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.     

Lateral migration and offsite surface emission of landfill gas at City of Montreal Landfill Site

An evaluation of lateral landfill gas migration was carried out at the Saint-Michel Environmental Complex in Montreal, City of Montreal Landfill Site, Canada, between 2003 and 2005. Biogas concentration measurements and gas-pumping tests were conducted in multilevel wells installed in the backfilled overburden beside the landfill site. A migration event recorded in autumn 2004 during the maintenance shutdown of the extraction system was simulated using TOUGH-LGM software. Eleven high-density instantaneous surface monitoring (ISM) surveys of methane were conducted on the test site. Gas fluxes were calculated by geostatistical analyses of ISM data correlated to dynamic flux chamber measurements. Variograms using normal transformed data showed good structure, and kriged estimates were much better than inverse distance weighting, due to highly skewed data. Measurement-based estimates of yearly off-site surface emissions were two orders of magnitude higher than modelled advective lateral methane flux. Nucleodensimeter measurements of the porosity were abnormally high, indicating that the backfill was poorly compacted. Kriged porosity maps correlated well with emission maps and areas with vegetation damage. Pumping tests analysis revealed that vertical permeability was higher than radial permeability. All results suggest that most of the lateral migration and consequent emissions to the atmosphere were due to the existence of preferential flow paths through macropores. In December 2006, two passively vented trenches were constructed on the test site. They were successful in countering lateral migration.     

Deficit analysis: service capacity assessment and planning in developing countries – case study in the Philippines

Current demand analysis methods do not formally cover the case of chronic deficits in quantity or quality of water and sanitation services. These services include drinking water supply (DWS), wastewater and sewage treatment (WST), and municipal solid waste management (MSW). Formal analysis of this case would, at minimum, define the deficit state and evaluate appropriate options for reducing it. This paper proposes for a formal analytical model for municipal sanitation systems (MSS) that operate with deficits in at least one of the constituent services of DWS, WST, or MSW. The model introduces definitions and notation for describing the deficit state for conducting demand analysis on municipal sanitation systems. This model of demand analysis for systems with chronic deficits will hereinafter be referred to as deficit analysis. A case study for Bacoor, Philippines is presented as an example.     

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.     

RESEARCH: Shrub Propagation Techniques for Biological Control of Invading Tree Species

Cornus stolonifera, Salix petiolaris, and Spiraea alba clones already located within the corridor of an electrical power line. To establish the efficiency of treatments, we examined the statistical differences of growth traits between species and treatments. An analysis of the effects of layering shows, after the first growth season, differences for all growth traits in only one species, Spiraea alba. After the second growth season, we observed the development of new aerial stems. Layering favors horizontal expansion of shrubs over height development. The third year after treatment, the effect of layering is reduced except for Cornus stolonifera, which continuously increases, as shown by the significant progression of the clone issued from the layer even five years after treatments. With the cutting back technique, we expected a distinct vertical growth of the shrubs at the expense of increasing the crown diameter. This technique would be best associated with the rejuvenation of clones, followed by a layering of new shoots to allow a horizontal expansion of the shrubs. Therefore, the formation of a dense shrub community by layering should be considered a valuable approach for the biological control of undesirable trees in powerline rights-of-way.     

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).     

Importance of eating habits and sample size in the estimation of environmental mercury contamination using biological indicators

The importance of eating habits and the number of fish sampled in the estimation of mercury environmental contamination through biological indicators was studied. The species used were one with piscivorous habits (Anguilla anguilla) and another with omnivorous habits (Ciprinus carpio). From one original sample for each species, randomized samples were generated using the subroutine GGSRS from the mathematics library IMSL, and later the statistical significance of Pearson's correlation coefficient for the relationship between fish weight and mercury concentrations in muscle was obtained for each random sample. The results show that the use of omnivorous species such as Ciprinus carpio as a biological indicator of contamination enables us to carry out estimations with a greater degree of confidence than when piscivorous species such as Anguilla anguilla are used.     

Processes involved in uptake and release of nitrogen dioxide from soil and building stones into the atmosphere

Atmospheric NO₂ was taken up by samples of various soils and building stones. The NO₂ uptake rate constants were highest in soil samples taken during the summer months. However, the NO₂ uptake rate constants of the soils and building stones were not significantly correlated with any of the following variables: moisture, pH, ammonium, nitrite, or nitrate. NO₂ uptake by soil and stone was not abolished by autoclaving indicating a chemical uptake process. NO₂ uptake by acidic and air-dry soils and stones resulted in nearly stoichiometric reduction of NO₂ to NO. This reduction was enhanced by the addition of ferrous iron and was further enhanced by incubation under 1 ppmv SO₂. The results suggest that NO₂ reduction may be coupled to oxidation of ferrous to ferric iron which may be reduced again by atmospheric SO₂ thus regenerating the ferrous iron content of the soil or stone. Conversion of NO₂ to NO was not observed in neutral or/and moist soils and stones. NO₂ was also taken up by purified and sterilized quartz sand moistend with water. This uptake was enhanced by addition of humic material but not by addition of bacteria which both had been extracted from genuine soil. Under most conditions, only uptake but no release of NO₂ was observed. However, NO₂ was released in air-dry soils that were heated to 45–65°C, or in ammonium-fertilized soil or stone that was drying up at room temperature. Under the latter conditions mimicking field practice, the NO₂ release reached rates that were similar to the NO release rates.