Linear and non-linear relationships mapping the Henry’s law parameters of organic pesticides

This work aims to predict the air to water partitioning for 96 organic pesticides by means of the Quantitative Structure–Property Relationships Theory. After performing structural feature selection with Genetics Algorithms and Replacement Method linear approaches, it is found that among the most important molecular features appears the Moriguchi octanol–water partition coefficient, and higher lipophilicities would lead to compounds having higher Henry’s law constants. We also compare the statistical performance achieved by four fully-connected Feed-Forward Multilayer Perceptrons Artificial Neural Networks. The statistical results found reveal that the best performing model uses the Levenberg–Marquardt with Bayesian regularization (BR) weighting function for achieving the most accurate predictions.     

Product Guide/1970

Abstract

In Mexico City, the use and composition of fuels determine that carbon monoxide (CO) comes mostly from mobile sources, and sulfur dioxide (SO₂) from fixed and mobile sources. By simultaneously measuring hydrocarbons (HC), CO, and SO₂ in the atmosphere of Mexico City, the relative amounts coming from different sources can be estimated. Assuming that some HC are emitted proportionally to CO emissions, we can establish that [HC]₁= m1? [CO], where the proportionality constant ml corresponds to the ratio of emissions factor for HC and CO in mobile sources. Similarly for fuels containing sulfur, it can be assumed that [HC]₂ = m2 ? [SO₂]. In this way, the total HC are [HC]_total=[HC]₀+ ml ? [CO]+ m2 ? [SO₂], where [HC]₀ corresponds mainly to other sources like solvent evaporation, gas consumption, and natural emissions. In this way, it can be estimated that in Mexico City 75% of average HC comes from mobile sources, 5% from sulfur-related sources, and 19% from natural sources and solvent evaporation. Compared with the HC/CO ratio measured in the exhaust pipe of vehicles, we estimated that 70% of HC emitted from mobile sources are evaporative losses, and only 30% come through the exhaust system.     

The bioaccumulation of Molybdenum in the earthworm Eisenia andrei: influence of soil properties and ageing

Mo bioaccumulation in the earthworm Eisenia andrei was determined after 28 d exposure in ten different European field soils (pH 4.4-7.8) and an artificial soil, freshly spiked with Na₂MoO₄ at concentrations between 3.2 and 3200 mg Mo kg⁻¹ dry soil. Three field soils were also tested after ageing for 11 months. Earthworm Mo concentrations generally levelled off at high exposure levels but in most soils showed a (nearly) linear increase with increasing soil concentrations in the lower, non-toxic range (below EC10 or NOEC for reproduction effects). Bioaccumulation (BAF) and Bioconcentration factors (BCF) were calculated as the ratio of earthworm concentration to soil and estimated porewater concentrations, respectively. BAFs (0.35-3.44) and BCFs (1.31-276) did not seem much affected by soil concentration, suggesting that earthworms are not capable of regulating their internal Mo concentrations. BAF was best predicted by ammonium oxalate-extractable iron (Fe_ox) and phosphor (P_ox) contents of the soils.     

Assessment of organochlorine pesticide residues in Atlantic Rain Forest fragments, Rio de Janeiro, Brazil

A superficial water quality survey in a watershed of the Paraíba do Sul River, the main water supply for the most populated cities of southeastern Brazil, was held in order to assess the impact of the expansion of agricultural activity in the near border of the Atlantic Rain Forest. The aim of this study was to investigate the presence of priority organochlorine pollutants in soils and superficial waters of Atlantic rainforest fragments in Teresópolis, Rio de Janeiro State. Soil sample preparations were compared by using ultrasound, microwave assisted extraction and Soxhlet extraction. Recoveries of matrix spiked samples ranged from 70 to 130%. Analysis of a certified soil material showed recoveries ranging from 71 to 234%. Although low concentrations of organochlorine residues were found in water and soil samples, this area is of environmental importance and concern, thus demanding a monitoring program of its compartments.     

Experimental testing of an annular denuder and filter system to measure gas–particle partitioning of semivolatile bifunctional carbonyls in the atmosphere

An annular denuder and filter-pack system was tested in combination with the use of the in-tube and on-fiber O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA)-derivatization technique to simultaneously sample and measure gaseous and particulate concentrations of semivolatile bifunctional carbonyl compounds in the atmosphere. Ozone was denuded from the sampling air to avoid oxidation and PFBHA was used as the sorbent by coating the sampling denuders and impregnating the filters. The collection efficiency of the system was evaluated under different conditions in photochemical smog chamber experiments and in field samplings of urban and suburban atmospheres. The effects of concentration level, temperature, and humidity on the collection efficiency were assessed. The system showed average collection efficiencies in one denuder from 81% for pyruvic acid and 82% for glyoxylic acid to 87% for hydroxyacetone and dihydroxyacetone. The capacity of the filters to collect the gaseous fraction that cannot be collected in the denuders was also evaluated, and the system allows a correction for this artifact. The application of this method to chamber experiments and field samplings offers an easy-to-apply technique with good results that can be used to evaluate the partition mechanisms of these compounds in the atmosphere.     

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.     

Growth,mortality and recruitment of the yellow clam Mesodesma mactroides on Uruguayan beaches

We studied some aspects of the population dynamics of the yellow clam Mesodesma mactroides (Deshayes, 1854) which inhabits the eastern sandy beaches of Uruguay. Observations were made from March 1983 through March 1985 (harvesting season), and additional data from January 1988 to December 1989 (closed season) were also included in the analyses. Parameters of growth and mortality were estimated by methods that make use of age or length information. An age/length relationship was constructed by counting growth rings. Results were consistent with those obtained with modal class progression analysis and other length/frequency methods. The growth curve obtained from the age/length relationship did not account for seasonality in growth rate, and a seasonal growth model explained growth oscillations in a better way. The instantaneous coefficient of natural mortality (M) estimated for the closed season was 1.64, whereas an increase in fishing mortality (F) was observed during 1984. Age composition did not change during the 2 yr of study, and the first 6 mm class accounted for over 50% of the population. The main contribution of recruits was observed between late summer and early fall (February to April), and the recruitment pattern suggested one main settlement period per year. Growth and recruitment success appeared to be regulated by density-dependence processes. Some implications for management are considered in this context. Methodological aspects concerning the reliability of empirical equations and programs for estimating growth and mortality are discussed.