Two sampling strategies for an overview of pesticide contamination in an agriculture-extensive headwater stream

Two headwaters located in southwest France were monitored for 3 and 2 years (Auvézère and Aixette watershed, respectively) with two sampling strategies: grab and passive sampling with polar organic chemical integrative sampler (POCIS). These watersheds are rural and characterized by agricultural areas with similar breeding practices, except that the Auvézère watershed contains apple production for agricultural diversification and the downstream portion of the Aixette watershed is in a peri-urban area. The agricultural activities of both are extensive, i.e., with limited supply of fertilizer and pesticides. The sampling strategies used here give specific information: grab samples for higher pesticide content and POCIS for contamination background noise and number of compounds found. Agricultural catchments in small headwater streams are characterized by a background noise of pesticide contamination in the range of 20–70 ng/L, but there may also be transient and high-peak pesticide contamination (2000–3000 ng/L) caused by rain events, poor use of pesticides, and/or the small size of the water body. This study demonstrates that between two specific runoff events, contamination was low; hence the importance of passive sampler use. While the peak pesticide concentrations seen here are a toxicity risk for aquatic life, the pesticide background noise of single compounds do not pose obvious acute nor chronic risks; however, this study did not consider the risk from synergistic “cocktail” effects. Proper tools and sampling strategies may link watershed activities (agricultural, non-agricultural) to pesticides detected in the water, and data from both grab and passive samples can contribute to discussions on environmental effects in headwaters, an area of great importance for biodiversity.     

Polycyclic aromatic hydrocarbons: bees, honey and pollen as sentinels for environmental chemical contaminants

Three beehive matrices, sampled in six different apiaries from West France, were analyzed for the presence of four polycyclic aromatic hydrocarbons (PAH4: benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene and chrysene). Samples were collected during four different periods in both 2008 and 2009. Honey samples showed the lowest levels of PAH4 contamination (min = 0.03 μg kg⁻¹; max = 5.80 μg kg⁻¹; mean = 0.82 μg kg⁻¹; Sd = 1.17). Bee samples exhibited higher levels of PAH4 contamination (min = 0.32 μg kg⁻¹; max = 73.83 μg kg⁻¹; mean = 7.03 μg kg⁻¹; Sd = 17.83) with a great dispersion of the concentrations due to four main events of high concentrations. Pollen samples showed only one major episode with the highest PAH4 concentration found (min = 0.33 μg kg⁻¹; max = 129.41 μg kg⁻¹; mean = 7.10 μg kg⁻¹; Sd = 22.28). The PAH4 concentrations found were significantly influenced by the landscape context for all beehive samples.     

Assessment of the interrelation between photooxidation and biodegradation of selected polyesters after artificial weathering

Three commercially available biodegradable polymers, two different aromatic-aliphatic copolyesters and polylactic acid, intended for the fabrication of agricultural mulching films, in addition to other applications, were subjected to a series of tests with the aim of studying the relationship between their photooxidation and biodegradation. Photooxidation resulted in the rearrangement of polymeric chains, in the case of both copolyesters the events led to polymeric chain crosslinking and the formation of insoluble polymeric gel. The tendency was significantly more pronounced for the copolyester with the higher content of the aromatic constituent. As regards polylactic acid photochemical reactions were not accompanied by crosslinking but instead provoked chain scissions. A biodegradation experiment showed that, despite marked structural changes, the extent of photooxidation was not the decisive factor, which significantly modified the rate of biodegradation in all three materials investigated. The specific surface area of the sample specimens was shown to be more important.     

Iophenoxic acid derivatives as markers of oral baits to wildlife

The bait-marker iophenoxic acid (IPA) and its derivatives are increasingly used for evaluating and optimizing the cost-effectiveness of baiting campaigns on wildlife, particularly on game species such as the wild boar. We aimed to determine whether concentrations of the three main IPA derivatives ethyl, methyl and propyl-IPA measured on thoracic liquid extracts (TLE) of hunted wild boars may be representative of two exposure doses, 40 and 200 mg, from 20 to 217 days after ingestion. Then we developed a method of detection of the three IPA derivatives by LC/ESI-MS-MS in muscle and liver to evaluate the suitability of these two other tissues for monitoring the marked bait consumption and for measuring available residues in the meat of marked animals. Three semi-captive wild boars received 40 mg of each IPA derivative, three received 200 mg, and three, as controls, did not receive IPA. Blood serum was sampled 20, 197 or 217 days after IPA exposure according to animals and to the derivative. Wild boars were shot by gun after the different times of serum sampling times, and TLE, muscle and liver were sampled. Our results suggest that TLE is not a relevant tissue for quantitatively expressing IPA exposure. Due to interference, no analytical method was validated on TLE containing digestive material. On the other hand, quantifications in the muscle and particularly in the liver could discriminate wild boars that had ingested the two IPA doses from 20 days until 7 months after exposure, especially for the two long term markers ethyl and propyl-IPA. So IPA quantifications in the liver sampled on hunted animals appear to be a reliable tool for monitoring bait consumption in the field at a large scale. Nevertheless, whatever the ingested dose, ethyl- and propyl-IPA concentrations measured in the muscle and the liver of tested animals until 217 days after exposure, remained higher than 0.01 mg/kg, the Maximal Residue Limit (MRL) is recommended for molecules for which no toxicological data are available. Based on the range of IPA residues available in these two tissues, implications for humans consuming marked animals are discussed.     

The drivers of risk to water security in Shanghai

Big cities are often said to have big water problems, and Shanghai is no exception. In this paper, we examine and compare the influence of the major factors that give rise to the risk of water insecurity in Shanghai. There is an extensive and diverse literature on these issues, dealt with in isolation, and here, we provide a synthesis of the literature, together with our own assessments and calculations, to assess what are the risks to Shanghai’s water supply and what is our degree of confidence in this assessment. We describe the systems that supply water to the city, and past and future changes in the systems, including changes in the glaciers that supply some water to the river, changes in climate, changes in land use, the construction of dams, and water diversions. We show how, at the same time as Shanghai is increasing its dependence on the Yangtze river, water diversions and sea level rise are increasing the risk that this water will be too saline to consume at certain times of the year. This analysis suggests that most of the major drivers of the risk to water security in Shanghai are within the power of environmental managers to control.     

Review of ozone and temperature lidar validations performed within the framework of the Network for the Detection of Stratospheric Change

The use of assimilation tools for satellite validation requires true estimates of the accuracy of the reference data. Since its inception, the Network for Detection of Stratospheric Change (NDSC) has provided systematic lidar measurements of ozone and temperature at several places around the world that are well adapted for satellite validations. Regular exercises have been organised to ensure the data quality at each individual site. These exercises can be separated into three categories: large scale intercomparisons using multiple instruments, including a mobile lidar; using satellite observations as a geographic transfer standards to compare measurements at different sites; and comparative investigations of the analysis software. NDSC is a research network, so each system has its own history, design, and analysis, and has participated differently in validation campaigns. There are still some technological differences that may explain different accuracies. However, the comparison campaigns performed over the last decade have always proved to be very helpful in improving the measurements. To date, more efforts have been devoted to characterising ozone measurements than to temperature observations. The synthesis of the published works shows that the network can potentially be considered as homogeneous within +/-2% between 20-35 km for ozone and +/-1 K between 35-60 km for temperature. Outside this altitude range, larger biases are reported and more efforts are required. In the lower stratosphere, Raman channels seem to improve comparisons but such capabilities were not systematically compared. At the top of the profiles, more investigations on analysis methodologies are still probably needed. SAGE II and GOMOS appear to be excellent tools for future ozone lidar validations but need to be better coordinated and take more advantage of assimilation tools. Also, temperature validations face major difficulties caused by atmospheric tides and therefore require intercomparisons with the mobile systems, at all sites.     

Polynomial Surrogates for Open-Channel Flows in Random Steady State

Assessing epistemic uncertainties is considered as a milestone for improving numerical predictions of a dynamical system. In hydrodynamics, uncertainties in input parameters translate into uncertainties in simulated water levels through the shallow water equations. We investigate the ability of generalized polynomial chaos (gPC) surrogate to evaluate the probabilistic features of water level simulated by a 1-D hydraulic model (MASCARET) with the same accuracy as a classical Monte Carlo method but at a reduced computational cost. This study highlights that the water level probability density function and covariance matrix are better estimated with the polynomial surrogate model than with a Monte Carlo approach on the forward model given a limited budget of MASCARET evaluations. The gPC-surrogate performance is first assessed on an idealized channel with uniform geometry and then applied on the more realistic case of the Garonne River (France) for which a global sensitivity analysis using sparse least-angle regression was performed to reduce the size of the stochastic problem. For both cases, Galerkin projection approximation coupled to Gaussian quadrature that involves a limited number of forward model evaluations is compared with least-square regression for computing the coefficients when the surrogate is parameterized with respect to the local friction coefficient and the upstream discharge. The results showed that a gPC-surrogate with total polynomial degree equal to 6 requiring 49 forward model evaluations is sufficient to represent the water level distribution (in the sense of the \(\ell _2\) norm), the probability density function and the water level covariance matrix for further use in the framework of data assimilation. In locations where the flow dynamics is more complex due to bathymetry, a higher polynomial degree is needed to retrieve the water level distribution. The use of a surrogate is thus a promising strategy for uncertainty quantification studies in open-channel flows and should be extended to unsteady flows. It also paves the way toward cost-effective ensemble-based data assimilation for flood forecasting and water resource management.     

The study of age influence on human bone lead metabolism by using a simplified model and X-ray fluorescence data

Long term lead metabolism in the human body has never been fully understood due to the lack of human data in this area. The technological improvement of bone lead measurement systems has made bone lead data of substantial populations available. In this study, a set of X-ray fluorescence bone lead data was used to test Leggett's lead metabolism model (R. W. Leggett, Environ. Health Perspect., 1993a, 101, 598-616), especially the model of metabolism in bone. The data set includes the bone lead concentration of 539 occupationally exposed workers, of whom 327 were measured twice in five years. The bone lead concentrations of both cortical bone (tibia) and trabecular bone (calcaneus) were obtained by Cd-109 gamma-ray induced XRF measurement. The histories of blood lead concentration for these workers were used to regulate the input file of the model. The results show that the bone lead concentrations predicted by Leggett's model greatly underestimate the measured values, especially for older workers. This data set was then organized into five age groups. A new simplified model was applied to estimate the lead transfer rates between blood and lead compartments for these age groups. The original transfer rates and the new transfer rates are compared, and the differences are discussed. When the transfer rates derived from measured bone lead data were put into the input file of the model to replace the existing parameters, the predicted values were much closer to the measured values for both cortical bone and trabecular bone.