Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.     

Soil and vegetation carbon stocks in Brazilian Western Amazonia: relationships and ecological implications for natural landscapes

The relationships between soils attributes, soil carbon stocks and vegetation carbon stocks are poorly know in Amazonia, even at regional scale. In this paper, we used the large and reliable soil database from Western Amazonia obtained from the RADAMBRASIL project and recent estimates of vegetation biomass to investigate some environmental relationships, quantifying C stocks of intact ecosystem in Western Amazonia. The results allowed separating the western Amazonia into 6 sectors, called pedo-zones: Roraima, Rio Negro Basin, Tertiary Plateaux of the Amazon, Javari-Juruá-Purus lowland, Acre Basin and Rondonia uplands. The highest C stock for the whole soil is observed in the Acre and in the Rio Negro sectors. In the former, this is due to the high nutrient status and high clay activity, whereas in the latter, it is attributed to a downward carbon movement attributed to widespread podzolization and arenization, forming spodic horizons. The youthful nature of shallow soils of the Javari-Juruá-Purus lowlands, associated with high Al, results in a high phytomass C/soil C ratio. A similar trend was observed for the shallow soils from the Roraima and Rondonia highlands. A consistent east–west decline in biomass carbon in the Rio Negro Basin sector is associated with increasing rainfall and higher sand amounts. It is related to lesser C protection and greater C loss of sandy soils, subjected to active chemical leaching and widespread podzolization. Also, these soils possess lower cation exchangeable capacity and lower water retention capacity. Zones where deeply weathered Latosols dominate have a overall pattern of high C sequestration, and greater than the shallower soils from the upper Amazon, west of Madeira and Negro rivers. This was attributed to deeper incorporation of carbon in these clayey and highly pedo-bioturbated soils. The results highlight the urgent need for refining soil data at an appropriate scale for C stocks calculations purposes in Amazonia. There is a risk of misinterpreting C stocks in Amazonia when such great pedological variability is not taken into account.     

Pesticide Residues in Bovine Milk from a Predominantly Agricultural State of Haryana, India

One hundred forty seven samples of bovine milk were collected from 14 districts of Haryana, India during December 1998–February 1999 and analysed for the presence of organochlorine pesticide (OCPs) residues. ∑HCH, ∑DDT, ∑endosulfan and aldrin were detected in 100%, 97%, 43% and 12% samples and with mean values of 0.0292, 0.0367, 0.0022 and 0.0036 μg/ml, respectively. Eight percent samples exceeded the maximum residue limit (MRL) of 0.10 mg/kg as recommended by WHO for ∑HCH, 4% samples of 0.05 mg/kg for α-HCH, 5% samples of 0.01 mg/kg for γ-HCH, 26% samples of 0.02 mg/kg for β-HCH as recommended by PFAA and 24% samples of 0.05 mg/kg as recommended by FAO for ∑DDT. Concentrations of β-HCH and p,p′-DDE were more as compared to other isomers and metabolites of HCH and DDT.     

Canopy Spectra and Remote Sensing of Ashe Juniper and Associated Vegetation

A study was conducted in central Texas to determine the potential of using remote sensing technology to distinguish Ashe juniper (Juniperus ashei Buchholz) infestations on rangelands. Plant canopy reflectance measurements showed that Ashe juniper had lower near-infrared reflectance than other associated woody plant species and lower visible reflectance than mixed herbaceous species in spring and summer. Ashe juniper could be distinguished on color-infrared aerial photographs acquired in March, April, June, and August and on QuickBird false color satellite imagery obtained in June, where it had a distinct dark reddish-brown tonal response. Unsupervised classification techniques were used to classify aerial photographic and satellite imagery of study sites. An accuracy assessment performed on a computer classified map of a photographic image showed that Ashe juniper had producer's and user's accuracies of 100% and 92.9%, respectively, whereas an accuracy assessment performed on a classified map of a satellite image of the same site showed that Ashe juniper had producer's and user's accuracies of 94.1% and 88.1%, respectively. Accuracy assessments performed on classified maps of satellite images of two additional study sites showed that Ashe juniper had producer's and user's accuracies that ranged from 87.1% to 96.4%. These results indicate that both color-infrared photography and false color satellite imagery can be used successfully for distinguishing Ashe juniper infestations.     

Rapid growth of clones of the red alga Chondrus crispus: applications in assays of toxic substances and in physiological studies

Growth rates of excised apical segments from three Chondrus crispus Stackhouse clones were rapid, reproducible and easily measured using simple equipment. Clonal segments exhibited a high degree of phenotypic stability, with coefficients of variation in growth rates being typically less than 5%. Sensitivity of the assay was demonstrated using 24-h pulses of the toxicants Cu²⁺ (10 to 150 ppb) and the molluscicide Bayluscide (100 to 500 ppb). As a further demonstration of applicability of this assay system, growth rates were measured over two consecutive 24-h photoperiods using a normally pigmented red gametophytic clone and a green colored mutant derived from it. Growth rates were highest in the first hours of the light phase for both clones, with growth of the green mutant being consistently inferior to that of the normally pigmented one. Significant changes were measured with intervals as short as 4 h using only five apical segments for each treatment. The C. crispus assay described is sensitive, relatively rapid, and statistically robust when applied to toxicant testing in seawater and to physiological studies.     

Stability of a Coal Waste Artificial Reef

The feasibility of using U.K. coal-fired power station waste materials for artificial reef production is being examined. in June, 1989, an experimental artificial reef was constructed in Poole Bay, off the central south coast of the U.K., using three different mixtures of pulverised fuel ash (PFA), flue gas desulphurisation (FGD) gypsum and slurry, stabilized with cement and formed into blocks. Fifty tonnes of 40 × 20 × 20 cm blocks were formed into eight conical reef units replicating three different PFA/gypsum mixtures and one concrete control. the reef structure is 10m below chart datum on a flat sandy sea-bed.

Combustion of coal concentrates the heavy metal content in the resultant ash. the purpose of stabilization of the ash as blocks is twofold: to immobilize heavy metals (or other components) and to provide hard substratum for the attachment of organisms. to examine the effectiveness of this stabilization and hence the environmental compatibility of the block materials, heavy metal (Cd, Cr, Cu, Pb, Mn, Ni, Zn) content of the blocks has been monitored routinely over two years, to determine leaching rates. Sectional profiles indicate partial replacement of calcium content by magnesium. Associated with this there has also been some redistribution of heavy metals. Only in the case of cadmium has there been a detectable loss from the surface of blocks. Chromium and manganese concentrations appear to have increased. the metal content of the reef epibiota (including ascidians, Ascidia mentula; hydroids, Halecium spp.; bryozoans, Bugula spp. and red algae) growing on the ash blocks has been compared to that of epibiota attached to the concrete controls and surrounding sea-bed. to date no evidence of excess bioaccumulation of metals has been detected.

The physical integrity of the ash reef blocks has been maintained. There is evidence that the blocks are increasing in compressive strength.

An indication of the fishery enhancement potential of the experimental structure is given by the presence of eight commercially fished species (crustaceans and molluscs) including lobsters (Homarus gammarus).     

The gill symbiont of the hydrothermal vent mussel Bathymodiolus thermophilus is a psychrophilic,chemoautotrophic, sulfur bacterium

Certain hydrothermal vent invertebrates, e.g. Riftia pachyptila and Calyptogena magnifica, are clearly established as harboring dense populations of chemoautotrophic sulfur bacteria in specialized tissues. By contrast, the physiological characteristics of the abundant intracellular gill symbiont of the vent mussel Bathymodiolus thermophilus have been questioned. The low activities of enzymes diagnostic for CO₂ fixation (Calvin cycle) and for sulfur-driven energy generation, as measured by other investigators, have been attributed to bacterial contamination of the gill surface. Based on research at the Galápagos Rift hydrothermal vents in 1988 and subsequent laboratory experiments, the current study confirms that the B. thermophilus symbiont is a psychrophile for which thiosulfate and sulfide stimulate CO₂ fixation. It strongly indicates that the symbiont is a chemoautotroph by establishing the following: (1) Sulfide and thiosulfate can stimulate CO₂ fixation by partially purified symbionts by up to 43-fold and 120-fold, respectively; (2) the ribulose-1,5-bisphosphate carboxylase/oxygenase activity of the symbiont is sufficient to account for its sulfide- or thiosulfate-stimulated CO₂ incorporation; (3) the symbiont's molar growth yield on thiosulfate, as judged by CO₂ incorporation, is indistinguishable from that of free-living chemoautotrophs. Due to the high protein-degrading activity of B. thermophilus gill lysate, it is also suggested that host lysis of symbionts plays a more important role in the nutrition of the vent mussel than in R. pachyptila or C. magnifica, for which no comparable protein-degrading activity was found.     

Is sex-biased maternal care limited by total maternal expenditure in polygynous ungulates?

We examined data on sex-specific differences in neonatal weight, litter size and adult female body weight in 32 populations of polygynous ungulates of 18 different species to test for the existence of a trade-off between sex-biased maternal care and the total amount of maternal expenditure. This corresponds to an extension of the hypothesis of Byers and Moodie (1990) that sex-biased maternal care is limited by a high level of maternal expenditure. We did not find any relationship between sex-biased care and two measures of total maternal expenditure. We highlighted high intraspecific variability in sex-biased care and very low intraspecific variability in total maternal expenditure. Even when this between-population variability in sex-biased care was accounted for, no relationship between sex-biased maternal care and maternal expenditure was detected. Apart from difficulties in finding suitable measures for both variables, two other reasons may account for the lack of a relationship between sex-biased maternal care and total maternal expenditure. Firstly, male offspring seem to be more affected than female offspring by harsh environmental conditions. This may lead to the variation observed in the extent of sex-specific differences in birth weight within a single species. If we assume that for a given maternal expenditure reproductive costs incurred by mothers are highest during harsh conditions, this could indicate the existence of a trade-off between sex-biased maternal care and maternal expenditure at the intra-specific level, thereby supporting the Byers and Moodie hypothesis. Secondly, polygyny is only a poor predictor of sex-biased care and factors such as compensatory growth or extended periods of growth may be expected to modify predictions for different species. Thus, environmental conditions and relative effects of maternal care on male and female lifetime reproductive success are better predictors of sex-biased care than total maternal expenditure.Communicated by P.M. Kappeler