Occurrence of UV filter compounds from sunscreens in surface waters: regional mass balance in two Swiss lakes

Consumer care products often contain UV filters, organic compounds which absorb ultraviolet light. These compounds may enter surface waters directly (when released from the skin during swimming and bathing) or indirectly via wastewater treatment plants (when released during showering or washed from textiles). Predicted and measured UV filter concentrations were compared in a regional mass balance study for two Swiss lakes: Lake Zurich, a typical midland lake which is also an important drinking water resource, and Hüttnersee, a small bathing lake. Both lakes are extensively used for recreational activities and considerable direct input of UV filters is thus expected. This input was estimated from the number of visitors at swimming areas around the lakes and a survey of the usage of sunscreen products among these visitors. Possible additional indirect input via wastewater treatment plants was not considered in this study. The quantitatively most important UV filters, as indicated by the survey data, ethylhexyl methoxycinnamate, octocrylene, 4-methylbenzylidene camphor, butyl methoxydibenzoylmethane, and benzophenone-3, all lipophilic compounds, were selected for analysis by gas chromatography-mass spectrometry. Concentrations of individual UV filters in water from Lake Zurich were low, ranging from <2 ng l(-1) (detection limit) to 29 ng l(-1), and somewhat higher at Hüttnersee, ranging from <2 to 125 ng l(-1), with the highest concentrations found in summer, consistent with direct inputs to the lakes during this time. The concentrations were clearly lower than predicted from input estimates based on the surveys. This may be in part due to (i) an overestimation of these inputs (e.g. less than the 50% wash-off of UV filters assumed to occur during swimming), and (ii) some removal of these compounds from the lakes by degradation and/or sorption/sedimentation. UV filters were also detected in semipermeable membrane devices (SPMDs) deployed at Lake Zurich and Greifensee, another midland lake, at concentrations of 80-950 ng SPMD(-1), confirming the presence of the compounds in surface waters and indicating a certain potential for bioaccumulation. SPMD-derived water concentrations were in the range of 1-10 ng l(-1) and thus corresponded well with those determined in water directly. No UV filters were detected above blank levels in SPMDs deployed at a remote mountain lake used for background measurements.     

Ecotoxic Effect of Photocatalytic Active Nanoparticles (TiO2) on Algae and Daphnids (8 pp)

Background, Aim and Scope Due to their large potential for manifold applications, the use of nanoparticles is of increasing importance. As large amounts of nanoparticles may reach the environment voluntarily or by accident, attention should be paid on the potential impacts on the environment. First studies on potential environmental effects of photocatalytic TiO2 nanoparticles have been performed on the basis of widely accepted, standardized test systems which originally had been developed for the characterization of chemicals. The methods were adapted to the special requirements of testing photocatalytic nanoparticles. Materials and Methods: Suspensions of two different nanoparticles were illuminated to induce their photocatalytic activity. For testing, the growth inhibition test with the green alga Desmodesmus subspicatus and the immobilization test with the daphnid Daphnia magna were selected and performed following the relevant guidelines (algae: ISO 8692, OECD 201, DIN 38412-33; daphnids: ISO 6341, OECD 202, DIN 38412-30). The guidelines were adapted to meet the special requirements for testing photocatalytic nanoparticles. Results: The results indicate that it is principally possible to determine the ecotoxicity of nanoparticles. It was shown that nanoparticles may have ecotoxicological effects which depend on the nature of the particles. Both products tested differ in their toxicity. Product 1 shows a clear concentration-effect curve in the test with algae (EC50: 44 mg/L). It could be proven that the observed toxicity was not caused by accompanying contaminants, since the toxic effect was comparable for the cleaned and the commercially available product. For product 2, no toxic effects were determined (maximum concentration: 50 mg/L). In the tests with daphnids, toxicity was observed for both products, although the concentration effect-curves were less pronounced. The two products differed in their toxicity; moreover, there was a difference in the toxicity of illuminated and non-illuminated products. Discussion: Both products differ in size and crystalline form, so that these parameters are assumed to contribute to the different toxicities. The concentration-effect curves for daphnids, which are less-pronounced than the curves obtained for algae, may be due to the different test organisms and/or the differing test designs. The increased toxicity of pre-illuminated particles in the tests with daphnids demonstrates that the photocatalytic activity of nanoparticles lasts for a period of time. Conclusions: The following conclusions can be drawn from the test results: (I) It is principally possible to determine the ecotoxicity of (photocatalytic) nanoparticles. Therefore, they can be assessed using methods comparable to the procedures applied for assessing soluble chemicals. - (II) Nanoparticles may exert ecotoxicological effects, which depend on the specific nanoparticle. - (III) Comparable to traditional chemicals, the ecotoxicity depends on the test organisms and their physiology. - (IV) The photocatalytic activity of nanoparticles lasts for a relevant period of time. Therefore, pre-illumination may be sufficient to detect a photocatalytic activity even by using test organisms which are not suitable for application in the pre-illumination-phase. Recommendations and Perspectives: First results are presented which indicate that the topic 'ecotoxicity and environmental effects of nanoparticles' should not be neglected. In testing photocatalytic nanoparticles, there are still many topics that need clarification or improvement, such as the cause for an observed toxicity, the improvement of the test design, the elaboration of a test battery and an assessment strategy. On the basis of optimized test systems, it will be possible to test nanoparticles systematically. If a potential risk by specific photocatalytic particles is known, a risk-benefit analysis can be performed and, if required, risk reducing measures can be taken.     

Identifikation der kfz-bürtigen Schadstoffbelastung mit Hilfe der Verh?ltnisse der stabilen Isotope von Kohlenstoff und Schwefel

Zusammenfassung  Reifen-, Ru?-, Motoren?l-, Asphalt-, Plastik- und Lackproben aus dem Stra?enverkehr wurden auf ihre Kohlenstoff- und Schwefel-isotopenverh?ltnisse mit dem Ziel untersucht, die Frage zu beant-worten, ob diese Isotopenverh?ltnisse als Indikatoren für die Belastungssituation und die Schadstoffquellen bei der Untersuchung von stra?ennahen B?den eingesetzt werden k?nnen. Die δ¹¹C-Werte der technischen Substrate lagen zwischen-30‰ und-18‰ relativ zum PDB-Standard, Dabei zeigte sich aufgrund der unterschiedlichen Herstellungsverfahren eine deutliche Abgrenzung der Substrate untereinander. Asphalt hatte Werte zwischen-23 und-18‰, Ru? zwischen -27 und -22‰ Die Ru?proben unterschieden sich je nach Art des verwendeten Kraftstoffs. Plastik, Lack und Motor?le zeigten ?hnliche δ¹³C-Werte, die zwischen-30 und-27‰ lagen. Reifen haben relativ konstante δ¹³C-Werte um -26‰ Der Einflu? des Stra?enverkehrs auf die δ¹³C-Werte im Stra?ensediment und in stra?ennahen B?den konnte anhand verschiedener Kohlenstoffspezies an einem Transekt an einer Landstra?e aufgezeigt werden. Ein Vergleich mit verkehrstypischen Schwermetallemissionen ergab bei einzelnen Kohlenstoffspezies einen ?hnlichen Verlauf der Schwermetallkonzentrationen und der δ¹³C-Werte. Die δ³⁴S-Werte lagen zwischen -6 und +8‰ relativ zum CDT-Standard. Eine Abgrenzung der Substrate in ihren δ¹⁴S-Werten war hierbei nicht m?glich.      

在波罗的海不同的气候条件下模拟的海面温度和热通量

本文使用由不同的全球模拟所产生的区域性耦合海洋-大气模型,通过数值模型试验探讨了波罗的海气候未来可能的物理状况.将一些情景以及近来的一些气候模拟情况作了比较,以估计气候变化.海面温度总体平均明显地增高2.9℃.平均年平均增温的水平模式主要可由冰盖的减少解释.由大气向波罗的海的热输送表现出季节性变化周期秋季热损失减少,春季热吸收增加,夏季热吸收减少.年际间海面温度的变化一般是在增加.这与北部一些中平滑的频率分布有关.全部热收支表示出海面太阳辐射在增加,而太阳辐射增加由热通量其他组成成分的变化所平衡.     

Agent-based framework for modeling and simulation of resources in self-sustainable human settlements: a case study on water management in an eco-village community in Croatia

A newly developed agent-based framework for modeling, simulation, and evaluation of resource management in self-sustainable human settlements is presented, along with the ability of the framework to prolong the self-sustainability of the observed human settlement system in the simulation environment. In this study the focus is on the analysis of a conducted water management simulation based on observations of an existing eco-village in Croatia, in the context of producing, storing, and consuming water as a resource. The conducted research shows that the developed framework was able to prolong the self-sustainability of localized water production, storage, and consumption dynamics when managing the water allocation with the use of self-sustainability mechanisms, in comparison to water management without using such mechanisms, under the same initial conditions. The work is placed within the context of sustainable development, Internet of Things, as well as Environmental Internet of Things areas of research, analyzing the ambiguous relationship between the terms ‘sustainable development’ and ‘self-sustainability’.     

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments.     

Short-run allocation of emissions allowances and long-term goals for climate policy

We use economic analysis to evaluate grandfathering, auctioning, and benchmarking approaches for allocation of emissions allowances and then discuss practical experience from European and American schemes. In principle, auctions are superior from the viewpoints of efficiency, fairness, transparency, and simplicity. In practice, auctions have been opposed by important sectors of industry, which argue that carbon pricing without compensation would harm international competitiveness. In the European Union's Emissions Trading System, this concern led to grandfathering that is updated at various intervals. Unfortunately, updating gives industry an incentive to change behavior to influence future allocation. Furthermore, the wealth transferred to incumbent firms can be significantly larger than the extra costs incurred, leading to windfall profits. Meanwhile, potential auction revenues are not available to reduce other taxes. By circumscribing free allocation, benchmarking can target competitiveness concerns, incur less wealth transfer, and provide a strategy consistent with transitioning to auctions in the long run.     

Phenomenological compensation of thermally caused position and orientation errors of rotary axes

Thermal errors of machine tools are one of the major sources of inaccuracy. Therefore, the reduction of temperature induced deviations or the compensation of the resulting tool center point (TCP) errors have been of strong interest to the manufacturing industry for a couple of years. Up to now, the observation of the environment, the main spindle, the linear axes and the machine bed were in the focus of research, but with the rising demand for 5-axis machine tools and the increasing requirements regarding their accuracy, the analysis of the thermal behavior of rotary axes becomes more and more important. This paper gives an overview of corresponding thermal measurements of machine tools. The thermal behavior of rotary and swiveling axes is analyzed in detail. A simulation model and an approach for a phenomenological compensation of the TCP error are introduced and verified by measurements.     

Endocrine disruption of water and sediment extracts in a non-radioactive dot blot/RNAse protection-assay using isolated hepatocytes of rainbow trout

Goal, Scope and Background In order to evaluate the estrogenic activity of sediments and XAD water extracts of selected sites of the catchment area of the River Neckar, a river system in Southern Germany, an integrative assessment approach was used to assess the ecological hazard potential of endocrine-disrupting compounds in sediment and water. Methods The approach is based on estrogen receptor-mediated vitellogenin synthesis induced in isolated hepatocytes of rainbow trout and quantified in a non-radioactive dot blot/RNAse protection-assay in parallel to comprehensive chemical analyses of estrogenic substances. Results and Discussion Numerous investigated extracts revealed an estrogen activity comparable to that of the positive control (1 nM 17?-estradiol corresponding to 270 ng/L in the test medium). Based on a concentration factor of 30 in the extracts and a recovery of XAD resins of approximately 80 %, 17?-estradiol equivalent concentrations between 20 and 26.7 ng/L could be calculated downstream of a sewage treatment plant (< 0.1 ng/L for a reference site). A comparison of the bioassay-derived Bio-TEQs (toxicity equivalents) and the Chem-TEQs revealed a high correlation with a Pearson coefficient of 0.85, indicating that the same ranking of the samples could be obtained with respect to the endocrine disrupting potential with both chemical and bioanalytical analysis. However, the TEQ concentrations computed from chemical analyses were significantly lower than the bioassay-derived TEQ concentrations. In fact, in none of the samples, more than 14 % of the vitellogenin-inducing potency could be attributed to the substances (steroids, alkylphenols, bisphenol A, diethylstilbestrol) analyzed. A comparison of the endocrine disrupting potential of sediments extracted by the solvents acetone and methanol revealed lower biological effects for acetone-extracted samples. Possible reasons may be a masking of endocrine effects in acetone extracts by cytotoxicity, a low extraction efficiency of the solvent acetone, or anti-estrogen potencies of some extracted sediment compounds. Using a mass balance approach, the contribution of the compounds analyzed chemically (Chem-TEQs) to the total endocrine activity (Bio-TEQs) was calculated. Based on the very low detection limits, particularly of the steroids with their high TEF factors, results revealed that a calculation of the Chem-TEQs is associated with considerable scale inaccuracy: Whereas only 7-15 % of the biological effectiveness (Bio-TEQs) could be explained by endocrine substances identified above the detection limits, the assumption of concentrations slightly below the given detection limits would result in a significant over estimation (137-197 %) of the Bio-TEQs. Even the interassay variation of the dot blot assay with different fish donors for primary hepatocyte (factor 2 - 2.5) is relatively low, when compared to the large range of the Chem-TEQ concentrations (factor 20) obtained when applying different modes of calculation. Conclusions and Outlook Overall, only a minor portion of the endocrine activity detected by bioassays could be linked to compounds identified by chemical analysis. In vitro assays for assessment of endocrine activities are useful as sensitive integrating methods that provide quantitative estimates of the total activity of particular receptor-mediated responses. Although discrepancies may also result from different bioanalytical approaches, it is overall likely that bioanalytical and not chemical analytical approaches give the correct estimate of endocrine disrupting potencies in environmental samples. As a conclusion, assessment of endocrine disruption based on chemical analysis alone does not appear sufficient and further research into the spectrum of substances with potential endocrine activity as well as into additive or even synergistic effects in complex environmental samples is urgently needed.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.