproduction strategies of these organisms. This seminal work is a breakthrough in the use of lichen microalgae in the assessment of micropollution effects on biodiversity.