Photocatalytic mechanisms of indoleamine destruction by the quinalphos metabolite 2-hydroxyquinoxaline: a study on melatonin and its precursors serotonin and N-acetylserotonin

The redox-active quinalphos main metabolite, 2-hydroxyquinoxaline, is particularly effective under excitation by light. We have studied the photocatalytic destruction of melatonin and its precursors, because the cytoprotective indoleamine has been detected in high quantities in mammalian skin. In photooxidation reactions, in which melatonin, N-acetylserotonin and serotonin are destroyed by 2-hydroxyquinoxaline, the photocatalyst is virtually not consumed. Rates of melatonin and serotonin destruction are not changed by the singlet oxygen quencher 1,4-diazabicyclo-(2,2,2)-octane, indicating that this oxygen species is not involved in the primary reactions, so that the persistence of 2-hydroxyquinoxaline has to be explained by redox cycling. This should imply formation of an organic radical, presumably the quinoxaline-2-oxyl radical, from which 2-hydroxyquinoxaline is regenerated by electron abstraction from indolic radical scavengers. Electron donation by 2-hydroxyquinoxaline is demonstrated by reduction of the 2,2′-azino-bis-(3-ethylbenzthiazolinyl-6-sulfonic acid) cation radical under ultrasound excitation. The compound 2-hydroxyquinoxaline interacts with the specific superoxide anion scavenger Tiron. Formation of oligomeric products from melatonin and serotonin is strongly inhibited by sodium dithionite. Products from photocatalytic indolamine conversion are predominantly dimers and oligomers. No kynuramines were detected in the case of serotonin oxidation, and melatonin's otherwise prevailing oxidation product N ¹-acetyl-N ²-formyl-5-methoxykynuramine, another cytoprotective metabolite, is only formed in relatively small quantities. The proportion between products from melatonin is changed by 1,4-diazabicyclo-(2,2,2)-octane: singlet oxygen, also formed under the influence of excited 2-hydroxyquinoxaline, only affects secondary reactions.     

Effects of light and temperature fluctuations on the growth of Myriophyllum spicatum in toxicity tests—a model-based analysis

Laboratory toxicity tests are a key component of the aquatic risk assessments of chemicals. Toxicity tests with Myriophyllum spicatum are conducted based on working procedures that provide detailed instructions on how to set up the experiment, e.g., which experimental design is necessary to get reproducible and thus comparable results. Approved working procedures are established by analyzing numerous toxicity tests to find a compromise between practical reasons (e.g., acceptable ranges of ambient conditions as they cannot be kept completely constant) and the ability for detecting growth alterations. However, the benefit of each step of a working procedure, e.g., the random repositioning of test beakers, cannot be exactly quantified, although this information might be useful to evaluate working procedures. In this paper, a growth model of M. spicatum was developed and used to assess the impact of temperature and light fluctuations within the standardized setup. It was analyzed how important it is to randomly reassign the location of each plant during laboratory tests to keep differences between the relative growth rates of individual plants low. Moreover, two examples are presented on how modeling can give insight into toxicity testing. Results showed that randomly repositioning of individual plants during an experiment can compensate for fluctuations of light and temperature. A method is presented on how models can be used to improve experimental designs and to quantify their benefits by predicting growth responses.     

Screening for potential effects of endocrine-disrupting chemicals in peri-urban creeks and rivers in Melbourne, Australia using mosquitofish and recombinant receptor–reporter gene assays

Sexually mature male mosquitofish (Gambusia holbrooki) were collected from various sites around Melbourne in 2009 to evaluate the performance of gonopodial indices as a biomarker for endocrine disruption in Melbourne's waterways. The mosquitofish indices assessed were body length (BL), gonopodial length (GL)/BL ratio, ray 4:6 ratio and the absence or presence of hooks and serrae, and these varied between sites. The study was complemented by measurements of estrogenic, retinoid, thyroid and aryl hydrocarbon (AhR) receptor activities of the water. Male mosquitofish were 16.3–21.5 mm in length, and although there was a statistically significant positive relationship showing that bigger fish had longer gonopodia than small fish (r2 = 0.52, p < 0.001), there were few significant differences in GL/BL ratio of fish between sites. Measured estrogenic activity was mostly in the range 0.1–1.7 ng/L EEQ, with one site having much higher levels (~12 ng/L EEQ). Aryl hydrocarbon (AhR) receptor activity was observed in all water samples (7–180 ng/L βNF EQ), although there was no consistent pattern in the level of AhR activity observed, i.e., ‘clean’ sites were as likely to return a high AhR activity response as urban or wastewater treatment plant (WWTP)-impacted sites. There was no correlation between measurements of receptor actvity and gonopodial length (GL):BL ratio and BL. We conclude that the mosquitofish gonopodia only fulfills part of the criteria for biomarker selection for screening. The mosquitofish indices assessed were cheap and easy-to-perform procedures; however, there is no baseline data from the selected sites to evaluate whether differences in the morpholical indices observed at a site were a result of natural selection in the population or due to estrogenic exposure.     

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.     

Dechlorination and organohalide-respiring bacteria dynamics in sediment samples of the Yangtze Three Gorges Reservoir

Several groups of bacteria such as Dehalococcoides spp., Dehalobacter spp., Desulfomonile spp., Desulfuromonas spp., or Desulfitobacterium spp. are able to dehalogenate chlorinated pollutants such as chloroethenes, chlorobenzenes, or polychlorinated biphenyls under anaerobic conditions. In order to assess the dechlorination potential in Yangtze sediment samples, the presence and activity of the reductively dechlorinating bacteria were studied in anaerobic batch tests. Eighteen sediment samples were taken in the Three Gorges Reservoir catchment area of the Yangtze River, including the tributaries Jialing River, Daning River, and Xiangxi River. Polymerase chain reaction analysis indicated the presence of dechlorinating bacteria in most samples, with varying dechlorinating microbial community compositions at different sampling locations. Subsequently, anaerobic reductive dechlorination of tetrachloroethene (PCE) was tested after the addition of electron donors. Most cultures dechlorinated PCE completely to ethene via cis-dichloroethene (cis-DCE) or trans-dichloroethene. Dehalogenating activity corresponded to increasing numbers of Dehalobacter spp., Desulfomonile spp., Desulfitobacterium spp., or Dehalococcoides spp. If no bacteria of the genus Dehalococcoides spp. were present in the sediment, reductive dechlorination stopped at cis-DCE. Our results demonstrate the presence of viable dechlorinating bacteria in Yangtze samples, indicating their relevance for pollutant turnover.     

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.     

Approximation and spatial regionalization of rainfall erosivity based on sparse data in a mountainous catchment of the Yangtze River in Central China

In densely populated countries like China, clean water is one of the most challenging issues of prospective politics and environmental planning. Water pollution and eutrophication by excessive input of nitrogen and phosphorous from nonpoint sources is mostly linked to soil erosion from agricultural land. In order to prevent such water pollution by diffuse matter fluxes, knowledge about the extent of soil loss and the spatial distribution of hot spots of soil erosion is essential. In remote areas such as the mountainous regions of the upper and middle reaches of the Yangtze River, rainfall data are scarce. Since rainfall erosivity is one of the key factors in soil erosion modeling, e.g., expressed as R factor in the Revised Universal Soil Loss Equation model, a methodology is needed to spatially determine rainfall erosivity. Our study aims at the approximation and spatial regionalization of rainfall erosivity from sparse data in the large (3,200 km²) and strongly mountainous catchment of the Xiangxi River, a first order tributary to the Yangtze River close to the Three Gorges Dam. As data on rainfall were only obtainable in daily records for one climate station in the central part of the catchment and five stations in its surrounding area, we approximated rainfall erosivity as R factors using regression analysis combined with elevation bands derived from a digital elevation model. The mean annual R factor (R _a) amounts for approximately 5,222 MJ?mm?ha^?1?h^?1?a^?1. With increasing altitudes, R _a rises up to maximum 7,547 MJ?mm ha^?1?h^?1 a^?1 at an altitude of 3,078 m a.s.l. At the outlet of the Xiangxi catchment erosivity is at minimum with approximate R _a?=?1,986 MJ?mm?ha^?1?h^?1?a^?1. The comparison of our results with R factors from high-resolution measurements at comparable study sites close to the Xiangxi catchment shows good consistance and allows us to calculate grid-based R _a as input for a spatially high-resolution and area-specific assessment of soil erosion risk.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Goals and remedial strategies for water quality and wildlife management in a coastal lagoon--a case-study of Ringkøbing Fjord, Denmark

The aim of this work is (1) to discuss approaches and tools to set management goals using operational indicators for coastal management (i.e., indicators that are easy to measure, understand and predict) and validated predictive models and (2) to discuss remedial strategies for sustainable coastal management regarding water quality and the abundance of fish, waterfowl and large aquatic plants. These approaches are exemplified using data from Ringkøbing Fjord, Denmark, which has undergone two major regime shifts during the last decades. This work discusses the changes taken place during the period from 1980 to 2004 (when there are good empirical data). For Ringkøbing Fjord, which is a very shallow, well-oxygenated lagoon dominated by resuspension processes, we have targeted on the following operational indicators, which are meant to reflect seasonal median values for the entire defined coastal area (the ecosystem scale) and not conditions at individual sites or data from shorter time periods: Secchi depth (as a standard measure of water clarity) and chlorophyll-a concentrations (as a key measure of algal biomass). The operational indicators are regulated by a set of standard abiotic factors, such as salinity, suspended particulate matter (SPM), nutrient concentrations (N and P), coastal morphometry and water exchange. Such relationships are quantified using well-tested, general quantitative models, which illustrate how these indicators are interrelated and how they reflect fundamental aspects of coastal ecosystems. We demonstrate that the regime shift in the lagoon can be modelled and quantitatively explained and is related to changes in salinity and nutrient inflow. A very important threshold is linked to increased salinities in the lagoon. For example, when the mean annual salinity is higher than about 9.5‰, large numbers of saltwater species of clams can survive and influence the structure and function of the ecosystem in profound ways. The model also illustrates the dynamic response to changes in nutrient loading. We have presented several management strategies with the goal of keeping the Secchi depth at 2 m, which would stimulate the growth of higher aquatic plants, which are fundamental for fish production and bird abundance in the lagoon. Given the fact that the Secchi depth depends on many variable factors (temperature, TP-inflow from land, salinity, changes in biomasses of macrophytes and clams, which are accounted for in these simulations), our results indicate that in practice it will likely be very difficult to reach that goal. However, it would be realistic to maintain a Secchi depth of 1.5 m if the variability in salinity is minimized and the mean salinity is kept at about 10.2‰.