Toxicity models of metal mixtures established on the basis of “additivity” and “interactions”

Observed effects of metal mixtures on animals and plants often differ from the estimates, which are commonly calculated by adding up the biological responses of individual metals. This difference from additivity is commonly referred to as being a consequence of specific interactions between metals. The science of how to quantify metal interactions and whether to include them in risk assessment models is in its infancy. This review summarizes the existing predictive tools for evaluating the combined toxicity of metals present in mixtures and indicates the advantages and disadvantages of each method. We intend to provide eco-toxicologists with background information on how to make good use of the tools and how to advance the methods for assessing toxicity of metal mixtures. It is concluded that statistically significant deviations from additivity are not necessarily biologically relevant. Incorporation of interactions between metals in a model does not on forehand mean that the model is more accurate than a model developed based on additivity only. It is recommended to first use a relatively simple method for effect prediction of uninvestigated metal mixtures. To improve the reliability of toxicity modeling for metal mixtures, further efforts should focus on balancing the relationship between the significance of statistics and the biological meaning, and unraveling the toxicity mechanisms of metals and their mixtures.

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An integrated approach to model the biomagnification of organic pollutants in aquatic food webs of the Yangtze Three Gorges Reservoir ecosystem using adapted pollution scenarios

The impounding of the Three Gorges Reservoir (TGR) at the Yangtze River caused large flooding of urban, industrial, and agricultural areas, and profound land use changes took place. Consequently, substantial amounts of organic and inorganic pollutants were released into the reservoir. Additionally, contaminants and nutrients are entering the reservoir by drift, drainage, and runoff from adjacent agricultural areas as well as from sewage of industry, aquacultures, and households. The main aim of the presented research project is a deeper understanding of the processes that determines the bioaccumulation and biomagnification of organic pollutants, i.e., mainly pesticides, in aquatic food webs under the newly developing conditions of the TGR. The project is part of the Yangtze-Hydro environmental program, financed by the German Ministry of Education and Science. In order to test combinations of environmental factors like nutrients and pollution, we use an integrated modeling approach to study the potential accumulation and biomagnification. We describe the integrative modeling approach and the consecutive adaption of the AQUATOX model, used as modeling framework for ecological risk assessment. As a starting point, pre-calibrated simulations were adapted to Yangtze-specific conditions (regionalization). Two exemplary food webs were developed by a thorough review of the pertinent literature. The first typical for the flowing conditions of the original Yangtze River and the Daning River near the city of Wushan, and the second for the stagnant reservoir characteristics of the aforementioned region that is marked by an intermediate between lake and large river communities of aquatic organisms. In close cooperation with German and Chinese partners of the Yangtze-Hydro Research Association, other site-specific parameters were estimated. The MINIBAT project contributed to the calibration of physicochemical and bathymetric parameters, and the TRANSMIC project delivered hydrodynamic models for water volume and flow velocity conditions. The research questions were firstly focused on the definition of scenarios that could depict representative situations regarding food webs, pollution, and flow conditions in the TGR. The food webs and the abiotic site conditions in the main study area near the city of Wushan that determine the environmental preconditions for the organisms were defined. In our conceptual approach, we used the pesticide propanil as a model substance.     

Solution by dilution?—A review on the pollution status of the Yangtze River

The Yangtze River has been a source of life and prosperity for the Chinese people for centuries and is a habitat for a remarkable variety of aquatic species. But the river suffers from huge amounts of urban sewage, agricultural effluents, and industrial wastewater as well as ship navigation wastes along its course. With respect to the vast amounts of water and sediments discharged by the Yangtze River, it is reasonable to ask whether the pollution problem may be solved by simple dilution. This article reviews the past two decades of published research on organic pollutants in the Yangtze River and several adjacent water bodies connected to the main stream, according to a holistic approach. Organic pollutant levels and potential effects of water and sediments on wildlife and humans, measured in vitro, in vivo, and in situ, were critically reviewed. The contamination with organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans, polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and others, of water and sediment along the river was described. Especially Wuhan section and the Yangtze Estuary exhibited stronger pollution than other sections. Bioassays, displaying predominantly the endpoints mutagenicity and endocrine disruption, applied at sediments, drinking water, and surface water indicated a potential health risk in several areas. Aquatic organisms exhibited detectable concentrations of toxic compounds like PCBs, OCPs, PBDEs, and PFCs. Genotoxic effects could also be assessed in situ in fish. To summarize, it can be stated that dilution reduces the ecotoxicological risk in the Yangtze River, but does not eliminate it. Keeping in mind an approximately 14 times greater water discharge compared to the major European river Rhine, the absolute pollution mass transfer of the Yangtze River is of severe concern for the environmental quality of its estuary and the East China Sea. Based on the review, further research needs have been identified.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Phyto/rhizoremediation studies using long-term PCB-contaminated soil

Purpose  

Polychlorinated biphenyls (PCBs) represent a large group of recalcitrant environmental pollutants, differing in the number of chlorine atoms bound to biphenyl ring. Due to their excellent technological properties, PCBs were used as heat-transfer media, for filling transformers and condensers, as paint additives, etc. With increasing knowledge of their toxicity, transfer to food chains and accumulation in living organisms, their production ended in most countries in the 1970s and in 1984 in the former Czechoslovakia. But even a quarter of century after the PCB production ceased, from contaminated areas, the volatile PCBs evaporate and contaminate much larger areas even at very distant parts of the world. For this reason, PCBs still represent a global problem. The main method of PCB removal from contaminated environment is at present the expensive incineration at high temperatures. With the aim of finding effective alternative approaches, we are studying biological methods for PCB removal from the environment. In this paper, we summarise 10 years of studies using long-term PCB-contaminated soil from a dumpsite in South Bohemia, targeted for the use of plants (phytoremediation) and their cooperation with microorganisms in the root zone (rhizoremediation).     

Behavior of a hammerhead ribozyme in aqueous solution at medium to high temperatures

The “RNA world” hypothesis proposes that—early in the evolution of life—RNA molecules played important roles both in information storage and in enzymatic functions. However, this hypothesis seems to be inconsistent with the concept that life may have emerged under hydrothermal conditions since RNA molecules are considered to be labile under such extreme conditions. Presently, the possibility that the last common ancestor of the present organisms was a hyperthermophilic organism which is important to support the hypothesis of the hydrothermal origin of life has been subject of strong discussions. Consequently, it is of importance to study the behavior of RNA molecules under hydrothermal conditions from the viewpoints of stability, catalytic functions, and storage of genetic information of RNA molecules and determination of the upper limit of temperature where life could have emerged. In the present work, self-cleavage of a natural hammerhead ribozyme was examined at temperatures 10–200?°C. Self-cleavage was investigated in the presence of Mg²⁺, which facilitates and accelerates this reaction. Self-cleavage of the hammerhead ribozyme was clearly observed at temperatures up to 60?°C, but at higher temperatures self-cleavage occurs together with hydrolysis and with increasing temperature hydrolysis becomes dominant. The influence of the amount of Mg²⁺ on the reaction rate was also investigated. In addition, we discovered that the reaction proceeds in the presence of high concentrations of monovalent cations (Na⁺ or K⁺), although very slowly. Furthermore, at high temperatures (above 60?°C), monovalent cations protect the ribozyme against degradation.