Dissolved antimony concentrations in contrasted watersheds: the importance of lithogenic origin

A large series of data on dissolved antimony concentrations (900 values) from the hydrological network of Canton Geneva, Switzerland, has been statistically analysed. Data were collected from 90 sampling sites over 12 years. The watercourses surveyed (178 km) accounted for 73% of the total network. Previous studies have classified these rivers as belonging to three clearly-differentiated lithogenic zones: Alps (rivers draining crystalline regions), Jura (rivers draining carbonate-rich zones) and Plain (rivers draining molasses derived from the Alps). Antimony concentrations in the different river waters have been found to be significantly dependent on the geological characteristics of the drainage basins (median values: 0.13, 0.08 and 0.16 microg L(-1) for Alps, Jura and Plain, respectively). For antimony, it is thus possible to define background levels of the element adapted to the lithogenic characteristics for a system of interest. Since establishing background levels is an unavoidable preliminary step in any study aiming to identify and evaluate the various sources of pollution, the behaviour described here has undeniable implications for environmental surveys.     

Using plant biomonitors and flux modelling to develop O3 dose-response relationships in Catalonia

We used tobacco Bel-W3 biomonitoring data and ozone flux modelling (WINDEP model) with the aim of developing the absorbed dose-response relationship, and comparing this approach with the most commonly used AOT40 (the sum of hourly ozone concentrations above a cut-off of 40 ppb during daylight hours, when global radiation exceeds 50 W m(-2)) in the estimation of exposure-damage curves. Leaf damage values were more related to OAD(15 days, potential) (potential ozone absorbed dose calculated over 15 consecutive days) than to AOT40 in all the studied stations. An OAD(15 days, potential) of 180 mg m(-2) was found to be the threshold for damage to the most sensitive species in this region under well watered conditions. The results show the applicability of the flux approach for risk assessment at the local scale, the improvement of the ozone damage estimation when the potential absorbed dose is modelled and used instead of just the ozone exposure, and finally, the possibilities opened by the use of biomonitoring networks.     

Mass scans from a proton transfer mass spectrometry analysis of air over Mediterranean shrubland browsed by horses

Plants usually emit large amount and varieties of volatiles after being damaged by herbivores. However, analytical methods for measuring herbivore-induced volatiles do not normally monitor the whole range of volatiles and the response to large herbivores such as large mammals is much less studied than the response to other herbivores such as insects. In this paper we present the results of using a highly sensitive proton transfer reaction-mass spectrometry (PTR-MS) technique that allows simultaneous monitoring of leaf volatiles in the pptv range. The resulting mass scans in air over Mediterranean shrubland browsed by horses show 70 to 100% higher concentrations of the masses corresponding to mass fragments 57, 43 and 41 (mostly hexenals, acetone and acetic acid) than scans over control non-browsed shrubland. These compounds are biogeochemically active and they are significant components of the volatile organic carbon found in the atmosphere. They influence the performance of living organisms and, the chemical and physical processes of Earth's atmosphere.     

Critical appraisal of available thermodynamic data for the complexation of antimony(III) and antimony(V) by low molecular mass organic ligands

Antimony is an element of increasing environmental significance but one whose chemical speciation has received little attention and, until recently, one which had not been modelled in any comprehensive way. This paper reports thermodynamic data for computer speciation models of antimony in aqueous, multicomponent solutions of environmental and biological interest involving low molecular mass organic ligands. The available data have been critically evaluated and entered into a thermodynamic database. The JESS suite of computer programs has been used to develop the thermodynamically-consistent mass balance equations used for modelling purposes. No data could be found for Sb(V) complexes and only a few of the existing data for Sb(III) complexes can be considered as being reliably described.     

Geochronology of anthropogenic radionuclides in Ribeira Bay sediments, Rio de Janeiro, Brazil

Ribeira Bay is located approximately 130 km south of the city of Rio de Janeiro and receives discharges of liquid effluent from the Angra dos Reis nuclear power plant (NPP) site, where two pressurized water reactors are located. To test whether the presence of anthropogenic radionuclides in sediments in Ribeira Bay could be correlated to the NPP operations, we sampled seven sediment cores and determined accumulation rates and chronologies. Only one sediment core did not exhibit a superficial mixing layer; this sample was used for dating purposes. Cesium-137 and ²⁰⁷Bi were observed in this sediment profile, but their presence was associated with atmospheric fall-out rather than the nearby NPP. The exponential decay of ²¹⁰Pb concentration with sediment layer depth was verified below a superficial mixing layer for all other sediment cores. Calculated accumulation rates ranged from 1.2 mm y⁻¹ in the inner bay to 6.2 mm y⁻¹ close to its entrance.     

Dependence of Ozone Biomonitoring on Meteorological Conditions of Different Sites in Catalonia (N.E. Spain)

Evaluation of visual symptoms of ozone damage was conducted in the network of bioindicator rural stations of Catalonia (NE Spain) every 14 days from May to October. Damage rates of ozone (and consequently, ozone biomonitoring capacity of bioindicators) were found to vary highly in time and space depending on the local environmental and meteorological conditions. Lower ozone damage to foliage was produced when meteorological conditions favour stomata resistance. Modulatory effects of meteorological conditions need to be considered in biomonitoring and when modeling plant ozone doses and damage.     

Freshwaters: which NOM matters?

One of the difficulties encountered in the study of natural organic matter (NOM) in aquatic environments concerns terminology: a large number of different names and acronyms are used. In fact, this diversity merely reflects the variety of approaches applied to the study of NOM, leading to the definition and measurement of different operationally-defined fractions. As a result, the choice of the ‘best’ method to use and of the ‘best’ fraction to work on in a particular case is far from straightforward. This has as a consequence that often very simple methods for NOM characterisation are used in applied environmental studies and surveys. This study includes, first, a review of the most widely applied terminology, as described in over 500 articles, and, second, a first attempt at assessing how the panoply of methods available is really used in applied environmental studies.     

Metal pollution in Spanish terrestrial ecosystems during the twentieth century

We show here additional biological evidence of the alteration in global biogeochemistry by human activities during the twentieth century. The mineral concentration of herbarium specimens of 24 species of vascular plants and three species of bryophytes collected in North and East regions of Spain have substantially changed throughout the twentieth century. While V, a proxy tracer of oil pollution, exponentially increased in the last decades, other metals such as Cr, Ba, Sr, Al, Fe, Pb, Cd and Ti increased up to 1960-1970 and started to decrease in 1985-1995, when environmental legal regulations started to be effective. Multivariate principal component analysis showed an overall change in plant elemental concentrations throughout the different decades of the century and a clear separation of vascular plants and bryophytes. Likely important consequences for ecosystem structure and functioning and even for human health may be expected from these changes in mineral concentration.     

The effect of the presence of trace metals on the oxidation of Sb(III) by hydrogen peroxide in aqueous solution

Despite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(iii) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater.