Degradation of freshwater ecosystems by uncontrolled human activities is a growing concern in the tropics. In this regard, we aimed at testing an integrative framework based on the IFEQ index to assess freshwater ecosystem health of river basins impacted by intense livestock and agricultural activities, using the Muchacho River Basin (MRB) as a case study. The IFEQ combine multiple lines of evidence such as riverine hydromorphological analysis (LOE 1), physicochemical characterization using ions and pesticides (LOE 2), aquatic macroinvertebrate monitoring (LOE 3), and phytotoxicological essays with L. sativa (LOE 4). Overall, results showed an important reduction in streamflow and an elevated increase in ion concentrations along the MRB caused by deforestation and erosion linked to agricultural and livestock activities. Impacts of the high ion concentrations were evidenced in macroinvertebrate communities as pollution-tolerant families, associated with high conductivity levels, represented 92 % of the total abundance. Pollution produced by organophosphate pesticides (OPPs) was critical in the whole MRB, showing levels that exceeded 270-fold maximum threshold for malathion and 30-fold for parathion, the latter banned in Ecuador. OPPs concentrations were related to low germination percentages of Lactuca sativa in sediment phytotoxicity tests. The IEFQ index ranged from 44.4 to 25.6, indicating that freshwater ecosystem conditions were “bad” at the headwaters of the MRB and “critical” along the lowest reaches. Our results show strong evidence that intense agricultural and livestock activities generated significant impacts on the aquatic ecosystem of the MRB. This integrative approach better explains the cumulative effects of human impacts, and should be replicated in other basins with similar conditions to help decision-makers and concerned inhabitants generate adequate policies and strategies to mitigate the degradation of freshwater ecosystems.

The present pilot study aimed to provide an overview of organic contaminant concentration levels in the littoral ecosystems of the Pertuis seas. The study determined the concentrations of twenty-nine pesticides, six nonylphenols and seven polybrominated diphenyl ethers (PBDEs) in sediments, seawater, Pacific oysters and blue mussels. Oysters accumulated a higher number of pesticides than blue mussels. Indeed, alpha BHC (0.60–0.72 ng/g, ww), chlorfenvinphos (1.65–2.12 ng/g, ww), chlorpyrifos (0.79–0.93 ng/g, ww), chlortoluron (2.50–4.31 ng/g, ww), metolachlor (up to 0.38 ng/g, ww) and parathion (0.56–0.69 ng/g, ww) were quantified in oysters whereas only alpha BHC (0.24–0.31 ng/g, ww), was quantified in mussels. The present results also revealed that the POPs detected in water or sediments were not ultimately found accumulated in bivalves. Other molecules such as methylparathion and BDE47 were quantified in sediments. These molecules, BDE99 and one nonylphenol (OP2OE) were quantified in seawater. Finally, the comparison with the available environmental guidelines showed that the values measured were at concentrations not considered to cause adverse effects at the populations' level except for chlortoluron in seawater (15–50 ng/L).

In this study, the effectiveness of subcritical water extraction (SCWE) was assessed by extracting four pesticides, namely diazinon, parathion, phenthoat, and EPN, from contaminated soil. The extraction efficiencies of different temperatures (25, 75, 100, 125, and 150 C); times (10, 20, 30, and 40 min); pressures (1, 2, and 3 MPa); and water flow rates (0.5, 0.7, 1.0, and 1.5 mL/min) were investigated. The optimum temperature, time, pressure, and flow rate were found to be 150 C, 20 min, 2 MPa, and 0.5 mL/min, respectively, in lab-scale. At this operating condition, the residual concentration of pesticide was less than 0.5 mg/kg, corresponding to an extraction efficiency of 99.9 %. The aim of this study was to also evaluate the removal efficiency on 30- and 167-fold scale-up extraction at optimum extraction condition obtained from lab-scale studies. The scale-up method considering constant ratio of the volume of water to soil mass was a feasible procedure. The results of our study suggest that SCWE is a promising option for effective disposal of pesticide- contaminated soil. © 2013 Springer Science+Business Media Dordrecht.

Adsorption of six neutral (chlorpyrifos, α-endosulfan, fenthion, parathion, parathion metyl, and cis permethrin) and six basic (pirimicarb, prochloraz, prometryn, pirimiphos ethyl, quinoxyfen, and triadimefon) pesticides was measured in ten natural soils in order to unravel the parameters influencing soil sorption. Linear regression confirmed that organic carbon content of soil is the determinant factor of soil sorption along with a secondary role of clay in the case of basic pesticides. Concerning pesticides themselves, their potential to be absorbed is governed by hydrophobic, electrostatic, and polar interactions. Electrostatic interactions can be expressed by considering the molecular fraction of positively charged species (F⁺). The combination of these parameters led to good prediction models, where the two expressions of lipophilicity, octanol-water partition (logP) and distribution coefficient (logD), showed similar performance. Finally, the role of electrostatic interactions to soil sorption and their successful expression by F⁺ parameter was further confirmed using artificial adjustment of the acidity of one soil at different pH values not covered by the natural acidity of the investigated soils.

Urinary metabolites of organophosphate (OP) and pyrethroid (PYR) pesticides and biomarkers of effects were studied in a population (n=40) residing in an important agricultural area of the province of Córdoba (Argentina). Detection frequencies (DF) higher than 85% were observed for the metabolites of pirimiphos (2-diethylamino-6-methylpyrimidin-4-ol –DEAMPY-, median 7.5 μg/g creatinine, DF: 100%), parathion (p-nitrophenol, 0.99 μg/g creatinine, 100%), and chlorpyrifos (3,5,6-trichloro-2-pyridinol, 0.25 μg/g creatinine, 85%). The DEAMPY concentrations doubled the levels found in other studies and were negatively associated with Er-AChE activity, suggesting the appearance of health effects already in environmental exposure levels below established acceptable daily intakes (ADIs). 3-Phenoxybenzoic acid, the metabolite of several PYR pesticides, was also found in all samples. This metabolite was also significantly negatively correlated with Er-AChE, indicating effects of pyrethroid pesticides on the acetylcholine system even at concentrations below the ADI.

The study presented in this paper evaluated the effectiveness of surfactants in enhancing mass removal of organophosphorus pesticides (OPPs) from soil under highly alkaline conditions and potential for enhancing in situ alkaline hydrolysis for treatment of OPPs, particularly parathion (EP3) and methyl parathion (MP3). In control and surfactant experiments, hydrolysis products EP2 acid, MP2 acid, and PNP were formed in non-stoichiometric amounts indicating instability of these compounds. MP3 and malathion were found to have faster hydrolysis rates than EP3 under the conditions studied. All surfactants evaluated increased solubility of OPPs under alkaline conditions with four nonionic alcohol ethoxylate products providing the greater affect over the polyglucosides, sulfonate, and propionate surfactants evaluated. The alcohol ethoxylates were shown to provide substantial mass removal of OPPs from soil. Hydrolysis rates were typically slower in the presence of surfactant, despite the relatively higher aqueous concentrations of OPPs; this was likely due to micellar solubilization of the OPPs which were therefore less accessible for hydrolysis. The results of this study support the use of surfactants for contaminant mass removal from soil, particularly under alkaline conditions, and may have implications for use of some surfactants in combination with other technologies for treatment of OPPs.