Re-evaluation of the conformational structure of sulfadiazine species using NMR and ab initio DFT studies and its implication on sorption and degradation

In the environment, the sorption and the degradation of organic pollutants are of increasing interest. The investigation of the chemical structures provides a basis for the development of a suitable binding model approach and for the mechanistic understanding of the chemical fate processes. The aim of this study was the identification of different species of the antibiotic compound sulfadiazine (SDZ) using (1)H and (13)C NMR experiments and ab initio density functional theory (DFT) calculations. In the neutral, aprotic solvent dimethylsulfoxide-d(6) (DMSO-d(6)), a new sulfadiazine structure containing an O-H-N hydrogen bond was identified. In the protic solvent water-d(2) and in dependence on pH and the position of the amidogen hydrogen atom nine possible SDZ conformations were analyzed and five structures were identified. Good conformity between theory and calculation of (1)H NMR was observed. Unfortunately, (13)C NMR is not sensitive enough for comparison and differentiation. In order to verify the identified structures, additional NBO/NLMO (natural localized molecular orbital) analyses were conducted (calculation of net atomic charges, bond polarity, atomic valence, and electron delocalization). Finally, conformation optimizations were performed in order to investigate the stability of the SDZ species. We showed that SDZ contains no S=O double bond, but that it has two S-O single bonds. Surprisingly, negative charges were observed at the pyrimidine nitrogen atom. With these results, the known structure of SDZ was revised. Studies of the geometrical structure and the torsion angles showed that SDZ is very flexible and can be easily fitted to the sorbent. These observations would explain the strong sorbance and hence the rapid formation of non-extractable residues in the environment because SDZ acts as a strong ligand. These results show that that the sulfonamide hydrogen is important for the biological activity but the pyrimidine nitrogen and the sulfonamide oxygen is responsible for the sorbance in environment.     

Impact of sewage sludge treatment processes on the removal of the endocrine disrupters nonylphenol ethoxylates

Several treatment processes of mixed sludge naturally contaminated with nonylphenol ethoxylates (NPE) were compared in order to evaluate their efficiency for the removal of these endocrine disrupters. Anaerobic and aerobic treatments were carried out in continuous stirred tank reactors, operated separately or combined together, at mesophilic and thermophilic temperatures and with or without ozone post-treatment. Anaerobic mesophilic removal of NPE consisted of complete removal of nonylphenol diethoxylate, incomplete removal of nonylphenol monoethoxylate and non stoechiometric production of nonylphenol, with consequently a NPE removal of 25%. At thermophilic temperature, anaerobic digestion led to an increase of the total solids removal efficiency, while improving NPE degradation (30%). Under thermophilic aerobic condition, the three compounds were removed simultaneously with a NPE removal efficiency higher than under anaerobic condition (39%). This removal is always well correlated to the total solids removal meaning that bioavailability remains the main limiting factor. Combination of either thermophilic aerobic-mesophilic anaerobic or mesophilic anaerobic-ozonation treatments enhanced the NPE removal by comparison to single systems (45% and 48%, respectively). These results confirm the high potential of existing and up-grading sewage sludge treatments to degrade such refractory and aged compounds.     

Social network characteristics and resource access among formerly displaced households in Lira,Uganda

In rural African communities, the support of extended family, friends, and neighbours is essential in borrowing or leveraging land, labour, food, and money, especially at times of social and financial turmoil. Little is known, though, about the nature of the networks and the conditions under which they may generate greater support in post‐conflict communities. This study, conducted in the Lira district of northern Uganda, examined the composition, proximity, and size of the networks that households utilise to gain access to resources during and after resettlement. Network structures with more kin and co‐resident ties were found to offer greater resource access to households in post‐conflict settings. Furthermore, there was a lack of meaningful linkages outside of a person's own village, especially with regard to households whose head has no or a low level of education. These findings enhance understanding of the specific role of relationships in social support for resource access among households in post‐conflict communities.     

Tackling Contentious Invasive Plant Species: A Case Study of Buffel Grass in Australia

Introduced plants that have both production values and negative impacts can be contentious. Generally they are either treated as weeds and their use prohibited; or unfettered exploitation is permitted and land managers must individually contend with any negative effects. Buffel grass (Cenchrus ciliaris) is contentious in Australia and there has been no attempt to broadly and systematically address the issues surrounding it. However, recent research indicates that there is some mutual acceptance by proponents and opponents of each others’ perspectives and we contend that this provides the basis for a national approach. It would require thorough and on-going consultation with stakeholders and development of realistic goals that are applicable across a range of scales and responsive to regional differences in costs, benefits and socio-economic and biophysical circumstances. It would be necessary to clearly allocate responsibilities and ascertain the most appropriate balance between legislative and non-legislative mechanisms. A national approach could involve avoiding the introduction of additional genetic material, countering proliferation in regions where the species is sparse, preventing incursion into conservation reserves where it is absent, containing strategically located populations and managing communities to prevent or reduce dominance by buffel grass. This approach could be applied to other contentious plant species.     

Control of Claus Plant Sulfur Compound Emissions

The body of information of this paper is directed to those individuals charged with selecting a process to control atmospheric sulfur emissions from Claus plants serving refineries, gas processing installations, and chemical plants. The TGT process developed by the French Petroleum Institute (IFP) is an extension of the Claus reaction itself in the liquid phase. Mixed H₂S and SO₂ in tail gas from Claus units is fed to a packed tower in which a solution of proprietary catalyst in a high BP polyglycol circulates countercurrent to the gas flow. The mixed gases react with the catalyst to form a complex, which in turn reacts with more gases to produce elemental sulfur. Reaction temperature keeps the sulfur above its melting point. Product accumulates in the boot of the tower and is drawn off continuously through a seal leg.

The IFP TGT process is simple in design and units have simple construction, characterized by use of low carbon steel and the use of very few pieces of equipment. Of all processes used today to take effluent sulfur values down to 1000 ppm SO₂ after incineration, the IFP TGT process requires the least capital investment and the lowest operating costs. Twenty-six full scale plants are operating or under design or construction: nine each in the U.S. and Japan, five in the U.S.S.R. and Poland, two in western Europe and one in Canada. Capacities of the Claus plants served range from 45 to 800 Lt/d sulfur.     

Assessment of Health Effects of Fluctuating Concentrations Using Simplified Pharmacokinetic Algorithms

Abstract

The purpose of this study was to develop a simple, practical method to improve the accuracy of assessing health effects by determining the concentration patterns inside the body resulting from fluctuating external pollutant concentrations. Linear pharmacokinetic processes were assumed, and the attenuations of the high- and low-frequency components of the external pattern when entering through the "biological window" were determined. Similar attenuations also were determined for the "time-averaged sampling window." It was shown that when the averaging time was less than 1/4 of the biological half-life, no information of biological significance was lost. Thus, a simple arithmetic step equation was proposed to convert external time-averaged concentrations to "biologically effective concentrations" proportional to internal concentrations. Calculations could readily be made in real time by a monitoring instrument, or even with a pocket calculator. Another simple algorithm was proposed for determining a "biological damage parameter" representative of cumulative damage if the body repair process is slow. Finally, simple algorithms were proposed for calculating body burdens from total absorbed mass rates, a procedure that should be useful for pollutants such as lead that may enter the body through multiple pathways. Results were compared with experimental and hypothetical data to show their utility.     

Full-Scale Evaluation of the Thermal Stability-Based Hazardous Organic Waste Incinerability Ranking

De nombreuses études épidémiologiques ont observé dans des contextes différents une faible relation à court terme entre les particules et la mortalité cardio-pulmonaire, même quand les normes de qualité de l'air n'étaient pas dépassées. La causalité de cette relation est un enjeu de santé publique en raison de l'importance de la population exposée. Notre objectif est de faire l'inventaire critique des arguments utilisés dans 15 revues de la littérature publiées.

Nous expliquons l'importance de distinguer la validité de la causalité et analysons de façon systématique les différents critères de jugement dans le contexte des études écologiques temporelles. Notre conclusion est que la relation observée est valide et que la plupart des critères de causalité sont respectés. Diminuer le niveau d'exposition des populations aux particules est souhaitable. En Europe, en agissant à la source, notamment sur les émissions Diesel, on diminuera aussi d'autres polluants qui peuvent jouer un rôle sanitaire. Aux États-Unis, la situation est plus complexe car les particules sont surtout secondaires.

Il est également indispensable de poursuivre les recherches pour mieux connaître les déterminants des expositions globales des individus et mieux comprendre le rôle toxique des différents facteurs physico-chimiques des particules.     

Comparison of specific versus literature species sensitivity distributions for herbicides risk assessment

Species sensitivity distributions (SSDs) are an important predictive tool in risk assessment. Usually, literature data are used to build SSDs that are mostly based on planktonic species. But, to get adequate protective thresholds for environmental communities, one could argue that SSD should be built on ecotoxicological data obtained from species found in the ecosystem that should be protected. This is particularly true when benthic algae are of concern. Due to the lack of literature data, building SSD on benthic microalgae is difficult. This paper aims in comparing SSDs, and thus protective thresholds (hazardous concentration that affects 5 % of the species of a community, HC₅), built on ecotoxicological data obtained (1) from literature and (2) with specific bioassays on benthic diatoms from a lake. Thresholds were derived for protection against four herbicides separately and for a mixture of them. Sensitivity data obtained from literature were statistically lower than the specific data for all herbicides: Species tested in the literature were usually more sensitive (mainly chlorophytes), leading to more protective lower HC₅. The HC₅ thresholds (literature or specific) derived for protection against the mixture were also compared to the observed sensitivity of an assemblage of benthic diatom species exposed to an increasing range of herbicide mixture concentrations. We observed that one species within the assemblage (Fragilaria rumpens) was affected at a concentration below both the literature and the specific HC₅ thresholds.     

Modeling Past and Future Acidification of Swedish Lakes

Decades of acid deposition have caused acidification of lakes in Sweden. Here we use data for 3000 lakes to run the acidification model MAGIC and estimate historical and future acidification. The results indicate that beginning in about 1920 a progressively larger number of lakes in Sweden fell into the category of “not naturally acidified” (∆pH > 0.4). The peak in acidification was reached about 1985; since then many lakes have recovered in response to lower levels of acid deposition. Further recovery from acidification will occur by the year 2030 given implementation of agreed legislation for emissions of sulphur (S) and nitrogen (N) in Europe. But the number of catchments with soils being depleted in base cations will increase slightly. MAGIC-reconstructed history of acidification of lakes in Sweden agrees well with information on fish populations. Future acidification of Swedish lakes can be influenced by climate change as well as changes in forest harvest practices.