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.     

Association between biotic and abiotic parameters and the occurrence of cyanobacteria in a Brazilian reservoir

The water reservoir of Vargem das Flores, Brazil, has been subject to eutrophication problems. The occurrence of cyanobacterial blooms in this water body has raised concerns regarding the presence of toxic metabolites. In order to understand the factors that promote the proliferation and distribution of cyanobacteria in the reservoir, physicochemical parameters, species composition, and toxicity of the reservoir water column were analyzed at monthly intervals over a 3-year period (2004-2007) using a range of analytical techniques. The results showed that cyanobacteria were absent in the dry period, returning after the onset of stratification. A succession pattern was observed within this group. The Aphanocapsa genus was dominant in the last rainy period of the study (October 2006 to March 2007). However toxicity was only detected when the genera Microcystis and Sphaerocavum were present (October 2005). The principal components analysis showed negative correlation between cyanobacteria and orthophosphate. The change of dominant cyanobacteria along the 3 years of study and the final prevalence of nontoxic genera in the reservoir is an evidence of water quality improvement in response to the management techniques implemented in the reservoir basin.     

Effects of anticholinesterase drugs on biomarkers and behavior of pumpkinseed, Lepomis gibbosus (Linnaeus, 1758)

The presence of pharmaceutical residues in the aquatic environment has recently received great attention, as potential adverse effects may arise from their presence. Inhibition of cholinesterases (ChE) has been widely used as an environmental biomarker of exposure to organophosphates (OP) and carbamate (CB) pesticides. However, other widespread anthropogenic contaminants - including pharmaceutical drugs - can exert toxic effects through ChE inhibition. Studies with aquatic species have shown that inhibition of ChE is associated with behavioral changes. Bearing this in mind, this work aimed to study the effects on individual behavior and acetylcholinesterase (AChE) activity of selected tissues of Lepomis gibbosus, after exposure to the anticholinesterasic drugs neostigmine and pyridostigmine. Results revealed that neostigmine significantly decreased the activity of AChE in the head (LOEC = 100 mg L(-1)), but not in dorsal muscle. On the other hand, pyridostigmine significantly decreased the activity of AChE in both the head (LOEC = 0.001 mg L(-1)) and dorsal muscle homogenates (LOEC = 100 mg L(-1)). The impairment of this enzymatic form was attained at ecologically relevant concentrations (in the case of pyridostigmine, for head AChE), which is an interesting finding, specially considering that these toxic effects occurred for a pharmaceutical compound. Contrarily, there were no significant differences in the behavior of L. gibbosus in any parameter, for neither drug. These results suggest that the behavioral parameters analyzed (scototaxis and lethargy) in L. gibbosus could not be regarded as suitable markers to assess the effects of drugs such as neostigmine and pyridostigmine. In contrast, the pattern of response elicited by cholinesterasic inhibition showed the usefulness of this toxicological parameter for the assessment of pharmaceuticals in the environment, namely anticholinesterasics.     

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

Studies concerning the lability and bioavailability of trace metals have played a prominent role in the search for contamination of water resources. This work describes the first application yet of the diffusive gradients in thin films technique (DGT) to the determination of the fraction of free plus labile metals in waters from the Amazon Basin. Due to the complexity of the use of DGT for samples with low ionic strength and high organic matter content (characteristic of Amazonian rivers), a new analytical procedure was developed. The method is based on the determinations of apparent diffusion coefficients (D_ap) in the laboratory, by performing deployments in samples collected in the corresponding sites of study. The D_ap thereby determined is then used for in situ measurements. The suitability of the proposed approach for determination of labile Al, Cd, Co, Cu, Mn, Ni, and Zn in the Amazon River and Rio Negro (English: Black River) was evaluated. Except for Co, Mn (in a deployment at Rio Negro), Ni and Zn (in a deployment at Amazon River), labile in situ measurements were lower or similar to dissolved concentrations, indicating suitability of the proposed approach.     

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.     

Pristine aquatic systems in a Long Term Ecological Research (LTER) site of the Brazilian Cerrado

The maintenance of limnological monitoring programs in the Cerrado Domain is crucial as a provision of useful information about temporal variations in land use and their respective water quality responses, considering its importance as water source for different Brazilian hydrographic basins. The purpose of this research was to describe limnological variables of low-order lotic systems located in the Cerrado Long Term Ecological Research (LTER) site (Environmental Protection Area (APA) Gama and Cabeça de Veado, Federal District of Brazil). Altogether, nine different streams were considered in this study. Samplings were conducted between 2010 and 2012, concentrated in the dry and rainy seasons. The sampling sites were generally characterized by low nutrient concentrations (e.g., medians, TP?=?14.8 μg L^?1, TN?=?20.0 μg L^?1, NO₃?=?13.8 μg L^?1) and slightly acidic waters (median, pH?=?5.3), with quite low electrical conductivity values (median?=?6.4 μS cm^?1). However, water quality degradation as a response to diffuse pollution was reported in some sampling points (e.g., Onça and Gama streams), expressed by relatively higher N and P concentrations, which were probably highlighted by the good water quality of the data set as whole. Although there was a trend to higher values of nitrogen forms during the dry season, significant statistical differences between the seasonal periods were reported only for the variables temperature and dissolved silica, which were higher in the dry and rainy season, respectively. The streams located in the preserved areas inside the ecological stations of APA Gama and Cabeça de Veado can still be considered good examples of reference lotic systems in the Cerrado Domain; notwithstanding, this study reported incipient signs of water quality degradation which cannot be overlooked in future limnological monitoring.     

Chlorophyll and suspended sediment mapping to the Caribbean Sea from rivers in the capital city of the Dominican Republic using ALOS AVNIR-2 data

This study aims to study the distribution of contaminants in rivers that flow into the Caribbean Sea using chlorophyll-a (Chl-a) and suspended sediment (SS) as markers and ALOS AVNIR-2 satellite sensor data. The Haina River (HN) and Ozama and Isabela Rivers (OZ-IS) that flow through the city of Santo Domingo, the capital of the Dominican Republic, were chosen. First, in situ spectral reflectance/Chl-a and SS datasets obtained from these rivers were acquired in March 2011 (case A: with no rain influence) and June 2011 (case B: with rain influence), and the estimation algorithm of Chl-a and SS using AVNIR-2 data was developed from the datasets. Moreover, the developed algorithm was applied to AVNIR-2 data in November 2010 for case A and August 2010 for case B. Results revealed that for Chl-a and SS estimations under cases A and B conditions, the reflectance ratio of AVNIR-2 band 4 and band 3 (AV4/AV3) and the reflectance of AVNIR-2 band 4 (AV4) were effective. The Chl-a and SS mapping results obtained using AVNIR-2 data corresponded with the field survey results. Finally, an outline of the distribution of contaminants at the mouth of the river that flows into the Caribbean Sea was obtained for both rivers in cases A and B.     

Investigation of the bacterial load and antibiotic susceptibility of dental units

The aim of this study was to evaluate the bacterial contamination level and to determine the antibiotic susceptibility of the isolated bacteria from dental unit waterlines (DUWLs) in Istanbul. Bacterial quality of DUWLs is very important, as patients and dental staff are regularly exposed to water and aerosols generated by the unit. If opportunistic pathogens such as Staphylococcus aureus, Pseudomonas aeruginosa, and Legionella pneumophila are present in DUWLs, patient and dental staff can be infected. One hundred water samples were collected from high-speed drills and input waters from 50 dental units. Aerobic heterotrophic bacteria counts and the presence of Legionella, Pseudomonas, oral streptococci, and Staphylococcus were investigated in dental unit waters and aerosol samples. In addition, the antibiotic susceptibility of the isolated and identified bacteria from DUWLs was examined. This research found that 37 out of 50 dental unit water samples exceeded the American Dental Association’s limit of 200 colony-forming units (CFU)/mL^?1. Legionella, oral streptococci, and S. aureus were not detected in any water or aerosol samples, but P. aeruginosa was isolated in three DUWLs. Also, Pseudomonas and Staphylococcus were found in water and aerosol samples. Cefoperazone, ofloxacin, gentamicin, ciprofloxacin, and piperacillin were the most effective antibiotics against the isolated bacteria from DUWLs.     

Assessment of trace metals and porphyrins in excreta of Humboldt penguins (Spheniscus humboldti) in different locations of the northern coast of Chile

To add data on trace metal contamination of Humboldt penguins in the South Pacific, levels of trace metals (As, Hg, Pb, Cu, Zn, and Cd) and porphyrins (copro-, uro-, and proto-) in excreta of Humboldt penguins that inhabit some important nesting sites on the northern coast of Chile were determined. Fresh excreta were collected on Pan de Azúcar Island, Chañaral Island, and Cachagua Island, from December 2011 to January 2012. Concentration of metals was determined by flame atomic absorption spectrophotometry, whereas porphyrins levels were measured by fluorimetric analysis. Concentrations (dry weight) of Cu (199.67 μg g^?1), As (7.85 μg g^?1), and Pb (12.78 μg g^?1) were higher (p?≤?0.05) in Cachagua Island. Colonies from Pan de Azúcar Island showed the highest levels of Hg (0.76 μg g^?1), Cd (47.70 μg g^?1), and Zn (487.10 μg g^?1). Samples from Cachagua Island showed the highest (p?≤?0.05) levels of copro- (2.16 nmol g^?1), uro- (2.20 nmol g^?1), and protoporphyrins (2.23 nmol g^?1). There was a positive correlation between the metals As, Pb, and Cu with uro-, copro-, and protoporphyrins. The results indicated that penguin colonies from Cachagua Island are more exposed to metal contamination than penguin colonies from Pan de Azúcar and Chañaral Islands, thus being more likely to develop certain diseases caused by contamination with metals. Considering biomagnification, the metals detected in the excreta of Humboldt penguins can be a source of contamination from marine environments to terrestrial ecosystems, which could also affect other living organisms.     

Dissolved inorganic nutrients and chlorophyll a in an estuary receiving sewage treatment plant effluents: Cachoeira River estuary (NE Brazil)

Sampling was conducted monthly during a transition period between the dry and rainy seasons in order to evaluate the effectiveness of a municipal sewage treatment plant (STP) in eutrophication control. STP effluent and fluvial input data were also estimated. In the dry period, high concentrations of nutrients, chlorophyll a (up to 360 μg?L^?1), and anoxia in bottom waters were observed in the upper portion of the estuary. Nitrate was scarce during the dry months, although high concentrations were observed at the river sources and the upper estuary. The N:P and Si:P molar ratios were usually below 16:1, and the Si:N ratio was higher than 1:1. The fluvial inputs were a greater source of nutrients to the estuary than the STP, but nutrient loading by these effluents were also important in contributing to the eutrophication of the upper estuarine zone, especially in the dry season when symptoms were more intense.