Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process

This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350 °C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H₂O and CO₂. The Arrhenius law data obtained for the phenol disappearance are the following: k = 1.8 × 10⁶ ± 3.9 × 10⁵ M⁻¹ s⁻¹ (pre-exponential factor) and E_a = 77 ± 8 kJ mol⁻¹ (activation energy).     

Environmental risks of farmed and barren alkaline coal ash landfills in Tuzla, Bosnia and Herzegovina

The disposal of coal combustion residues (CCR) has led to a significant consumption of land in the West Balkan region. In Tuzla (Bosnia and Herzegovina) we studied previously soil-covered (farmed) and barren CCR landfills including management practises, field ageing of CCR and the transfer of trace elements into crops, wild plants and wastewaters. Soil tillage resulted in mixing of cover soil with CCR. Medicago sativa showed very low Cu:Mo ratios (1.25) which may cause hypocuprosis in ruminants. Total loads of inorganic pollutants in the CCR transport water, but not pH ( approximately 12), were below regulatory limits of most EU countries. Arsenic concentrations in CCR transport water were <2microgl(-1) whereas reductive conditions in an abandoned landfill significantly enhanced concentrations in leachates (44microgl(-1)). The opposite pattern was found for Cr likely due to large initial leaching of CrVI. Public use of landfills, including farming, should be based on a prior risk assessment due to the heterogeneity of CCR.     

Transformation of diclofenac by the indigenous microflora of river sediments and identification of a major intermediate

Diclofenac is a non-steroidal anti-inflammatory drug, which tends to be relatively persistent in the environment. Now, a fixed-bed column bioreactor filled with sediment from the creek Münzbach (Freiberg/Saxony) under aerobic conditions showed rapid removal of diclofenac in a concentration range of 3-35 microM without previous adaptation. The conversion of higher concentrations up to 260 microM was accompanied by conspicuously decreased turnover rates indicating a toxic effect of this drug or its resulting metabolic burden on the indigenous microflora. A major metabolite occurred transiently and was identified by NMR and MS to be the p-benzoquinone imine of 5-hydroxydiclofenac. Abiotic adsorption to the biofilm was shown to determine the further fate of this reactive product of 5-hydroxydiclofenac (aut-)oxidation. The apparent lack of a degradative potential for this compound as well as the failure to detect an enrichment of diclofenac-depleting microbial activity both indicate a cometabolic nature of diclofenac transformation. 4'-Hydroxy-diclofenac, the favoured transformation product of eucaryotic diclofenac metabolism, could not be identified. The ability to convert diclofenac was shown to be widespread among biofilms from different river sediments, but measured rates obviously do not correlate with the total microbial activity. In addition, application of sediments from locations exposed to communal waste water effluents did not indicate any form of adaptation measured as an increased specific diclofenac depletion rate.     

Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

Impact of biogas digestates on soil microbiota in agriculture: a review

Environmental Chemistry Letters - The global production of biogas has increased threefold during the last decade to partly replace fossil fuels, yet biogas production by anaerobic digestion...     

Urine concentrations of selected trace metals in a cohort of Irish adults

Environmental Science and Pollution Research - Human biomonitoring studies are of increasing importance in regulatory toxicology; however, there is a paucity of human biomonitoring data for the...     

Innovative technologies to remove alkylphenols from wastewater: a review

Environmental Chemistry Letters - Alkylphenols and alkylphenol polyethoxylates are emerging hazardous contaminants due in particular to their endocrine-disrupting properties. These compounds...     

Professor Casu’s contribution to cyclodextrins,the remarkable cage-shaped molecules: a review

Cyclodextrins are cage-shaped molecules having the remarkable ability to trap smaller compounds, and have thus led to applications in many disciplines such as medicine to increase the bioavailability of hydrophobic drugs. This historical review summarizes the outstanding contribution of the late Professor Benito Casu to cyclodextrin research and, more generally, to the chemistry and biochemistry of linear and cyclic oligosaccharides, polysaccharides, glycosaminoglycans, and heparin. Professor Casu was the first to elucidate the structure and conformations of cyclodextrins by infrared spectroscopy and proton nuclear magnetic resonance (NMR). In particular, he showed that trapped compounds induced a shift of H peaks in NMR due to the shielding effect of cyclodextrins. He also demonstrated that the d-glucopyranose cyclodextrin units are in the C-1 chair conformation by analyzing α-cyclodextrin by NMR in dimethylsulfoxide-d₆.

     

Removal of emerging contaminants from wastewater using advanced treatments. A review

Environmental Chemistry Letters - The rise of emerging contaminants in waters challenges the scientific community and water treatment stakeholders to design remediation techniques that are simple,...     

The effect of the Sars-Cov-2 pandemic on the use of personal protective equipment in hospitals

The Covid pandemic has strongly affected the use of personal protective equipment (PPE) in the medical sector. Our aim was to assess the influence of Covid on PPE use within a German hospital by analyzing PPE use in four years prior to Covid and in 2020/2021. Numbers of items and mass of different types of PPE were determined based on procurement data. The results show that for the use of gloves the pandemic only had a small effect on the number of items. For body protection there was a clear trend toward a decrease in the number of items used in the years before the pandemic due to actions by the hospital toward a better environmental footprint which was partially reversed by the pandemic. The number of masks on the other hand doubled during the pandemic. Expressed in mass of PPE per patient and day, 15 g of masks, 121 g of gloves, and 183 g of body protection are used, resulting in a total of 319 g of PPE per patient and day. As medical waste has a specific treatment, no direct environmental effects of PPE use in hospitals in a region with well-developed waste treatment system are expected.