Influence of fly ash aided phytostabilisation of Pb, Cd and Zn highly contaminated soils on Lolium perenne and Trifolium repens metal transfer and physiological stress

Due to anthropogenic activities, large extends of soils are highly contaminated by Metal Trace Element (MTE). Aided phytostabilisation aims to establish a vegetation cover in order to promote in situ immobilisation of trace elements by combining the use of metal-tolerant plants and inexpensive mineral or organic soil amendments. Eight years after Coal Fly Ash (CFA) soil amendment, MTE bioavailability and uptake by two plants, Lolium perenne and Trifolium repens, were evaluated, as some biological markers reflecting physiological stress. Results showed that the two plant species under study were suitable to reduce the mobility and the availability of these elements. Moreover, the plant growth was better on CFA amended MTE-contaminated soils, and the plant sensitivity to MTE-induced physiological stress, as studied through photosynthetic pigment contents and oxidative damage was lower or similar. In conclusion, these results supported the usefulness of aided phytostabilisation of MTE-highly contaminated soils.     

Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain)

Background, aim, and scope  The first step in the restoration of a medieval stained glass window is the evaluation of its degree of degradation. This implies the study of the chemical composition of the stained glass as well as the new mineral phases developed on its surface (patinas). Patinas are clearly related to glass composition, time, environmental conditions, microenvironments developed in local zones, bioactivity, physical and chemical factors, etc. This study was carried out on patinas developed in selected Na-rich stained glass of the Santa Maria de Pedralbes Monastery (Barcelona, Spain). The location of this monument in the city (about 5 km from the shoreline and close to the Collserola hill flank) helped to determine the environmental conditions in which patinas developed. The aim of our study was to characterize the patinas formed on the surface of the selected glass of this monastery in order to understand the role of the chemical composition of the original glass (Na-rich) as well as the environmental conditions in which they developed. Materials and methods  Powdered samples of two different color-type patinas (ochre-orange and brownish) were collected in the external and internal parts of the stained glass windows of the Prebystery and Chapter House of the Pedralbes Monastery by using a precision (odontological) drill. These patinas were subsequently analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Results  XRD analyses evidenced the presence of sulfates (gypsum and thenardite), calcite, Ca-oxalates (whewellite and weddellite), and quartz forming part of the patinas. Although these mineral phases can be found in both color-type patinas, whewellite and thenardite are more common in the ochre-orange patinas. The results obtained were validated by the FTIR measurements. It has been observed, when thenardite is present, that gypsum occurs as traces. Thenardite is in most of the cases associated with whewellite and mainly occurs in the internal parts of the glass. In contrast, weddellite is limited to the absence of thenardite and whewellite and to the external parts of the stained glass. Quartz is present in all the patinas independent of their location and color. Calcite also occurs in many samples. It appears in both color-type patinas and, in some cases, is associated to the presence of weddellite but not to whewellite and/or thenardite. Discussion  Glass composition together with environmental conditions and location of the patinas (internal or external parts of the stained glass window), as well as the provenance of the glass within the monastery, are the main factors that define the development of the new mineral phases. Moreover, the action of microorganisms, when present, can also strongly influence the development of some mineral phases. For example, the formation of calcite in the external parts of the stained glass (associated with the presence of oxalates) is related to the action of microorganisms. When calcite is formed in the internal parts of the glass and it is not associated with the presence of Ca-oxalates, an inorganic origin can be invoked. The presence of weddellite requires a very humid microenvironment with very little exposure to sunlight. In fact, this mineral phase has only been observed in the external parts of some glass located in the humid and shady side of the monastery. Whewellite (which only appears in the internal parts) needs a low degree of relative humidity. It has been observed that sulfur precipitating in basically one mineral phase (thenardite or gypsum) depends on the microenvironmental conditions of the moment and the glass composition. When thenardite occurs, it can be maintained that the original glass is of Na composition. The occurrence of quartz in all samples is interpreted as being due to the deposition of atmospheric particulate matter. The color of the patinas can be originated by different processes (presence of carotenes, organic pigmentation, atmospheric contamination, etc.). Conclusions  In the case of moderately weathered stained glass windows, the combination of XRD and FTIR techniques is very useful to obtain a fast preliminary evaluation of the degree of weathering of a stained glass window. The presence of specific mineral phases in the patina (e.g., thenardite) confirms the Na composition of the original stained glass. This is important since Na-rich glass underwent a lesser degree of weathering than K- or K-Ca-rich glass. However, their absence cannot preclude other possibilities. It has been extensively evidenced through time that environmental conditions play an important role on the formation of the different mineral phases which form part of the patinas. Recommendations and perspectives  The first step in the restoration of a stained glass window is the evaluation of the degree of deterioration of the glass. This evaluation includes a chemical analysis of the glass as well as a characterization of the patinas developed on their surfaces. The obtained results will be essential in order to define the best restoration practices to be followed.     

Measuring atmospheric composition change

Scientific findings from the last decades have clearly highlighted the need for a more comprehensive approach to atmospheric change processes. In fact, observation of atmospheric composition variables has been an important activity of atmospheric research that has developed instrumental tools (advanced analytical techniques) and platforms (instrumented passenger aircrafts, ground-based in situ and remote sensing stations, earth observation satellite instruments) providing essential information on the composition of the atmosphere. The variability of the atmospheric system and the extreme complexity of the atmospheric cycles for short-lived gaseous and aerosol species have led to the development of complex models to interpret observations, test our theoretical understanding of atmospheric chemistry and predict future atmospheric composition. The validation of numerical models requires accurate information concerning the variability of atmospheric composition for targeted species via comparison with observations and measurements.In this paper, we provide an overview of recent advances in instrumentation and methodologies for measuring atmospheric composition changes from space, aircraft and the surface as well as recent improvements in laboratory techniques that permitted scientific advance in the field of atmospheric chemistry. Emphasis is given to the most promising and innovative technologies that will become operational in the near future to improve knowledge of atmospheric composition. Our current observation capacity, however, is not satisfactory to understand and predict future atmospheric composition changes, in relation to predicted climate warming. Based on the limitation of the current European observing system, we address the major gaps in a second part of the paper to explain why further developments in current observation strategies are still needed to strengthen and optimise an observing system not only capable of responding to the requirements of atmospheric services but also to newly open scientific questions.     

High levels of natural radioactivity in biota from deep-sea hydrothermal vents: a preliminary communication

Hydrothermal deep-sea vent fauna is naturally exposed to a peculiar environment enriched in potentially toxic species such as sulphides, heavy metals and natural radionuclides. It is now well established that some of the organisms present in such an environment accumulate metals during their lifespan. Though only few radionuclide measurements are available, it seems likely that hydrothermal vent communities are exposed to high natural radiation doses. Various archived biological samples collected on the East Pacific Rise and the Mid-Atlantic Ridge in 1996, 2001 and 2002 were analysed by ICP-MS in order to determine their uranium contents (²³⁸U, ²³⁵U and ²³⁴U). In addition ²¹⁰Po–Pb were determined in 2 samples collected in 2002. Vent organisms are characterized by high U, and Po–Pb levels compared to what is generally encountered in organisms from outside hydrothermal vent ecosystems. Though the number of data is low, the results reveal various trends in relation to the site, the location within the mixing zone and/or the organisms' trophic regime.     

Comparison of annual dry and wet deposition fluxes of selected pesticides in Strasbourg, France

This work summarizes the results of a study of atmospheric wet and dry deposition fluxes of Deisopropyl-atrazine (DEA), Desethyl-atrazine (DET), Atrazine, Terbuthylazine, Alachlor, Metolachlor, Diflufenican, Fenoxaprop-p-ethyl, Iprodione, Isoproturon and Cymoxanil pesticides conducted in Strasbourg, France, from August 2000 through August 2001. The primary objective of this work was to calculate the total atmospheric pesticide deposition fluxes induced by atmospheric particles. To do this, a modified one-dimensional cloud water deposition model was used. All precipitation and deposition samples were collected at an urban forested park environment setting away from any direct point pesticide sources. The obtained deposition fluxes induced by atmospheric particles over a forested area showed that the dry deposition flux strongly contributes to the total deposition flux. The dry particle deposition fluxes are shown to contribute from 4% (DET) to 60% (cymoxanil) to the total deposition flux (wet + dry).     

Back-extrapolation of estimates of exposure from current land-use regression models

Land use regression has been used in epidemiologic studies to estimate long-term exposure to air pollution within cities. The models are often developed toward the end of the study using recent air pollution data. Given that there may be spatially-dependent temporal trends in urban air pollution and that there is interest for epidemiologists in assessing period-specific exposures, especially early-life exposure, methods are required to extrapolate these models back in time. We present herein three new methods to back-extrapolate land use regression models. During three two-week periods in 2005–2006, we monitored nitrogen dioxide (NO₂) at about 130 locations in Montreal, Quebec, and then developed a land-use regression (LUR) model. Our three extrapolation methods entailed multiplying the predicted concentrations of NO₂ by the ratio of past estimates of concentrations from fixed-site monitors, such that they reflected the change in the spatial structure of NO₂ from measurements at fixed-site monitors. The specific methods depended on the availability of land use and traffic-related data, and we back-extrapolated the LUR model to 10 and 20 years into the past. We then applied these estimates to residential information from subjects enrolled in a case–control study of postmenopausal breast cancer that was conducted in 1996.Observed and predicted concentrations of NO₂ in Montreal decreased and were correlated in time. The estimated concentrations using the three extrapolation methods had similar distributions, except that one method yielded slightly lower values. The spatial distributions varied slightly between methods. In the analysis of the breast cancer study, the odds ratios were insensitive to the method but varied with time: for a 5 ppb increase in NO₂ using the 2006 LUR the odds ratio (OR) was about 1.4 and the ORs in predicted past concentrations of NO₂ varied (OR～1.2 for 1985 and OR～1.3–1.5 for 1996). Thus, the ORs per unit exposure increased with time as the range and variance of the spatial distributions decreased, and this is due partly to the regression coefficient being approximately inversely proportional to the variance of exposure. Changing spatial variability complicates interpretation and this may have important implications for the management of risk. Further studies are needed to estimate the accuracy of the different methods.     

Plant responses to a phytomanaged urban technosol contaminated by trace elements and polycyclic aromatic hydrocarbons

Medicago sativa was cultivated at a former harbor facility near Bordeaux (France) to phytomanage a soil contaminated by trace elements (TE) and polycyclic aromatic hydrocarbons (PAH). In parallel, a biotest with Phaseolus vulgaris was carried out on potted soils from 18 sub-sites to assess their phytotoxicity. Total soil TE and PAH concentrations, TE concentrations in the soil pore water, the foliar ionome of M. sativa (at the end of the first growth season) and of Populus nigra growing in situ, the root and shoot biomass and the foliar ionome of P. vulgaris were determined. Despite high total soil TE, soluble TE concentrations were generally low, mainly due to alkaline soil pH (7.8–8.6). Shoot dry weight (DW) yield and foliar ionome of P. vulgaris did not reflect the soil contamination, but its root DW yield decreased at highest soil TE and/or PAH concentrations. Foliar ionomes of M. sativa and P. nigra growing in situ were generally similar to the ones at uncontaminated sites. M. sativa contributed to bioavailable TE stripping by shoot removal (in g ha^?1 harvest^?1): As 0.9, Cd 0.3, Cr 0.4, Cu 16.1, Ni 2.6, Pb 4, and Zn 134. After 1 year, 72 plant species were identified in the plant community across three subsets: (I) plant community developed on bare soil sowed with M. sativa; (II) plant community developed in unharvested plots dominated by grasses; and (III) plant community developed on unsowed bare soil. The shoot DW yield (in mg ha^?1 harvest^?1) varied from 1.1 (subset I) to 6.9 (subset II). For subset III, the specific richness was the lowest in plots with the highest phytotoxicity for P. vulgaris.     

Pre-hatching fluoxetine-induced neurochemical,neurodevelopmental, and immunological changes in newly hatched cuttlefish

Embryonic and early postembryonic development of the cuttlefish Sepia officinalis (a cephalopod mollusk) occurs in coastal waters, an environment subject to considerable pressure from xenobiotic pollutants such as pharmaceutical residues. Given the role of serotonin in brain development and its interaction with neurodevelopmental functions, this study focused on fluoxetine (FLX), a selective serotonin reuptake inhibitor (SSRI, antidepressant). The goal was to determine the effects of subchronic waterborne FLX exposure (1 and 10 μg L^?1) during the last 15 days of embryonic development on neurochemical, neurodevelopmental, behavioral, and immunological endpoints at hatching. Our results showed for the first time that organic contaminants, such as FLX, could pass through the eggshell during embryonic development, leading to a substantial accumulation of this molecule in hatchlings. We also found that FLX embryonic exposure (1 and 10 μg L^?1) (1) modulated dopaminergic but not serotonergic neurotransmission, (2) decreased cell proliferation in key brain structures for cognitive and visual processing, (3) did not induce a conspicuous change in camouflage quality, and (4) decreased lysozyme activity. In the long term, these alterations observed during a critical period of development may impair complex behaviors of the juvenile cuttlefish and thus lead to a decrease in their survival. Finally, we suggest a different mode of action by FLX between vertebrate and non-vertebrate species and raise questions regarding the vulnerability of early life stages of cuttlefish to the pharmaceutical contamination found in coastal waters.