Adsorption/thermal desorption-GC/MS for the analysis of pesticides in the atmosphere

An analytical methodology using Automatic Thermal Desorption (ATD) and GC/MS was developed for the determination of the pesticides alachlor, atrazine, captan, formothion, lindane and phosalone in atmospheric samples. This methodology was developed to evaluate the atmospheric contamination by pesticides during treatments and by post-application. Atmospheric samples were collected by using (4 i.d. x 89 mm) stainless steel sampling tubes containing 125 mg of adsorbents at a flow rate of 80 ml min-1. Different types of adsorbents were tested for their ability to efficiently trap pesticides under study: Tenax TA, Carbopack Y, Carbopack B, Carbotrap, Carboxen, Chromosorb 106 and XAD-4. Results of experiment show that Tenax gives the better results for all the pesticides used but the use of the thermal-desorption method, especially for pesticides with low volatility and/or poor thermal stability presents some difficulties. This method was validated by the analysis of the contamination of atmosphere, through volatilization by post-application processes, of atrazine in a parcel of 1 ha.     

Transuranium radionuclide pollution in the waters of the La Maddalena National Marine Park

Following the grounding and subsequent explosion, in October 2003, of a nuclear submarine in the waters of the La Maddalena National Marine Park, fears arose of possible radioactive leakages. However, isotopic analyses on algae showed that the gamma-ray emitting artificial radionuclides that one might expect to leak from a damaged nuclear reactor (such as U-235, I-131, Cs-137) were absent, and that U-238/U-234 activities were in equilibrium with values typical of sea water; this excluded any direct anthropogenic contamination as a result of the accident. We used alpha autoradiographic techniques to detect possible traces of transuranium radionuclides; 160 samples of algae, granites, sea urchins, gastropods, limpets, cuttlefish and jellyfish were collected from the area, as well as from other Mediterranean coastlines and the Baltic Sea. All samples were autoradiographed, and selected samples further analysed by alpha spectrometry. There were no alpha track concentrations above background levels in our control Mediterranean specimens. In the samples from the La Maddalena and Baltic areas two different track distributions were observed: --those homogeneously distributed over the surfaces examined; --groups (10 to over 500) of radially distributed alpha tracks (forming "star" bursts, or "hot spots") emanating from point sources. By comparing radionuclide activities measured by alpha spectroscopy with alpha track densities, we extrapolated Pu activities for all samples. About 74% of algae had Pu activities of less than 1 Bq/kg and 0.25 Bq/kg, 16% had accumulated Pu to levels between 1 and 2 Bq/kg, and a very few specimens had concentrations between 2 and 6 Bq/kg. Plots showed that alpha tracks and stars concentrate around the northern and eastern margins of the Rada (Basin) di Santo Stefano, sites facing the nuclear submarine base on the eastern shore of the island of Santo Stefano. What is the source of these nuclides: last century's atmospheric nuclear testing, Chernobyl or a local source? Their concentrated, extremely localised occurrence seems difficult to explain in terms of left-over worldwide nuclear pollution. A local source seems more plausible.     

Aid in the midst of plenty: oil wealth, misery and advocacy in Angola

This paper examines advocacy initiatives by humanitarian and human rights organisations to address problems of governance in resource-rich and conflict-affected countries, focussing on the case of Angola. Humanitarian principles preclude the use of indiscriminate conditionality and point towards a cautious approach to advocacy aimed at assisting vulnerable populations. Furthermore, the relatively insignificant amount of aid supplied to resource-rich local authorities means that individual agencies have precious little leverage, especially when commercial interests rather than humanitarian or 'good governance' principles influence the priorities of bilateral donors. A context of resource wealth calls for: high levels of coordination and cooperation between human rights groups, aid agencies and donors; balanced use of conditionality, based on the drawing, by donors, of a clear distinction between emergency and development-oriented assistance; and a sustained effort to highlight the responsibilities of local authorities, foreign governments and businesses in meeting humanitarian and development objectives.     

Uranium-thorium disequilibrium in north-east Atlantic waters

In this paper we report and compare the concentrations of 234Th and 238U measured in surface and subsurface waters collected in the course of a sampling campaign in the north east Atlantic in June-July 1998. Dissolved 234Th concentrations in surface waters ranged from 5 to 20 Bq m(-3), showing a large deficiency relative to 238U concentrations (typically 42 Bq m-3). This disequilibrium is indicative of active 234Th scavenging from surface waters. Observed 234Th/238U activity ratios, together with corresponding 234Th particulate concentrations, were used to calculate mean residence times for 234Th with respect to scavenging onto particles (tau(diss)) and subsequent removal from surface waters (tau(part)). Residence times in the range 5-30 days were determined for tau(diss) and 4-18 days for tau(part) (n=14). In addition, ultrafiltration experiments at six stations in the course of the same expedition revealed that in north-east Atlantic surface waters a significant fraction (46+/-17%; n=6) of the thorium in the (operationally-defined) dissolved phase (<0.45 microm) is in colloidal form. These observations are consistent with the 'colloidal pumping' model in which it is assumed that 234Th is rapidly absorbed by colloidal particles, which then aggregate, albeit at a slower rate, into larger filterable particles. In essence, colloids act as intermediaries in the transition from the fully dissolved to the filter-retained (>0.45 microm) phase. Thus, the time (tau(c)) for fully dissolved 234Th to appear in the filter-retained fraction is dependent on the rate of colloidal aggregation. Here, we determined tau(c) values in the range 3-17 days.     

Lifetime and intergenerational fitness consequences of harmful male interactions for female lizards

Male mating behaviors harmful to females have been described in a wide range of species. However, the direct and indirect fitness consequences of harmful male behaviors have been rarely quantified for females and their offspring, especially for long-lived organisms under natural conditions. Here, lifetime and intergenerational consequences of harmful male interactions were investigated in female common lizards (Lacerta vivipara) using field experiments. We exposed females to male harm by changing the population sex ratio from a normal female-biased to an experimental male-biased sex ratio during the first experimental year. Thereafter, females and their first generation of offspring were monitored during two additional years in a common garden with a female-biased sex ratio. We found strong immediate fitness costs and lower lifetime reproductive success in females subjected to increased male exposure. The immediate fitness costs were partly mitigated by direct compensatory responses after exposure to male excess, but not by indirect benefits through offspring growth, offspring survival, or mating success of offspring. These results support recent empirical findings showing that the direct costs of mating are not outweighed by indirect benefits.     

Territory ownership and familiarity status affect how much male root voles (Microtus oeconomus) invest in territory defence

Neighbour–stranger discrimination occurs when individuals respond with more aggression to strangers than to territorial neighbours—a phenomenon termed the “dear enemy phenomenon” (DEP). We investigated the DEP with male and female root voles (Microtus oeconomus Pallas 1776) using field dyadic arena tests conducted in enclosures where we could test for the effects of familiarity (familiar versus stranger), ownership (resident versus intruder status) and resource-holding potential (body mass) on territorial behaviours. The results showed that males put more effort into territorial defence than females, and males could discriminate between neighbours and strangers. In males, aggressiveness was influenced by a significant two-way interaction between treatment and ownership. Male residents were more aggressive towards stranger intruders than towards neighbour intruders, while male intruders were less aggressive towards stranger residents than towards neighbour residents. In females, neither treatment nor ownership status had a significant effect on aggressiveness. Familiar males performed more social behaviours but less non-social behaviours than stranger males. Furthermore, there was a clear dominance hierarchy between residents and intruders in stranger dyads, with the male territory holders dominating the intruder in pairwise interactions. To our knowledge, these results demonstrate for the first time DEP in a small mammal with a known pedigree and present the first evidence for “prior resident advantage” in voles. We argue that both ownership status and familiarity status affect how much an individual invests in territory defence. The benefits of neighbour–stranger discrimination for male root voles and the absence of neighbour–stranger discrimination in female root voles are discussed.     

Designing environmental monitoring networks to measure extremes

This paper discusses challenges arising in the design of networks for monitoring extreme values over the domain of a random environmental space-time field {X _ij } i = 1, . . . , I denoting site and j = 1, . . . denoting time (e.g. hour). The field of extremes for time span r over site domain i = 1, . . . ,I is given by \(\{Y_{i(r+1)}=\max_{j=k}^{k+n-1} X_{ij}\}\) for k = 1 + rn, r = 0, . . . ,. Such networks must not only measure extremes at the monitored sites but also enable their prediction at the non-monitored ones. Designing such a network poses special challenges that do not seem to have been generally recognized. One of these problems is the loss of spatial dependence between site responses in going from the environmental process to the field of extremes it generates. In particular we show empirically that the intersite covariance Cov(Y _i(r+1),Y _i′(r+1)) can generally decline toward zero as r increases, for site pairs i ≠ i′. Thus the measured extreme values may not predict the unmeasured ones very precisely. Consequently high levels of pollution exposure of a sensitive group (e.g. school children) located between monitored sites may be overlooked. This potential deficiency raises concerns about the adequacy of air pollution monitoring networks whose primary role is the detection of noncompliance with air quality standards based on extremes designed to protect human health. The need to monitor for noncompliance and thereby protect human health, points to other issues. How well do networks designed to monitor the field monitor their fields of extremes? What criterion should be used to select prospective monitoring sites when setting up or adding to a network? As the paper demonstrates by assessing an existing network, the answer to the first question is not well, at least in the case considered. To the second, the paper suggests a variety of plausible answers but shows through a simulation study, that they can lead to different optimum designs. The paper offers an approach that circumvents the dilemma posed by the answer to the second question. That approach models the field of extremes (suitably transformed) by a multivariate Gaussian-Inverse Wishart hierarchical Bayesian distribution. The adequacy of this model is empirically assessed in an application by finding the relative coverage frequency of the predictive credibility ellipsoid implied by its posterior distribution. The favorable results obtained suggest this posterior adequately describes that (transformed) field. Hence it can form the basis for designing an appropriate network. Its use is demonstrated by a hypothetical extension of an existing monitoring network. That foundation in turn enables a network to be designed of sufficient density (relative to cost) to serve its regulatory purpose.