Activated soil filters for removal of biocides from contaminated run-off and waste-waters

Building facades can be equipped with biocides to prevent formation of algal, fungal and bacterial films. Thus run-off waters may contain these highly active compounds. In this study, the removal of several groups of biocides from contaminated waters by means of an activated soil filter was studied.A technical scale activated vertical soil filter (biofilter) with different layers (peat, sand and gravel), was planted with reed (Phragmites australis) and used to study the removal rates and fate of hydrophilic to moderate hydrophobic (log K_ow 1.8-4.4) biocides and biocide metabolites such as: Terbutryn, Cybutryn (Irgarol® 1051), Descyclopropyl-Cybutryn (Cybutryn and Terbutryn metabolite), Isoproturon, Diuron, and its metabolite Diuron-desmonomethyl, Benzo-isothiazolinone, n-Octyl-isothiazolinone, Dichloro-n-octylisothiazolinone and Iodocarbamate (Iodocarb). Three experiments were performed: the first one (36 d) under low flow conditions (61 L m⁻² d⁻¹) reached removal rates between 82% and 100%. The second one was performed to study high flow conditions: During this experiment, water was added as a pulse to the filter system with a hydraulic load of 255 L m⁻² within 5 min (retention time <1 h). During this experiment the removal rates of the compounds decreased drastically. For five compounds (Cybutryn, Descyclopropyl-Cybutryn, Diuron, Isoproturon, and Iodocarb) the removal dropped temporarily below 60%, while it was always above 70% for the others (Terbutryn, Benzo-isothiazolinone, n-Octyl-isothiazolinone, Dichloro-n-octylisothiazolinone). However, this removal is a considerable improvement compared to direct discharge into surface waters or infiltration into soil without appropriate removal. In the last experiment the removal efficiencies of the different layers were studied. Though the peat layer was responsible for most of the removal, the sand and gravel layers also contributed significantly for some compounds. All compounds are rather removed by degradation than by sorption.     

Environmental and health effects of nanomaterials in nanotextiles and façade coatings

Engineered nanomaterials (ENM) are expected to hold considerable potential for products that offer improved or novel functionalities. For example, nanotechnologies could open the way for the use of textile products outside their traditional fields of applications, for example, in the construction, medical, automobile, environmental and safety technology sectors. Consequently, nanotextiles could become ubiquitous in industrial and consumer products in future. Another ubiquitous field of application for ENM is fa?ade coatings. The environment and human health could be affected by unintended release of ENM from these products. The product life cycle and the product design determine the various environmental and health exposure situations. For example, ENM unintentionally released from geotextiles will probably end up in soils, whereas ENM unintentionally released from T-shirts may come into direct contact with humans and end up in wastewater. In this paper we have assessed the state of the art of ENM effects on the environment and human health on the basis of selected environmental and nanotoxicological studies and on our own environmental exposure modeling studies. Here, we focused on ENM that are already applied or may be applied in future to textile products and fa?ade coatings. These ENM's are mainly nanosilver (nano-Ag), nano titanium dioxide (nano-TiO(2)), nano silica (nano-SiO(2)), nano zinc oxide (nano-ZnO), nano alumina (nano-Al(2)O(3)), layered silica (e.g. montmorillonite, Al(2)[(OH)(2)/Si(4)O(10)]nH(2)O), carbon black, and carbon nanotubes (CNT). Knowing full well that innovators have to take decisions today, we have presented some criteria that should be useful in systematically analyzing and interpreting the state of the art on the effects of ENM. For the environment we established the following criteria: (1) the indication for hazardous effects, (2) dissolution in water increases/decreases toxic effects, (3) tendency for agglomeration or sedimentation, (4) fate during waste water treatment, and (5) stability during incineration. For human health the following criteria were defined: (1) acute toxicity, (2) chronic toxicity, (3) impairment of DNA, (4) crossing and damaging of tissue barriers, (5) brain damage and translocation and effects of ENM in the (6) skin, (7) gastrointestinal or (8) respiratory tract. Interestingly, some ENM might affect the environment less severely than they might affect human health, whereas the case for others is vice versa. This is especially true for CNT. The assessment of the environmental risks is highly dependent on the respective product life cycles and on the amounts of ENM produced globally.     

Oxidative degradation of chlorophenol derivatives promoted by microwaves or power ultrasound: a mechanism investigation

Background, aim, and scope

Phenols are the most common pollutants in industrial wastewaters (particularly from oil refineries, resin manufacture, and coal processing). In the last two decades, it has become common knowledge that they can be effectively destroyed by nonconventional techniques such as power ultrasound (US) and/or microwave (MW) irradiation. Both techniques may strongly promote advanced oxidation processes (AOPs). The present study aimed to shed light on the effect and mechanism of US- and MW-promoted oxidative degradation of chlorophenols; 2,4-dichlorophenoxyacetic acid (2,4-D), a pesticide widespread in the environment, was chosen as the model compound.

Materials and methods

2,4-D degradation by AOPs was carried out either under US (20 and 300 kHz) in aqueous solutions (with and without the addition of Fenton reagent) or solvent-free under MW with sodium percarbonate (SPC). All these reactions were monitored by gas chromatography–mass spectrometry (GC–MS) analysis and compared with the classical Fenton reaction in water under magnetic stirring. The same set of treatments was also applied to 2,4-dichlorophenol (2,4-DCP) and phenol, the first two products that occur a step down in the degradation sequence. Fenton and Fenton-like reagents were employed at the lowest active concentration.

Results

The effects of US and MW irradiation were investigated and compared with those of conventional treatments. Detailed mechanisms of Fenton-type reactions were suggested for 2,4-D, 2,4-DCP, and phenol, underlining the principal degradation products identified. MW-promoted degradation under solvent-free conditions with solid Fenton-like reagents (viz. SPC) is extremely efficient and mainly follows pyrolytic pathways. Power US strongly accelerates the degradation of 2,4-D in water through a rapid generation of highly reactive radicals; it does not lead to the formation of more toxic dimers.

Discussion

We show that US and MW enhance the oxidative degradation of 2,4-D and that a considerable saving of oxidants and cutting down of reaction times is thereby achieved. The results support the interpretation of previously published data and improve the understanding of the factors of direct degradation along different pathways.

Conclusions

Oxidative pathways for 2,4-D, 2,4-DCP, and phenol were proposed by a careful monitoring of the reactions and detection of intermediates by GC–MS.

Recommendations and perspectives

The understanding of the factors that affect chlorophenols degradation along different pathways may facilitate the optimization of the treatment. Type of energy source (US or MW), power, and frequency to be applied could be designed in function of the operative scenario (amount of pollutant in soil, water, or oils).     

2,5,6,9,10-Pentabromocyclododecanols (PBCDOHs): a new class of HBCD transformation products

Pentabromocyclododecanols (PBCDOHs) are potential environmental transformation products of hexabromocyclododecanes (HBCDs). They are also potential stage one metabolites of biological HBCD transformations. Herein, we present analytical evidence that PBCDOHs are also constituents of technical HBCDs and flame-proofed polystyrenes (FP-PSs). PBCDOHs are possibly formed during the synthesis of technical HBCD, presumably during the bromination of cyclododecatrienes in aqueous isobutanol together with isobutoxypentabromocyclododecanes (iBPBCDs), which have been identified in these materials recently. Of the 64 stereoisomers possible, eight pairs of enantiomers, named α-, β-, γ-, δ-, ε-, ζ-, η-, and θ-PBCDOHs were separated with a combination of normal-, reversed- and chiral-phase LC. Crystal structure analysis revealed the stereochemistry of the α-PBCDOH pair of enantiomers, which was assigned to (1S,2S,5R,6S,9S,10R)-2,5,6,9,10-pentabromocyclododecanol and its enantiomer. Mass spectrometric data are in accordance with the expected isotope patterns. On a C₁₈-RP-column, the polar PBCDOHs eluted before the HBCD and iBPBCD classes of compounds. PBCDOHs were also found in FP-PS materials. The stereoisomer patterns varied considerably in these materials like those of HBCDs and iBPBCDs. Expanded polystyrenes were rich in late-eluting stereoisomers, similar to technical HBCD mixtures. Extruded polystyrenes contained more of the polar, faster-eluting isomers. The presented chromatographic and analytical methods allow a stereoisomer-specific search for PBCDOHs in biota samples, which might have experienced metabolic HBCD transformation reactions. Besides this potential source, it has to be recognized that PBCDOHs are by-products in technical HBCDs and in flame-proofed polystyrenes. Therefore, it is likely that PBCDOHs and iBPBCDs are released to the environment together with HBCD-containing plastic materials.     

Comparison of percolation to batch and sequential leaching tests: Theory and data

Leaching tests are becoming more relevant in assessing solid waste material, particularly with respect to groundwater risks. In the field, water infiltration is the dominant leaching mechanism, which is simulated in the lab with batch and column tests. In this study, we compared percolation, through analytical solutions of the advection–dispersion equation, to laboratory batch and sequential leaching tests. The analytical solutions are supported with comprehensive data from various field and laboratory leaching of different solutes from waste materials and soils collected in long-term joint research projects funded by the German Federal Ministry for Education and Research and the Federal Environment Agency. The comparison of theory and data is facilitated if concentrations and cumulative release are plotted versus the liquid–solid ratios (LS). Both theory and data indicate that leaching behaviour is independent of duration and physical dimensions of the leaching tests. This holds even if field lysimeters are compared to laboratory columns of different size, different flow velocities as well as different contact times. In general, laboratory batch tests over predict effluent concentrations (for LS < K_d). Leaching of solutes from solid samples of certain materials (e.g. chloride from incineration ashes or sulphate from demolition waste) in column and lysimeter tests compares very well and agrees with the analytical solutions. Overall, reproducibility and agreement with theory of column tests are better than batch tests, presumably because the latter are prone to artefacts (e.g. in liquid–solid separation steps). Theory and data fit surprisingly well, despite the fact that the theory is based on the local equilibrium assumption; non-linear sorption and chemical reactions in the solid waste materials are not considered.