Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - evidence of changing silver sources

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg⁻¹; dry weight) in Gironde oysters, we compared long-term (∼1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ∼0.3 mg kg⁻¹; Cd: ∼0.8 mg kg⁻¹) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg⁻¹; Ag: from 6.7 to 0.43 mg kg⁻¹) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg⁻¹, dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg⁻¹, dw after 1993. Based on the Cd/Ag ratio (Cd/Ag ∼ 2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at λ = 254 nm. The photolysis of (α + β: 2 + 1) endosulfan, α-endosulfan and β-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 × 10^?4 s^?1; 1 × 10^?4 s^?1; and 2 × 10^?5 s^?1, respectively, and the calculated quantum yields (φ) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

阿尔罕伯拉宫和格拉纳达：旅游业与可持续性

和其它文化旅游胜地一样，阿尔罕伯拉宫和格拉纳达的旅游业也面临着在文化遗产的保存、管理和合理利用等方面进行战略革新的挑战 .改革基本参照《对阿尔罕伯拉宫和阿里哈雷斯特别规划修正案的预先研究》中的观点和举措 .其中包括旅游的可持续性、对参观者动机的考虑、“阿尔罕伯拉宫地区”的独特性、把参观按文化性质和生活经历性质进行分类、寻求在阿尔罕伯拉宫和格拉纳达及其周边环境之间建立一种良好关系的模式 .     

Evaluation of the best compromise between the urban air quality monitoring resolution by diffusive sampling and resource requirements

The need to collect data representative of overall urban pollution is all-important in order to monitor the population exposure. High spatial resolution monitoring using diffusive samplers allows studying of the urban pollutant distribution, thus enabling deeper investigation of their generation and diffusion mechanisms. Nevertheless, such a monitoring campaign has a certain cost. In this study we point out how to find the best compromise between the number of necessary measurements and the affordable costs for monitoring campaigns. We also describe an innovative method for the proper design of a fixed urban monitoring network by means of preliminary high spatial resolution campaigns using diffusive samplers. Four European capital cities (Dublin, Madrid, Paris and Rome) were monitored six times, each time for seven days. Benzene, toluene, ethylbenzene, xylenes (BTEX) and NO(2) concentrations were measured at 146 sites in Dublin, 293 in Madrid, 339 in Paris and 290 in Rome. Multiscale grids have been drawn which ranged in mesh size from 500 m to 2 km. The statistical processing of data produced a twofold result: the creation of isoconcentration maps with geostatistical procedures, and an algorithm aimed at locating the minimum number of sampling sites where the fixed monitoring stations should be placed. Average urban levels estimated on the basis of these selected sites differ by less than 8% from those calculated on the whole populations of the sampled points. The aim of this work is to investigate how far the resolution of a monitoring campaign of urban pollution by diffusive sampling can be reduced, thus making the monitoring less expensive in terms of human and financial resources, while preserving the same quality of the results that could be achieved with a higher resolution. We found that there is no significant loss of information when the resolution of the monitoring grid for BTEX is lowered to a mesh size of 1.85 km, that is a sampling site each 3.4 km(2), and that the minimum number of sampling sites to be used is N = 0.29 A, where A is the urban surface to be monitored (in km(2)). As the spatial distribution of NO(2) is less sensitive to the distance from the emission source than that of BTEX, this relationship could be retained as a valid lower limit for the mesh grid size also for NO(2) monitoring.     

Spatial distribution of lindane in topsoil of Northern France

Lindane is a persistent organochlorine insecticide and the use of this insecticide in agriculture was banned in France in 1998. In this study we investigated the concentrations of lindane in topsoil in Northern France and used robust geostatistics to map the geographical distribution of lindane. The study was based on a 16 km × 16 km grid covering an area of ca 25 000 km². Lindane was found in all soils, even those from non-agricultural-application areas. Very low ratios of α-/γ-HCH and δ-/γ-HCH suggested that a long time had passed since technical HCH was used in the studied area, or that emission sources of lindane were still present. A strong gradient in lindane concentration was observed, with the highest lindane concentrations in an area located in the northern region. Results suggested that some of the lindane observed in the high concentration area may have come from volatilization of old lindane applied to intensively cultivated areas, which was then transported by prevailing winds coming from the south-west and deposited in a densely inhabited depression.     

Metal speciation in landfill leachates with a focus on the influence of organic matter

This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.     

Precopulatory sexual interaction in an arctiid moth (Utetheisa ornatrix): Role of a pheromone derived from dietary alkaloids

Summary Males of Utetheisa ornatrix have a pair of brushlike glandular structures, the coremata, which they evert from the abdomen during close-range precopulatory interaction with the female. Males experimentally deprived of coremata are less acceptable to females. The principal chemical associated with the coremata, identified as a pyrrolizine (hydroxydanaidal), has a proven pheromonal role: males raised under conditions where they fail to produce hydroxydanaidal are also less likely to succeed in courtship, and the compound itself, as its (-)-isomer, is capable of inducing the principal receptive response (wing raising) of the female. Evidence is presented indicating that Utetheisa derive hydroxydanidal from defensive pyrrolizidine alkaloids that they sequester from their larval foodplants (Crotalaria spp.). It is proposed that in addition to signalling male presence to the female, hydroxydanaidal may provide the means whereby the female assesses the alkaloid content of the male and therefore his degree of chemical protectedness. The argument is made that such pheromonal assessment of defensive capacity may occur also in other insects, including danaid butterflies, many of which share with Utetheisa a dependence on pyrrolizidine alkaloids for sex-pheromone production.     

Effect of Liquefied Petroleum Gas on Ozone Formation in Guadalajara and Mexico City

Abstract

Leakages of liquefied petroleum gas (LPG) are suspected to contribute greatly to ozone (O₃) formation in Mexico City. We tested such a hypothesis by outdoor captive-air irradiation (CAI) experiments in the two largest Mexican metropolitan areas: Guadalajara (GMA) in 1997 and Mexico City (MCMA) in 2000. O₃ was monitored in each city for 20 days (8:00 a.m.–6:00 p.m.) in smog chambers containing unaltered morning air or morning air enriched with either commercial LPG or LPG synthetic mixture 60/40 (propane and butane). Tested additions of both components were 35% (by volume) in GMA and 60% (by volume) in MCMA. The addition effects on O₃ (max) were compared with effects from diluting LPG components or total nonmethane hydrocarbons (tNMHCs) by 50%. Diluting tNMHCs had the greatest absolute effect at both cities: it lowered O₃ (max) by 24% in GMA and 55% in MCMA. Adding commercial LPG increased O₃ (max) by 6% in GMA and 28% in MCMA; whereas adding LPG synthetic mixture 60/40 caused a similar increase in O₃ (max), 4 and 21% in GMA and MCMA, respectively. Compared with dilution of tNMHCs, dilution of LPG-associated compounds had a smaller decreasing effect on O₃ (max), only 4% in GMA and 15% in MCMA. These results show that commercial LPG and LPG synthetic mixture 60/40 affect O₃ formation to a lesser extent than estimated previously.     

Application of SMR to Modeling Watersheds in the Catskill Mountains

Very few hydrological models commonly used in watershed management are appropriate for simulating the saturation excess runoff. The Soil Moisture Routing model (SMR) was developed specifically to predict saturation excess runoff from variable source areas, especially for areas where shallow interflow controls saturation. A recent version of SMR was applied to two rural catchments in the Catskill Mountains to evaluate its ability to simulate the hydrology of these systems. Only readily available meteorological, topographical, and landuse information from published literature and governmental agencies was used. Measured and predicted streamflows showed relatively good agreement; the average Nash–Sutcliffe efficiency for the two watersheds were R ²=72% and R ²=63%. Distributed soil moisture contents and the locations of hydrologically sensitive areas were also predicted well.