Estimating contaminant mass discharge: a field comparison of the multilevel point measurement and the integral pumping investigation approaches and their uncertainties

In this field study, two approaches to assess contaminant mass discharge were compared: the sampling of multilevel wells (MLS) and the integral groundwater investigation (or integral pumping test, IPT) that makes use of the concentration-time series obtained from pumping wells. The MLS approached used concentrations, hydraulic conductivity and gradient rather than direct chemical flux measurements, while the IPT made use of a simplified analytical inversion. The two approaches were applied at a control plane located approximately 40m downgradient of a gasoline source at Canadian Forces Base Borden, Ontario, Canada. The methods yielded similar estimates of the mass discharging across the control plane. The sources of uncertainties in the mass discharge in each approach were evaluated, including the uncertainties inherent in the underlying assumptions and procedures. The maximum uncertainty of the MLS method was about 67%, and about 28% for the IPT method in this specific field situation. For the MLS method, the largest relative uncertainty (62%) was attributed to the limited sampling density (0.63 points/m(2)), through a novel comparison with a denser sampling grid nearby. A five-fold increase of the sampling grid density would have been required to reduce the overall relative uncertainty for the MLS method to about the same level as that for the IPT method. Uncertainty in the complete coverage of the control plane provided the largest relative uncertainty (37%) in the IPT method. While MLS or IPT methods to assess contaminant mass discharge are attractive assessment tools, the large relative uncertainty in either method found for this reasonable well monitored and simple aquifer suggests that results in more complex plumes in more heterogeneous aquifers should be viewed with caution.     

A biology-based dynamic approach for the reconciliation of acute and chronic toxicity tests: application to Daphnia magna

There is the need to integrate existing toxicity data in a coherent framework for extending their domain of applicability as well as their extrapolation potential. This integration would also reduce time and cost-consuming aspects of these tests and reduce animal usage. In this work, based on data extracted from literature, we have assessed the advantages that a dynamic biology-toxicant fate coupled model for Daphnia magna could provide when assessing toxicity data, in particular, the possibility to obtain from short-term (acute) toxicity test long-term (chronic) toxicity values taking into account the inherent variability of D. magna populations and the multiple sources of data. The results show that this approach overcomes some of the limitations of existing toxicity tests and that the prediction errors are considerably reduced when compared with the factor from 2 to 5 obtained using acute-to-chronic ratios.     

Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs

A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L⁻¹) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ¹³C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ¹³C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ¹³C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ¹³C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ¹³C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.     

Validation of an analytical method for the quantification of pyrethrins on lemons and apricots using high-performance liquid chromatography/mass spectrometry

An analytical procedure has been developed for the determination of natural pyrethrins (pyrethrin I, pyrethrin II, jasmolin I, jasmolin II, cinerin I and cinerin II) in lemon and apricot. The QuEChERS method, which stands for quick, easy, cheap, effective, rugged and safe was used for extraction. Analysis of the extract was performed by liquid-chromatography-electrospray ionisation-tandem mass spectrometry. The ions prominent in the ESI spectra were [M+H]+ for the six compounds. A Zorbax SB-C18 column was used with a programmed gradient mobile phase consisting of (A) water containing 0.1% formic acid and 5 mM ammonium formate and (B) ACN. The method was linear within the investigated concentration range, displaying a calibration curve correlation factor of 0.99. The coefficients of variation obtained (RSD) were below 20% and the recoveries were in the 70-110% range.     

Determination of sixteen pesticides in peppers using high-performance liquid chromatography/mass spectrometry

A method for the detection and quantification of 16 pesticides: flufenoxuron, fenoxycarb, dimethomorph, acetamiprid, imidacloprid, lufenuron, thiacloprid, thiabendazole, thiophanate-methyl, spinosad, fenbutatin oxide, methoxyfenozide, oxamyl, clothianidin, thiamethoxam and carbendazim has been developed based on high-performance liquid chromatography-mass spectrometry. Pesticide residues were extracted from the samples according to the QuEChERS method which stands for quick, essay, cheap, effective, rugged and safe. Homogenised analytical portions (10 g ± 0.1) of samples of peppers were spiked at two levels (10 and 100 μg kg?1) with a small volume of an appropriate standard mixture solution containing each pesticide. Analyses were performed using electrospray ionization (ESI) and a MSD trap system. Chromatography separation was achieved using a ZORBAX SB-C18 3.5 μm particle size analytical column, 2.1 × 50 mm from Agilent, with gradient elution at a flow-rate of 0.4 mL/min with mobile phases: waters-0.1 % HCOOH-5 mM HCOONH? and MeOH-5 mM HCOONH?. The method has been validated based on the SANCO European Guidelines. Under the optimized conditions the recoveries (n = 7) were in the range 70-110 % with satisfactory precision (CV ≤ 20 %). A linear dynamic range was obtained over a range of concentrations from 10 to 100 μg kg?1 for each of the analytes, with correlation coefficients >0.997.     

The endocrine disrupting potential of sediments from the Upper Danube River (Germany) as revealed by in vitro bioassays and chemical analysis

Introduction  

The present study was part of a comprehensive weight-of-evidence approach with the goal of identifying potential causes for the declines in fish populations, which have been observed during the past decades in the Upper Danube River.     

Accumulation,biotransformation, and biochemical responses after exposure to arsenite and arsenate in the estuarine polychaete <Emphasis Type="BoldItalic">Laeonereis acuta</Emphasis> (Nereididae)

Introduction  

This study aimed to analyze antioxidant responses and oxidative damage induced by two inorganic forms of arsenic (As; As^III and As^V) in an estuarine polychaete species, Laeonereis acuta (Nereididae). The capacity of arsenic biotransformation was also evaluated through the methylation process considering the activity of a key enzyme involved in the metabolization process.     

Spectrofluorimetric study of the ageing of mixtions used in the gildings of mediaeval wall paintings

Introduction  

In the Middle Ages, we could find gildings on mural paintings. Gold, silver or tin leaves were applied according to distemper or mixtion technique. For the first one, a binder as glue is necessary, and for the second, a lipidic binder is used to stick the metallic leaf. Studies of gildings materials characterization show that the mixtion technique, with a mordant, is the most common. Linseed oil seems to be the binder used. It is always mixed with a siccative agent as lead. Because of bad conditions of conservation, the gildings do not resist anymore, only remain traces of metal or the adhesive under-layer. Thanks to the binder fluorescence, we can nowadays detect ancient gildings.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

Building resilience to water scarcity in southern Spain: a case study of rice farming in Doñana protected wetlands

Agricultural water management needs to evolve in view of increased water scarcity, especially when farming and natural protected areas are closely linked. In the study site of Doñana (southern Spain), water is shared by rice producers and a world heritage biodiversity ecosystem. Our aim is to contribute to defining adaptation strategies that may build resilience to increasing water scarcity and minimize water conflicts among agricultural and natural systems. The analytical framework links a participatory process with quantitative methods to prioritize the adaptation options. Bottom-up proposed adaptation measures are evaluated by a multi-criteria analysis (MCA) that includes both socioeconomic criteria and criteria of the ecosystem services affected by the adaptation options. Criteria weights are estimated by three different methods—analytic hierarchy process, Likert scale and equal weights—that are then compared. Finally, scores from an MCA are input into an optimization model used to determine the optimal land-use distribution in order to maximize utility and land-use diversification according to different scenarios of funds and water availability. While our results show a spectrum of perceptions of priorities among stakeholders, there is one overriding theme that is to define a way to restore part of the rice fields to natural wetlands. These results hold true under the current climate scenario and even more so under an increased water scarcity scenario.