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.     

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.     

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).     

Mikrobielle Sanierung von 2,4,6-Trinitrotoluol (TNT) kontaminierten Böden

Within the limits of a feasability study abouton-site bioremediation methods for TNT-contaminated soils, composting was chosen as a very promising and cheap method. This method was critically compared with those described in the literature and was primarily rated under ecotoxicological aspects. The investigated location is the former munition plant «Tanne» in the aerea of Clausthal-Zellerfeld in Lower Saxony, Germany. To estimate the autochtonic microflora, we assessed the number of aerobic heterotrophic bacteria and determined their respiration activity in soils. In addition, we isolated bacteria and examined their capacity to metabolize TNTin vitro. Both the amount of autochtonic microrganisms (4.7×10⁸ to 1.2×10¹⁰ colony forming units (cfu)/kg dryweight) as well as their respiration activity did not correlate with the concentrations of nitrotoluenes in the soils. With high contaminated soil (20 g TNT/kg dry weight) we carried out a small compost in the range of 10 liters. During 28 days of composting TNT-concentration decrease over 90% and only minor amounts of monoaminodinitrotoluenes were generated. However, an acidic pretreatment of the compost material at the end of the reaction showed that TNT could be partially resolved under these extreme conditions and that an ecotoxicological risk may still exist. Possible changes in the realization of the composting process in order to make sure that the contaminants are savely bound to the humin matrix are discussed.     

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     

ARSENIC CONSUMPTION AND HEALTH RISK PERCEPTIONS IN A RURAL WESTERN U.S. AREA1

ABSTRACT: Churchill County, Nevada, has approximately 23,000 residents, among whom an estimated 13,500 relied on private wells for water supply in 2002. This study examined exposure to arsenic in water supplies among residents with private domestic wells and factors related to householder choice to consume tap water. It compared opinions and concerns about water quality with consumption habits and observed concentrations from tap water samples. The results from 351 households indicated that a majority (75 percent) of respondents consumed tap water and that a minority (38 percent) applied treatment. Approximately 66 percent of those who consumed tap water were exposed to concentrations of arsenic that exceeded 10 ppb. Water consumption was related to application of treatment. Among 98 respondents who were not at all concerned about the health effects of aqueous arsenic, 59 (60 percent) reported consuming tap water with concentrations of arsenic exceeding 10 ppb. Conversely, among 86 respondents who were highly concerned about arsenic, 33 (37 percent) consumed tap water with concentrations of arsenic exceeding 10 ppb. Results from a national sampling effort showed that 620 of 5,304 private wells sampled (11.7 percent) had arsenic concentrations above 10 ppb. The paradox of awareness of arsenic in water supplies coupled with consumption of aqueous arsenic in concentrations greater than 10 ppb may be common in other parts of the nation. Enhanced educational efforts, especially related to tap water sampling and explanations of efficacy of available treatment, may be useful means of reducing exposure through private water supplies.     

Seasonal fluctuations in sand temperature: effects on the incubation period and mortality of loggerhead sea turtle (<Emphasis Type="Italic">Caretta</Emphasis><Emphasis Type="Italic">caretta</Emphasis>) pre-emergent hatchlings in Minabe,Japan

Incubation period, hatching success, and emergence percentage in loggerhead (Caretta caretta) nests were quantified during the 1993 and 1995 nesting seasons and following incubation seasons in Minabe, Wakayama, Japan. Sand and nest temperatures were also monitored. Over the seasons, daily mean sand temperature at nest depth fluctuated between 18.0°C and 33.3°C, with a steep increase in the second week of July and a peak in late August. Temperatures inside the nest chambers were a few degrees above those of the surrounding sand at the end of incubation. The incubation period ranged from 46 to 82 days. A significant negative correlation was found between mean sand temperature and incubation period. The relationship conformed to the day-degree concept. There was no significant seasonal trend in hatching success, but many pre-emergent hatchlings were found dead in most of the clutches during the warmest part of the season. Emergence percentage was correlated with mean sand temperature calculated for 4 days before emergence, suggesting that mortality may be due to heat. This heat-related mortality is considered to be a common phenomenon at our study site, because the peak in emergences coincides with the peak in high temperatures. These temperature effects on hatchling mortality must be taken into account in estimates of hatchling sex ratios. Because sand temperatures already exceed the optimal thermal range for incubation, this population is vulnerable to even small temperature increases resulting from global warming.     

Preimplantation genetic diagnosis of the fragile X syndrome by use of linked polymorphic markers

Fragile X syndrome is the most common cause of familial mental retardation. The most common mutation is expansion of a triplet (CGG)_n repeat in the 5′ untranslated region of the FMR1 gene on Xq27.3. The expansion is refractory to PCR due to preferential amplification of the smaller allele in heterozygous cells and the high GC content of the repeat and surrounding sequences. Direct detection of the normal parental alleles in preimplantation embryos has been used for preimplantation genetic diagnosis (PGD) of this disorder. However, this approach is only suitable for approximately 63% of couples due to the heterozygosity of the repeat in the normal population. As an alternative we investigated the use of polymorphic markers flanking the mutation to track the normal and premutation carrying maternal chromosomes in preimplantation embryos. Using a panel of 11 polymorphisms, six (CA)_n repeats and five single nucleotide polymorphisms, diagnosis was developed for 90% of referred couples. Multiplex amplification of informative markers was tested in 300 single buccal cells from interested couples with efficiency and allele drop out (ADO) rates ranging from 69% to 96% and 6% to 18%, respectively. Use of this approach is accurate and applicable to a larger number of patients at risk of transmitting fragile X to their offspring. Copyright © 2001 John Wiley & Sons, Ltd.