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.     

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.     

Migration and animal husbandry: Competing or complementary livelihood strategies.Evidence from Kyrgyzstan

Animal husbandry and labour migration are important livelihood strategies for a large proportion of the rural population in developing countries. Up to now, the two strategies have usually been studied by looking at either one or the other; their interlinkages have rarely been examined. Based on a case study in rural Kyrgyzstan, the aim of this paper is to explore the links between animal husbandry and labour migration. Results show that for most rural households, livestock is crucial yet not sufficient to make a living. Therefore, many people diversify their income sources by migrating to work elsewhere. This generates cash for daily expenses and the acquisition of new livestock, but also leads to an absence of workforce in households. Yet since remittances usually exceed the expenses for hiring additional workforce, most people consider migration profitable. From a socio‐economic point of view, migration and animal husbandry can thus be considered important complementary livelihood strategies for the rural Kyrgyz population, at least for the time being. In the long term, however, the failure of young migrants to return to rural places and their settlement in urban areas might also cause remittance dependency and lead to an increasing lack of qualified labour. From an environmental point of view, the investment of remittances into animal husbandry poses challenges to sustainable pasture management. Increasing livestock numbers in rural areas raise pressure on pasture resources. Since most people consider animal husbandry their main future prospect while continuing to use pastures in a fairly unsustainable way, this may further exacerbate the over‐utilization of pastures in future.     

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).     

Humanarzneimittel im aquatischen Ökosystem

Goal

In the Brandenburg State Office for the Environment an approach to assess the potential risk of drug residues in aquatic ecosystems has been developed based on an investigation of the consumption amounts in 1999 to identify or to exclude a potential environmental risk of important human drugs and further to define priority substances for monitoring programs in Brandenburg in the future.

Method

This assessment approach tested with 60 drug agents is based on an exposure estimation considering the main path for the entry human—waste water—sewage plant—surface water, on a substance specific analysis of effects and on an analysis of the environmental fate as compartment distribution, bioaccumulation and persistence.

Results

In Brandenburg surface waters the drug agent concentration for eight of the considered substances is supposed to be greater than 1 μg/l and for at least 13 of the considered substanoes the PNEC in aquatic ecosystems is assumed to be lower than 1 μg/l. A potential risk for the environment can be seen for the antibiotics Ciprofloxacin-HCl and Clarithromycin, the disinfectants Benzalkonium Chloride, Cocospropylendiaminguaniacetat, Glucoprotamine, Laurylpropylenediamine and Polyvidone-iodine, the sexual hormon Ethinylestradiol, the antidiabetic Metformin-HCl, the antiepileptic Carbamazepine and the lipid regulator Clofibrinic acid on the basis of effects because their PEC:PNEC-relation is about 1 or higher. For further 19 drug agents an environmental risk is to be assumed because of their environmental behaviour without support by ecotoxicological data at present.

Conclusion

Although there is only a small base of valid ecotoxicological data, this risk assessment shows that adverse effects in the aquatic environment by some drug agents cannot be excluded. However, it should be noted that this first assessment gives only a crude orientation. Appropriate test data are necessary to refine the assessment in future.     

Moosmonitoring als Spiegel der Landnutzung?

Goal, Scope and Background

The study was conducted to test the hypothesis that the regional variability of nitrogen (N) and metal accumulations in terrestrial ecosystems are due to historical and recent ways of land use. To this end, in two regions of Central Europe the metal and N accumulations in both regions should be examined by comparative moss analysis. The regions should be of quantitatively specified representativity for selected ecological characteristics of Europe. Within both regions these characteristics should be covered by the sites where the moss samples were collected. The number of samples should allow for geostatistical estimation of the measured nitrogen and metal loads.

Methods

The two regions of investigation were selected according to an ecological land classification of Europe which was computed by classification trees. Within each of both research areas the sampling points were localized according to the areas occupied by the ecologically defined land classes. The sampling and chemical analysis of mosses was conducted in accordance with an appropriate UNECE guideline by means of ICP-MS (metals) and combustion analysis (N). The quality of measurements was assured using certified reference materials. The differences of deposition loads were tested for statistical significance with regard to time and space. Variogram analysis was used to examine and model the spatial autocorrelation function of the measurements. Ordinary kriging was then applied for surface estimations.

Results

By use of the ecological regionalisation of Europe the Weser-Ems Region (WER) and the Euro Region Nissa (ERN) were selected for investigation. The sampling sites represent quite well the natural landscapes and the land use categories of both regions. The measurement values corroborate the decline of metal accumulation observed since the beginning of the European Mosses Monitoring Survey in 1990. The metal loads of the mosses in the ERN exceed those in the WER significantly. The opposite holds true for the N concentrations: those in the WER are significantly higher than those in the ERN.

Discussion

The decrease of heavy metal emissions is correlated with lowered deposition and accumulation rates in terrestrial ecosystems. The accumulation of nitrogen in the biosphere is not following this trend.

Conclusions

The technique of moss analysis is adequate for spatially valid biomonitoring of spatial and temporal trends of metals and nitrogen in terrestrial ecosystems. By this, it enables to prove the efficiency of environmental policies.

Recommendations and Perspectives

The accumulation of N in ecosystems is still a serious environmental problem. Related ecological impacts are the eutrophication of aquatic ecosystems like ground waters, lakes, rivers and oceans as well as the biocoenotic changes in terrestrial ecosystems. Thus, a statistically valid exposure analysis must encompass both, accumulation of metals and N bioaccumulation. Further, the bioaccumulation of persistent organic pollutants should be monitored. Finally, environmental biomonitoring should be conducted in much closer contact with human health aspects.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

Energy at work: A measurement validation and linkage to unit effectiveness

We introduce the notion that the energy of individuals can manifest as a higher‐level, collective construct. To this end, we conducted four independent studies to investigate the viability and importance of the collective energy construct as assessed by a new survey instrument—the productive energy measure (PEM). Study 1 (n = 2208) included exploratory and confirmatory factor analyses to explore the underlying factor structure of PEM. Study 2 (n = 660) cross‐validated the same factor structure in an independent sample. In study 3, we administered the PEM to more than 5000 employees from 145 departments located in five countries. Results from measurement invariance, statistical aggregation, convergent, and discriminant‐validity assessments offered additional support for the construct validity of PEM. In terms of predictive and incremental validity, the PEM was positively associated with three collective attitudes—units' commitment to goals, the organization, and overall satisfaction. In study 4, we explored the relationship between the productive energy of firms and their overall performance. Using data from 92 firms (n = 5939_employees), we found a positive relationship between the PEM (aggregated to the firm level) and the performance of those firms. Copyright © 2011 John Wiley & Sons, Ltd.