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.     

Carbon monoxide from composting due to thermal oxidation of biomass

Emissions of carbon monoxide (CO) were observed from decomposing organic wastes and litter under laboratory, pilot composting plant, and natural conditions. Field studies included air from inside a compost heap of about 200 m3, emissions from composting of livestock wastes at a biologically operating farm, and leaf litter pile air samples. The concentration of CO was up to 120 micromol mol(-1) in the compost piles of green waste, and up to 10 micromol mol(-1) in flux chambers above livestock waste windrow composts. The mean CO flux rates were approximately 20 mg CO m(-2) h(-1) for compost heaps of green waste, and varied from 30 to 100 mg CO m(-2) h(-1) for fresh dung windrows. Laboratory studies using a temperature and ventilation-controlled substrate container were performed to elucidate the origin of CO, and included hay samples of fixed moisture content at temperatures between 5 and 65 degrees C, including nonsterilized as well as sterilized samples. The concentration of CO was up to 160 micromol mol(-1) in these experiments, and Arrhenius-type plot analyses resulted in activation energies of 65 kJ mol(-1) for thermochemically produced CO from the nonsterilized compost substrate. Sterilized samples showed dramatically reduced CO2 but virtually unchanged CO emissions, albeit at a slightly lower activation energy, likely a result of the high-temperature sterilization. Though globally and regionally these CO emissions are only a minor source, thermochemically produced CO emissions might affect local air quality in and near composting facilities.     

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.     

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.     

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.     

Biodegradation of crosslinked acrylic polymers by a white-rot fungus

Two synthetic superabsorbent crosslinked acrylic polymers were mineralized by the white-rot fungusPhanerochaete chrysosporium. The amount of polymer converted to CO₂ increased as the amount of polymer added to the cultures increased. In the presence of sufficiently large amounts of the superabsorbents, such that all of the culture fluid was absorbed and a gelatinous matrix was formed, the fungus still grew and mineralization was observed. Neither the polymers, nor their degradation products were toxic to the fungus. While the rates of mineralization were low, all of the polymers incubated in the liquid fungal cultures were completely depolymerized to water soluble products within 15–18 days. The depolymerization of the polymers was observed only in nitrogen limited cultures of the fungus which secrete the lignin degradation system, however, the water soluble products of depolymerization were mineralized in both nutrient limited and sufficient cultures of the fungus. The rate of mineralization of the depolymerized metabolites was more than two times greater in nutrient sufficient cultures. Following longer incubation periods, most (> 80 %) of the radioactivity was recovered in the fungal mycelial mat suggesting that carbon of the polymer had been converted to fungal metabolites.     

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.