The endocrine disrupting potential of sediments from the Upper Danube River (Germany) as revealed by in vitro bioassays and chemical analysis

Introduction  

The present study was part of a comprehensive weight-of-evidence approach with the goal of identifying potential causes for the declines in fish populations, which have been observed during the past decades in the Upper Danube River.     

Analysis and fit of surface CO2 concentrations at a rural site

Purpose

The impact of CO₂ urban plume in a rural area was investigated by concentrations recorded near surface.

Methods

CO₂ dry concentrations at three levels near surface were recorded for about 8 months at a rural site. Daily cycles were obtained and directional analysis was made with percentiles. Several functions were used to fit background and plume concentrations and the goodness of fit was evaluated with different statistics, which were also compared.

Results

Daily cycle showed a difference of around 2 ppm during the night between the lowest (1.8 m) and the highest (8.3 m) levels. Weighting functions of the directional analysis revealed the influence of the Valladolid urban plume. Two regions were established, with local factors prevailing below 3 m?s^?1 and transport dominating above 6 m?s^?1. The best fit was achieved with a quadratic function for the background and a cubic function for the plume due to the lack of symmetry observed. Gamma and Weibull distributions were also successfully used. Some statistics, such as the root mean square error (RMSE), stood out when evaluating the goodness of fit, whilst others were discarded due to their extremely low values and the lack of sensitivity against the functions used. Finally, a comprehensive metric merging several statistics was also tested with slight differences against RMSE.     

Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs��a global perspective on the management of Lindane and its waste isomers

Purpose

Hexachlorocyclohexane (HCH) isomers (??-, ??- and ??- (Lindane)) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention, and therefore, the legacy of HCH and Lindane production became a contemporary topic of global relevance. This article wants to briefly summarise the outcomes of the Stockholm Convention process and make an estimation of the amount of HCH waste generated and dumped in the former Lindane/HCH-producing countries.

Results

In a preliminary assessment, the countries and the respective amount of HCH residues stored and deposited from Lindane production are estimated. Between 4 and 7 million tonnes of wastes of toxic, persistent and bioaccumulative residues (largely consisting of alpha- (approx. 80%) and beta-HCH) are estimated to have been produced and discarded around the globe during 60 years of Lindane production. For approximately 1.9 million tonnes, information is available regarding deposition. Countries are: Austria, Brazil, China, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, USA, and former USSR. The paper highlights the environmental relevance of deposited HCH wastes and the related POPs?? contaminated sites and provides suggestions for further steps to address the challenge of the legacy of HCH/Lindane production.

Conclusion

It can be expected that most locations where HCH waste was discarded/stockpiled are not secured and that critical environmental impacts are resulting from leaching and volatilisation. As parties to the Stockholm Convention are legally required to take action to stop further POPs pollution, identification and evaluation of such sites are necessary.     

Effects of perfluorinated compounds on development of zebrafish embryos

Perfluorinated compounds (PFCs) have been widely used in industrial and consumer products and frequently detected in many environmental media. Potential reproductive effects of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) have been reported in mice, rats and water birds. PFOS and PFOA were also confirmed developing toxicants towards zebrafish embryos; however, the reported effect concentrations were contradictory. Polyfluorinated alkylated phosphate ester surfactants (including FC807) are precursor of PFOS and PFOA; however, there is no published information about the effects of FC807 and PFNA on zebrafish embryos. Therefore, this study was conducted to determine the effects of these four PFCs on zebrafish embryos. Normal fertilized zebrafish embryos were selected to be exposed to several concentrations of PFOA, PFNA, PFOS or FC807 in 24-well cell culture plates. A digital camera was used to image morphological anomalies of embryos with a stereomicroscope. Embryos were observed through matching up to 96-h post-fertilization (hpf) and rates of survival and abnormalities recorded. PFCs caused lethality in a concentration-dependent manner with potential toxicity in the order of PFOS > FC807 > PFNA > PFOA based on 72-h LC(50). Forty-eight-hour post-fertilization pericardial edema and 72- or 96-hpf spine crooked malformation were all observed. PFOA, PFNA, PFOS and FC807 all caused structural abnormalities using early stages of development of zebrafish. The PFCs all retarded the development of zebrafish embryos. The toxicity of the PFCs was related to the length of the PFC chain and functional groups.     

Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.     

Biochemical biomarkers in Nile tilapia (Oreochromis niloticus) after short-term exposure to diesel oil, pure biodiesel and biodiesel blends

Fossil fuels such as diesel are being gradually replaced by biodiesel, a renewable energy source, cheaper and less polluting. However, little is known about the toxic effects of this new energy source on aquatic organisms. Thus, we evaluated biochemical biomarkers related to oxidative stress in Nile tilapia (Oreochromis niloticus) after two and seven exposure days to diesel and pure biodiesel (B100) and blends B5 and B20 at concentrations of 0.01 and 0.1 mL L⁻¹. The hepatic ethoxyresorufin-O-deethylase activity was highly induced in all groups, except for those animals exposed to B100. There was an increase in lipid peroxidation in liver and gills in the group exposed to the higher concentration of B5. All treatments caused a significant increase in the levels of 1-hydroxypyrene excreted in the bile after 2 and 7 d, except for those fish exposed to B100. The hepatic glutathione-S-transferase increased after 7 d in animals exposed to the higher concentration of diesel and in the gill of fish exposed to the higher concentration of pure diesel and B5, but decreased for the two tested concentrations of B100. Superoxide dismutase, catalase and glutathione peroxidase also presented significant changes according to the treatments for all groups, including B100. Biodiesel B20 in the conditions tested had fewer adverse effects than diesel and B5 for the Nile tilapia, and can be suggested as a less harmful fuel in substitution to diesel. However, even B100 could activate biochemical responses in fish, at the experimental conditions tested, indicating that this fuel can also represent a risk to the aquatic biota.     

Redistribution of free tropospheric chemical species over West Africa: radicals (OH and HO₂), peroxide (H₂O₂) and acids (HNO₃ and H₂SO₄)

The purpose of this paper is to study the redistribution of chemical species (OH, HO₂, H₂O₂, HNO₃ and H₂SO₄) over West Africa, where the cloud cover is ubiquitously present, and where deep convection often develops. In this area, because of these cloud systems, chemical species are redistributed by the ascending and descending flow, or leached if they are soluble. So, we carry out a mesoscale study using the Regional Atmospheric Modelling System (RAMS) coupled to a code of gas and aqueous chemistry (RAMS_Chemistry). It takes into account all processes under mesh. We examine several cases following the period (November and July), with inputs emissions (anthropogenic, biogenic and biomass burning). The radicals OH and HO₂ are an indicator of possibilities for chemical activity. They characterize the oxidizing power of the atmosphere and are very strong oxidants. The acids HNO₃ and H₂SO₄ are interesting in their transformation into nitrates and sulfates in precipitation. In November, when photochemistry is active during an event of biomass burning, concentrations of chemical species are higher than those of November in the absence of biomass burning. The concentrations of nitric acid double and sulfuric acid increases 70 times. In addition, the concentrations are even lower in July if there is a deep convection. Compared to measures of the African Monsoon Multidisciplinary Analysis (AMMA), the results and observations of radicals OH and HO₂ are the same order of magnitude. Emissions from biomass burning increase the concentrations of acid and peroxide, and a deep convection cloud allows the solubility and the washing out of species, reducing their concentration. Rainfalls play a major role in solubility and washing out acids, peroxides and radicals in this region.     

Salinity increases mobility of heavy metals in soils

The effect of salinity induced by CaCl₂, MgCl₂, NaCl and Na₂SO₄ on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl₂ and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl₂ was applied, Cd and Cu were mobilized the most. Finally, an increase of Na₂SO₄ also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl₂ and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca²⁺ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg²⁺. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca²⁺ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.     

Mobility of Cd and Cu in formulated sediments coated with iron hydroxides and/or humic acids: a DGT and DGT-PROFS modeling approach

The diffusive gradients technique in thin films (DGT) was used to investigate the kinetic resupply of Cd and Cu to pore water from the solid phase. For the sake of simplification, experiments were performed using formulated sediments that differed in the presence or absence of humic acids (HA) and/or of iron hydroxides (i.e., goethite and ferrihydrite). The effects of the time after the contamination of the solid phase (aging effect) on formulated sediments that were coated with goethite and HA and spiked with Cd were also evaluated. Kinetic DGT results were interpreted using the newly developed, multi-compartmental model DGT-PROFS.Due to Cu humate formation, the addition of HA slightly increased the Cu concentration in the pore water independent of the effect of the iron hydroxide coating on the formulated sediments and slightly decreased that of Cd. The impact of 8-190 d of aging resulted in a significant decrease in the Cd concentration of the pore water over an increasing incubation time.Modeling our results with DGT-PROFS led to the following conclusions concerning the impact of HA and iron hydroxides on Cd and Cu availability. First, in the presence of HA and absence of iron hydroxides, Cd is associated mainly with weak sites, while Cu is bound to strong sites. Similarly, in the presence of both iron hydroxides and HA, Cu appeared to be more heavily associated with the strong sites than did Cd. When the incubation time increased from 8 to 190 d, a proportion of Cd initially adsorbed onto weak sites transferred to the strong sites, suggesting that the adsorption of Cd on sediments is controlled partially by slow kinetic processes.