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.     

Evaluation of hexachlorocyclohexane contamination from the last lindane production plant operating in India

Purpose

??-Hexachlorocyclohexane (HCH), ??-HCH, and lindane (??-HCH) were listed as persistent organic pollutants by the Stockholm Convention in 2009 and hence must be phased out and their wastes/stockpiles eliminated. At the last operating lindane manufacturing unit, we conducted a preliminary evaluation of HCH contamination levels in soil and water samples collected around the production area and the vicinity of a major dumpsite to inform the design of processes for an appropriate implementation of the Convention.

Methods

Soil and water samples on and around the production site and a major waste dumpsite were measured for HCH levels.

Results

All soil samples taken at the lindane production facility and dumpsite and in their vicinity were contaminated with an isomer pattern characteristic of HCH production waste. At the dumpsite surface samples contained up to 450?g?kg^?1 ?? HCH suggesting that the waste HCH isomers were simply dumped at this location. Ground water in the vicinity and river water was found to be contaminated with 0.2 to 0.4?mg?l^?1 of HCH waste isomers. The total quantity of deposited HCH wastes from the lindane production unit was estimated at between 36,000 and 54,000?t.

Conclusions

The contamination levels in ground and river water suggest significant run-off from the dumped HCH wastes and contamination of drinking water resources. The extent of dumping urgently needs to be assessed regarding the risks to human and ecosystem health. A plan for securing the waste isomers needs to be developed and implemented together with a plan for their final elimination. As part of the assessment, any polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) generated during HCH recycling operations need to be monitored.     

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.     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

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.     

Biotic and abiotic degradation of illicit drugs, their precursor, and by-products in soil

This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories.     

Reducing phosphorus flux from organic soils in surface flow treatment wetlands

Treatment wetlands have a finite period of effective nutrient removal after which treatment efficiency declines. This is due to the accumulation of organic matter which decreases the capacity and hydraulic retention time of the wetland. We investigated four potential solutions to improve the soluble reactive P (SRP) removal of a municipal wastewater treatment wetland soil including; dry down, surface additions of alum or calcium carbonate and physical removal of the accreted organic soil under both aerobic and anaerobic water column conditions. The flux of SRP from the soil to the water column under aerobic conditions was higher for the continuously flooded controls (1.1 ± 0.4 mg P m⁻² d⁻¹), dry down (1.5 ± 0.9 mg P m⁻² d⁻¹) and CaCO₃ (0.8 ± 0.7 mg P m⁻² d⁻¹) treatments while the soil removal and alum treatments were significantly lower at 0.02 ± 0.10 and −0.07 ± 0.02 mg P m⁻² d⁻¹, respectively. These results demonstrate that the two most effective management strategies at sequestering SRP were organic soil removal and alum additions. There are difficulties and costs associated with removal and disposal of soils from a treatment wetland. Therefore our findings suggest that alum addition may be the most cost effective and efficient means of increasing the sequestering of P in aging treatment wetlands experiencing reduced P removal rates. However, more research is needed to determine the longer term effects of alum buildup in the organic soil on the wetland biota, in particular, on the macrophytes and invertebrates. Since alum effectiveness is time limited, a longer term solution to P flux may favor the organic soil removal.     

Partitioning of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) between water and sediment

Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (K_OC) decreased in the following order: PFOSA (log K_OC = 4.1 ± 0.35 cm³ g⁻¹) > PFOS (3.7 ± 0.56 cm³ g⁻¹) > PFOA (2.4 ± 0.12 cm³ g⁻¹). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate.