Decomposition and oxidation of sodium 3,5,6-trichloropyridin-2-ol in sub- and supercritical water

Sodium 3,5,6-trichloropyridin-2-ol (STCP) is a necessary precursor compound for the production of chlorpyrifos and triclopyr, which are extensively used as pesticide and herbicide, respectively. In the process of STCP production, however, large amount of wastewater containing STCP is discharged, which causes increasingly environmental concerns. Therefore, it is of great significance to develop a rapid and effective method for the disposal of containing STCP contaminants. In this work, the thermal decomposition of STCP in sub- and supercritical water was investigated using a continuous tubular reactor. While STCP was stable below 280 °C, it could be effectively decomposed at elevated temperature. FT-IR spectra of the decomposition products indicated that the pyridine ring structure in the STCP molecule was stable even at temperatures up to 400 °C. The decomposition reaction was mainly caused by the substitution of Cl groups in the STCP molecule with OH groups, resulting in polyhydroxylated pyridines as the major decomposition product. Moreover, high pressure favored the substitution reaction. To completely decompose STCP into non-toxic or low toxic compounds, supercritical water oxidation (SCWO) was employed to evaluate the oxidation of STCP using H₂O₂ as an oxidant. It was found that STCP could be completely oxidized to H₂O, CO₂ and corresponding inorganic ammonium salts with an oxidation rate of 99%.     

Landfill gas generation after mechanical biological treatment of municipal solid waste. Estimation of gas generation rate constants

Mechanical biological treatment (MBT) of residual municipal solid waste (RMSW) was investigated with respect to landfill gas generation. Mechanically treated RMSW was sampled at a full-scale plant and aerobically stabilized for 8 and 15 weeks. Anaerobic tests were performed on the aerobically treated waste (MBTW) in order to estimate the gas generation rate constants (k,y(-1)), the potential gas generation capacity (L(o), Nl/kg) and the amount of gasifiable organic carbon. Experimental results show how MBT allowed for a reduction of the non-methanogenic phase and of the landfill gas generation potential by, respectively, 67% and 83% (8 weeks treatment), 82% and 91% (15 weeks treatment), compared to the raw waste. The amount of gasified organic carbon after 8 weeks and 15 weeks of treatment was equal to 11.01+/-1.25kgC/t(MBTW) and 4.54+/-0.87kgC/t(MBTW), respectively, that is 81% and 93% less than the amount gasified from the raw waste. The values of gas generation rate constants obtained for MBTW anaerobic degradation (0.0347-0.0803y(-1)) resemble those usually reported for the slowly and moderately degradable fractions of raw MSW. Simulations performed using a prediction model support the hypothesis that due to the low production rate, gas production from MBTW landfills is well-suited to a passive management strategy.     

Reducing acid leaching of manganiferous ore: effect of the iron removal operation on solid waste disposal

The process of reducing acid leaching of manganiferous ore is aimed at the extraction of manganese from low grade manganese ores. This work is focused on the iron removal operation. The following items have been considered in order to investigate the effect of the main operating conditions on solid waste disposal and on the process costs: (i) type and quantity of the base agent used for iron precipitation, (ii) effective need of leaching waste separation prior to the iron removal operation, (iii) presence of a second leaching stage with the roasted ore, which might also act as a preliminary iron removal step, and (iv) effect of tailings washing on the solid waste classification. Different base compounds have been tested, including CaO, CaCO3, NaOH, and Na2CO3. The latter gave the best results concerning both the precipitation process kinetics and the reagent consumption. The filtration of the liquor leach prior to iron removal was not necessary, implying significant savings in capital costs. A reduction of chemical consumption and an increase of manganese concentration in the solution were obtained by introducing secondary leaching tests with the previously roasted ore; this additional step was introduced without a significant decrease of global manganese extraction yield. Finally, toxicity characteristic leaching procedure (TCLP) tests carried out on the leaching solid waste showed: (i) a reduction of arsenic mobility in the presence of iron precipitates, and (ii) the need for a washing step in order to produce a waste that is classifiable as not dangerous, taking into consideration the existing Environmental National Laws.     

Zn biomineralization processes and microbial biofilm in a metal-rich stream (Naracauli,Sardinia)

Several decades after the closure of the Ingurtosu mine (SW Sardinia), a variety of seasonal Zn biomineralizations occurs. In this work, waters, microbial consortia, and seasonal precipitates from the Naracauli stream were sampled to investigate chemical composition of stream waters and biominerals, and microbial strain identity. Molecular and morphological analysis revealed that activity of dominant cyanobacterium Leptolyngbya frigida results in precipitation of Zn silicate. The activity of the cyanobacterium was associated to other bacteria and many kind of diatoms, such as Halamphora subsalina and Encyonopsis microcephala, which are trapped in the process of biomineral growth. In this work, the precipitation process is shown to be the result of many different parameters such as hydrologic regime, microbial community adaptation, and biological mediation. It results in a decrease of dissolved Zn in the stream water, and is a potential tool for Zn pollution abatement.     

Multilingual education of students on a global scale and perspective—international networking on the example of bioindication and biomonitoring (B&B technologies)

Living or formerly living organisms are being used to obtain information on the quality of the general health status of our environment by bioindication and biomonitoring methods for many decades. Thus, different roads toward this common scientific goal were developed by a lot of different international research groups. Global cooperation in between various scientific teams throughout the world has produced common ideas, scientific definitions, and highly innovative results of this extremely attractive working field. The transdisciplinary approach of different and multifaceted scientific areas—starting from biology, analytical chemistry, via health physics, up to social and economic issues—have surpassed mental barriers of individual scientists, so that “production” of straightforward common results related to the influence of material and immaterial environmental factors to the well-being of organisms and human life has now reached the forefront of international thinking. For the further sustainable development of our common scientific “hobby” of bioindication and biomonitoring, highest personal energy has to be given by us, being teachers to our students and to convince strategically decision makers as politicians to invest (financially) into the development of education and research of this innovative technique. Young people have to be intensively convinced on the “meaning” of our scientific doing, e.g., by extended forms of education. One example of multilingual education of students on a global scale and perspective is given here, which we started about 3 years ago.     

Influence of salinity and temperature on the activity of biosurfactants by polychaete-associated isolates

Influence of different parameters on biosurfactant (BS) activity was carried out on strains that were isolated from the polychaetes Megalomma claparedei, Sabella spallanzanii and Branchiomma luctuosum and additional 30 strains that were previously identified as potential BS producers from crude oil enrichments of the same polychaete specimens. The selection of BS-producing strains from polychaete natural samples was carried out by using standard screening tests. The BS activity by each isolate was evaluated for the effect of salinity and temperature on emulsion production and surface tension reduction, during incubation in mineral medium supplemented with tetradecane or diesel oil. All isolates showed a similar time course of BS activity, and the latter was more influenced by salinity rather than temperature. Some of the BS producers belonged to genera that have not (i.e. Citricoccus, Cellulophaga, Tenacibaculum and Maribacter) or have poorly been (Psychrobacter, Vibrio, and Pseudoalteromonas) reported as able to produce BSs. This is remarkable as some of them have previously been detected in hydrocarbon-enriched samples. Results confirm that filter-feeding polychaetes are an efficient source for the isolation of BS producers.     

Global atmospheric cycle of mercury: a model study on the impact of oxidation mechanisms

Mercury (Hg) is a global pollutant since its predominant atmospheric form, elemental Hg, reacts relatively slowly with the more abundant atmospheric oxidants. Comprehensive knowledge on the details of the atmospheric Hg cycle is still lacking, and in particular, there is some uncertainty regarding the atmospherically relevant reduction-oxidation reactions of mercury and its compounds. ECHMERIT is a global online chemical transport model, based on the ECHAM5 global circulation model, with a highly customisable chemistry mechanism designed to facilitate the investigation of both aqueous- and gas-phase atmospheric mercury chemistry. An improved version of the model which includes a new oceanic emission routine has been developed. Results of multiyear model simulations with full atmospheric chemistry have been used to examine the how changes to chemical mechanisms influence the model’s ability to reproduce measured Hg concentrations and deposition flux patterns. The results have also been compared to simple fixed-lifetime tracer simulations to constrain the possible range of atmospheric mercury redox rates. The model provides a new and unique picture of the global cycle of mercury, in that it is online and includes a full atmospheric chemistry module.     

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year^?1 of elemental Hg.     

Respiration induced by substrate and bacteria diversity after application of diuron,hexazinone, and sulfometuron-methyl alone and in mixture

Abstract

After application, herbicides often reach the soil and affect non-target soil microorganisms, decreasing their population, diversity or affecting metabolic activity. Therefore, laboratory studies were performed to evaluate the effects of diuron, hexazinone and sulfometuron-methyl alone and mixed upon carbon transformation by soil microorganisms in clayey and sandy soils and the effect on bacterial diversity and structure. Control treatment without herbicide application was also performed. Sub-samples from the control and herbicide treatments (10?g – in triplicate) were collected before herbicide application and 7, 14, 28 and 42?days after treatment (DAT), then 1?mL of ¹⁴C-glucose solution was applied. The released ¹⁴CO₂ was trapped in 2?M NaOH solution and the radioactivity was analyzed by liquid scintillation counting (LSC), 12?h after glucose application. The effect of herbicides on bacterial diversity was evaluated by T-RFLP. The experiment was conducted in a complete randomized design. Hexazinone did not affect ¹⁴CO₂ evolution. Diuron showed a greater ¹⁴CO₂ evolution in sandy and clayey soil, while sulfometuron-methyl led to an increase in sandy soil, at 42 DAT. A greater evolution of carbon was observed in the treatment with herbicide mixture in sandy soil, compared with the same treatment in clayey soil or control. However, the herbicide mixture application did not affect the soil biological activity measured by the respiration rate induced by substrate. On the other hand, the herbicide mixtures affected the bacterial diversity in both soils, being the strongest effect to diuron and sulfometuron-methyl in clayey soil and hexazinone in sandy soil.     

Breeding Birds as a Farm Product

Abstract: Since the 1950s, meadowbird populations have been under increasing threat from radical changes in farming practices. We studied the possibilities for conserving meadowbirds on modern, intensive dairy farms in the Netherlands. Here, the conventional strategy for the conservation of meadowbirds is to restrict farming intensity and compensate farmers for their production losses. To increase the breeding success of meadowbirds, however, dairy farmers can fine-tune farming practices to yearly and local circumstances. Because this fine-tuning is difficult to enforce by legislation, we propose that farmers be paid for clutches bred on their land. Thus, farmers are paid for what they produce, but not restricted in their farming practices. The results of the first small-scale experiments, in which breeding success was compared between farms where farmers were paid for meadowbird clutches and farms where farmers were not paid, are encouraging. Breeding success of meadowbirds was significantly higher where farmers were paid than where they were not ( breeding success of Lapwing [   Vanellus vanellus ]: 64.7% on paid farms, 48.2% on unpaid farms; Black-tailed Godwit [   Limosa limosa ]: 63.1% paid, 39.3% unpaid). The effects on meadowbird populations could not yet be detected. The per-clutch payment system is less expensive than compensation for income losses: paying for clutches costs 40 Euro per clutch, whereas compensating for income losses costs 100–400 Euro per clutch (1 Euro is approximately equal to 1 U.S. dollar). Farmers are enthusiastic, and the system encourages cooperation between farmers and nature conservationists.