Statistical evaluation of chronic toxicity data on aquatic organisms for the hazard identification: the chemicals toxicity distribution approach

Presently, in the Globally Harmonised System of Classification and Labelling of Chemicals the classification of substances for long-term effects to aquatic life is based on acute toxicity in combination with degradation and/or bioaccumulation potential. Recently an OECD Working Group was created to develop the classification scheme to accommodate chronic toxicity data related to aquatic organisms for assigning a chronic hazard category. This study focuses on a new approach for setting chronic toxicity cut-off values based on Chemicals Toxicity Distributions (CTDs). A CTD is obtained through statistical fitting of the data used by regulatory bodies for setting hazard-based classifications. The CTDs were made using the lowest aquatic NOEC value of each chemical. A review of different toxicological sources reporting acute aquatic toxicities was carried out. Initially, the data were arranged according to the specific source and distributions for key taxonomic groups (i.e. fishes, crustaceans and algae) were evaluated separately. In most cases, no significant departures from normality were observed. Thereafter, a compiled database containing >900 values was developed and the CTDs were constructed for each taxonomic group. Significant deviation from normality (P < 0.05) was observed in the fishes and crustaceans' CTDs. However, this deviation was apparently produced by the presence of only seven values with NOECs <1 x 10(-5) mg l(-1), while high correlation between the data and the normal scores (r-values>or= 0.989) indicated that the data were samples from normal distributions. From these observations, potential cut-off values would allow quantitative estimations of the percentage of chemicals falling into each specific category. This approach results in a simple classification hazard scheme where most chemicals are covered in one of the categories, allowing a clear distribution of the chemicals among three categories for chronic toxicity.     

Enantiomeric fractions and congener specific determination of polychlorinated biphenyls in eggs of predatory birds from Doñana National Park (Spain)

The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Do?ana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 microg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 microg/g f.w.) and booted eagle (0.10-1.5 microg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 microg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF not = 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values.     

Heavy metals and organic carbon in sediments from the Tuy River basin,Venezuela

The Tuy River basin, located in north-central Venezuela with an annual average temperature of 27°C and precipitation of 140 cm, was selected to conduct a geochemical study of bottom sediments, with the object of establishing the natural and human influences in the abundance and distribution of Fe, Mn, Cr, Co, Cu, Ni, Pb, Zn and organic carbon. The basin is lithologically divided into two sub-basins, north and south. The north sub-basin drains a iow-grade metasedimentary terrain with a population density of 800 persons km^–2 and approximateiy 600 industrial sites, while the south sub-basin in underlain by metavolcanic and ultramafic rocks, with a population density of less than 10 persons km^–2.Stream bottom sediment samples (150) were collected during the years of 1979–1986 in 16 unpolluted sites and 13 polluted sites. The sediments were air dried at room temperature and sieved through a 120 stainless steel mesh (125 m). Samples of grain size smaller than 125 m were analysed, the heavy metals being determined by atomic absorption spectrometry and the organic carbon (Corg) by dry combustion.The higher concentrations of heavy metals and organic carbon found in the pristine areas were in the south sub-basin, especially in those areas with higher annual precipitation and tropical forest. This indicated that the metavolcanic and ultramafic rocks yield higher concentrations of heavy metals than the metasedimentary rocks. It was also noted that the higher concentrations of Cr and Ni are associated with the ultramafic rocks. The results obtained from the sediment samples collected in the polluted sites showed that the elements Pb, Zn and Corg are enriched up to 4 times as a result of ail the human activities taking place in the basin. Organic carbon is an excellent indicator of domestic wastewater, Pb and Zn are good indicators of the automotive traffic and industrial effluents. The concentrations of each heavy metal did not show any significant correlation with grain size fractions; however, the concentration of organic carbon did show a negative correlation with grain size. The lithological, climatic and vegetation influence in the abundance of heavy metals and organic carbon in stream sediments clearly indicates the necessity of establishing background levels for the area under study when carrying out studies in environmental geochemistry.     

Lévy walk patterns in the foraging movements of spider monkeys (<Emphasis Type="Italic">Ateles geoffroyi</Emphasis>)

Scale invariant patterns have been found in different biological systems, in many cases resembling what physicists have found in other, nonbiological systems. Here we describe the foraging patterns of free-ranging spider monkeys (Ateles geoffroyi) in the forest of the Yucatan Peninsula, Mexico and find that these patterns closely resemble what physicists know as Lévy walks. First, the length of a trajectorys constituent steps, or continuous moves in the same direction, is best described by a power-law distribution in which the frequency of ever larger steps decreases as a negative power function of their length. The rate of this decrease is very close to that predicted by a previous analytical Lévy walk model to be an optimal strategy to search for scarce resources distributed at random. Second, the frequency distribution of the duration of stops or waiting times also approximates to a power-law function. Finally, the mean square displacement during the monkeys first foraging trip increases more rapidly than would be expected from a random walk with constant step length, but within the range predicted for Lévy walks. In view of these results, we analyze the different exponents characterizing the trajectories described by females and males, and by monkeys on their own and when part of a subgroup. We discuss the origin of these patterns and their implications for the foraging ecology of spider monkeys.Communicated by D. Watts     

Chemical ornaments of male lizards <Emphasis Type="Italic">Psammodromus algirus</Emphasis> may reveal their parasite load and health state to females

Evidence for parasite-mediated sexual selection has been found in many species that use visual ornaments to attract females. However, in many animals, variation in female responses to scents of parasitized males suggests that parasitic infections might also affect information conveyed by pheromones (i.e., chemical ornaments). Thus, pheromones might also function in parasite-mediated sexual selection. We show here that female lizards Psammodromus algirus responded differently to femoral gland secretions of males according to the parasite load and health of these males. Scents of healthier males elicited more tongue flicks (a chemosensory behavior) by females, suggesting that these scents were more attractive. Chemical analyses showed that parasite load and the T-cell-mediated immune response were related to the variability in the proportions of some lipids in secretions of males. Further trials testing the chemosensory responses of females to chemical standards indicated that females actually discriminated the chemicals related to males’ health from other chemicals found in secretions. We suggest that these chemical ornaments may provide reliable information on the health and degree of parasitic infection of a male.     

Fly ash content and distribution in lake sediments around a large power station: inferences from magnetic susceptibility analysis

The bulk magnetic susceptibility of sediments from artificial and natural lakes around a large coal-fired power station in NE Spain has been measured. Higher magnetic susceptibility values are found in lake sediments located SE of the power station. This distribution of susceptibility values is compatible with environmental and meterological studies of emissions from the power station, which indicate a dominant SE plume direction. Mineralogical studies, by means of X-ray diffraction and scanning electron microscopy, show that the highest susceptibility values found in the sediments are caused by magnetic iron spinels in the fly ash that is transferred to the environment by the power station particulate emissions. After the quantitative mineralogical studies of fly ash, two different methods of fly ash content determination in the sediments have been devised, showing very similar results. The low background magnetic susceptibility of the sediments in the study area and the high susceptibility resulting from the input of magnetic fly ash particles allows both delimitation of the polluted area around the power station, and quantification of the fly ash input into the natural sediments.     

Sequestration of pyrrolizidine alkaloids by larvae ofTellervo zoilus (Lepidoptera: Ithomiinae) and their role in the chemical protection of adults against the spiderNephila maculata (Araneidae)

Summary Life stages of the primitive Australian ithomiine butterflyTellervo zoilus and its larval hostplant, the apocynaceous vineParsonsia straminea, were quantitatively assayed for pyrrolizidine alkaloids (PAs). PAs were found in all stages, mainly as N-oxides, being most concentrated in larvae and freshly-emerged adults. Although adults feed at various confirmed PA sources this probably does not compensate for losses, as wild-caught adults had considerably lower concentrations of PAs. The main alkaloid present in both freshly-emerged adults and in leaves of the host-plant was lycopsamine (1b), stored by butterflies in the N-oxide form. Its presence in higher proportion, in relation to intermedine (1a), in larvae, pupae and adults ofTellervo in relation to the host-plants suggests the inversion of intermedine to lycopsamine by the insects. No 14-member ring macrocyclic PAs were detected in either food-plant or butterflies. Several other PAs were found in wild-caught adults reflecting visits to other PA sources. PAs were also found in high concentrations in freshly-emerged individuals of the danaineEuploea core bred onParsonsia straminea. Wild-caughtDanaus affinis had high PA levels acquired from adult feeding. Freshly emergedEuploea raised onIschnocarpus frutescens andDanaus raised onIschnostemma carnosum (both PA-free) were preyed on by the orb weaving spiderNephila maculata, and showed no PAs. In all cases where PAs were present, most butterflies were liberated, usually cut out of the web unharmed, byNephila. The spider's response was not closely linked to PA concentration, however, and may also depend on hunger levels and previous experience with PA-containing butterflies. All control and other non-PA containing butterflies were consumed although rejection of some body parts of freshly-emergedDanaus affinis suggests that compounds other than PAs may be involved.     

Comparing aquatic risk assessment methods for the photosynthesis-inhibiting herbicides metribuzin and metamitron

Three different risk assessment procedures are described that aim to protect freshwater habitats from risks of the photosynthesis-inhibiting herbicides metribuzin and metamitron. These procedures are (1) the first-tier approach, based on standard toxicity tests and the application of an assessment factor, (2) the Species Sensitivity Distribution (SSD) approach, based on laboratory tests with a wider array of species and the application of a statistical model to calculate the HCx (the Hazardous Concentration for x% of the species), and (3) the model ecosystem approach, based on the evaluation of treatment-related effects in field enclosures. A comparison of the risk assessment procedures reveals that the first-tier approach is the most conservative for metamitron and metribuzin, and that HC5 values (and even HC10 values) based on acute EC50 values of algae and aquatic vascular plants may be used to derive maximum permissible concentrations for single applications. For both compounds these HC5 values were very similar to the ecological threshold concentrations in the enclosure studies. In contrast to model ecosystem experiments, however, HCx values based on lab toxicity tests do not provide information on the recovery potential of sensitive endpoints and on indirect effects, which may be important for regulatory decision-making. In the enclosure study, indirect effects of metribuzin on invertebrate populations were observed at an exposure concentration that was approximately 20 times lower than the corresponding HC5 value based on lab toxicity data for aquatic invertebrates.     

Inclusion complexes of alpha- and gamma-cyclodextrins and the herbicide norflurazon: I. Preparation and characterisation. II. Enhanced solubilisation and removal from soils

The interaction of norflurazon with alpha- and gamma-cyclodextrins (CDs) yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution and in the solid state. Apparent stability constants of 50.7+/-1.6 and 37+/-1.7 M(-1) and an increase in herbicide solubility by up to five and fourfold for alpha- and gamma-CD, respectively, were determined from the phase solubility diagrams at 25 degrees C in water. Three processing methods (kneading, spray-drying and vacuum evaporation) were used to prepare norflurazon-CD solid inclusion complexes, which were characterised by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. A high increase in the norflurazon dissolution rate was obtained with all the solid complexes with gamma-CD, but when alpha-CD was used, only the solid system obtained after the vacuum evaporation process showed a higher dissolution rate. This finding is a first step in the development of new, environmentally sound formulations of norflurazon (NFL), due to the capacity for increasing its dissolution rate and hydrosolubility, and thus diminishing the use of organic solvents. On the other hand, the effect of alpha- and gamma-cyclodextrin on the solubility of norflurazon in solution was also considered as a way of modifying its behaviour in the soil environment. Desorption studies of NFL from soils in the presence of alpha- and gamma-cyclodextrin were carried out using a batch equilibration method. The results obtained showed that alpha- and gamma-cyclodextrin greatly increased the removal of norflurazon previously adsorbed, proving the potential use of these CDs for in situ remediation of pesticide-contaminated soils.