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.     

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.     

Measurement of transferable chemical residue from nylon carpet using the California roller and a new mega-California roller

Human chemical exposures resulting from transfer of surface deposition on indoor nylon carpets may be estimated by measuring transferable residues (mu g chemical/cm2 carpet). A weighted roller developed at California Department of Food and Agriculture (CDFA) has been extensively used to sample transferable residue for estimates of human exposure in risk characterization. A modified roller has been developed to evaluate the influence of pressure on transferable chemical residue since weight and force (or pressure, kg/m2) may vary person-to-person and activity-to-activity. A 30.5 cm diameter roller was used to apply 60 to 2100 kg/m2 to bracket pressures exerted by humans on a flat nylon-carpeted surface. Measurements of transferable cyfluthrin residues were made after 1, 7, and 21 days. Total Soxhlet extractable cyfluthrin residues were relatively constant during the test period. Residue transferability decreased during the study period. Modest increases in the transferability of surface residues were observed over the broad range of pressures applied by the modified roller.     

The toxicity of cadmium-copper mixtures on daphnids and microalgae analyzed using the Biotic Ligand Model

For the prediction of metal mixture ecotoxicity, the BLM approach is promising since it evaluates the amount of metals accumulated on the biotic ligand on the basis of water chemistry, i.e., species (major cations) competing with metals, and related toxicity. Based on previous work by Farley et al. (2015) (MMME research project), this study aimed at modeling toxicity of Cd:Cu mixtures (0:1 - 1:1 - 1:0 - 1:2 - 1:3 - 2:1 - 3:1 - 4:1 - 5:1 - 6:1) to the crustacean Daphnia magna(48-h immobilization tests) and the microalga Pseudokirchneriella subcapitata (72-h growth inhibition tests). The 2012 version of the USGS model was chosen, assuming additivity of effects and accumulation of metals on a single site. The assumption that EDTA could contribute to toxicity through metals complexing was also tested, and potential effects due to reduction of ions Ca²⁺ absorption by metals were considered. Modeling started with parameter values of Farley et al. (2015) and some of these parameters were adjusted to fit modeled data on observed data. The results show that toxicity can be correctly predicted for the microalgae and that the hypothesis of additivity is verified. For daphnids, the prediction was roughly correct, but taking into account CuEDTA led to more realistic parameter values close to that reported by Farley et al. (2015). However, It seems that, for daphnids responses, metals interact either antagonistically or synergistically depending on the Cu:Cd ratio. Furthermore, synergy could not be explained by additional effects linked to a reduction of Ca absorption since this reduction, mainly due to Cd, increased inversely to synergy. Finally, the USGS model applied to our data was able to predict Cu:Cd mixture toxicity to microalgae and daphnids, giving rise to estimated EC50s roughly reflecting EC50s calculated from observed toxicity.

     

Microplastic Pollution in Agricultural Soils and Abatement Measures – a Model-Based Assessment for Germany

Environmental Modeling & Assessment - Microplastic pollution in soils is a recent environmental problem and the lack of knowledge about the impacts and the extent of the problem are raising...     

Hydrochemical characteristics and quality assessment of shallow groundwater in Yangtze River Delta of eastern China

Environmental Science and Pollution Research - Water resource is in high demand within the Yangtze River Delta, given its developed economy. Long-term exploitation of this resource has posed risks...