Characterization of silver release from commercially available functional (nano)textiles

Silver, both in the nano as well as in other forms, is used in many applications including antimicrobial textiles. Washing of such textiles has already been identified as an important process that results in the release of silver into wastewater. This study thus investigated the release of silver from eight different commercially available silver-textiles during a washing and rinsing cycle. The silver released was size-fractionated and characterized using electron microscopy. In addition, the antimicrobial functionality of the textiles was tested before and after washing. Three of the textiles contained nanosized silver (labeled or confirmed by manufacturers’ information), another used a metallic silver wire and four contained silver in undeclared form. The initial silver content of the textiles was between 1.5 and 2925 mg Ag/kg. Only four of the investigated textiles leached detectable amounts of silver, of which 34-80% was in the form of particles larger than 450 nm. Microscopic analysis of the particles released in the washing solutions identified Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large AgCl particles, nanosilver sulfide and metallic nano-Ag, respectively. The nanoparticles were mainly found in highly agglomerated form. The identified nanotextiles showed the highest antimicrobial activity, whereas some of the other textiles, e.g. the one with a silver wire and the one with the lowest silver content, did not reduce the growth of bacteria at all. The results show that different silver textiles release different forms of silver during washing and that among the textiles investigated AgCl was the most frequently observed chemical form in the washwater.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Captopril and its dimer captopril disulfide: photodegradation, aerobic biodegradation and identification of transformation products by HPLC-UV and LC-ion trap-MS(n)

In some countries effluents from hospitals and households are directly emitted into open ditches without any further treatment and with very little dilution. Under such circumstances photo- and biodegradation in the environment can occur. However, these processes do not necessarily end up with the complete mineralization of a chemical. Therefore, the biodegradability of photoproduct(s) by environmental bacteria is of interest. Cardiovascular diseases are the number one cause of death globally. Captopril (CP) is used in this study as it is widely used in Egypt and stated as one of the essential drugs in Egypt for hypertension. Three tests from the OECD series were used for biodegradation testing: Closed Bottle test (CBT; OECD 301 D), Manometric Respirometry test (MRT; OECD 301 F) and the modified Zahn-Wellens test (ZWT; OECD 302 B). Photodegradation (150 W medium-pressure Hg-lamp) of CP was studied. Also CBT was performed for captopril disulfide (CPDS) and samples received after 64 min and 512 min of photolysis. The primary elimination of CP and CPDS was monitored by LC-UV at 210 nm and structures of photoproducts were assessed by LC-UV-MS/MS (ion trap). Analysis of photodegradation samples by LC-MS/MS revealed CP sulfonic acid as the major photodegradation product of CP. No biodegradation was observed for CP, CPDS and of the mixture resulting from photo-treatment after 64 min in CBT. Partial biodegradation in the CBT and MRT was observed in samples taken after 512 min photolysis and for CP itself in MRT. Complete biodegradation and mineralization of CP occurred in the ZWT.     

Toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles

This study evaluates the toxic effects of deltamethrin and λ-cyhalothrin on Xenopus laevis tadpoles after 168 h of exposure. The LC(50) of deltamethrin and λ-cyhalothrin at 168 h was calculated as the μg of active ingredient per liter (μg AI/L). According to these values, the LC(50) was 6.26 and 3.94 μg AI/L for deltamethrin and λ-cyhalothrin, respectively. Several enzymes were studied for early signs of intoxication following exposure to the pesticides for 24 h. Glutathione-S-transferase,carboxylesterase, and lactate dehydrogenase were inhibited by λ-cyhalothrin, and both pesticides inhibited acid phosphatase and aspartate aminotransferase. In contrast, acetylcholinesterase was activated by deltamethrin. The results suggest that X. laevis is sensitive to the pyrethroids that were tested, and the enzyme responses suggest that they are potential biomarkers for evaluating the toxic effect of pyrethroids on amphibians in environmental conditions.     

Developmental exposure to diuron causes splenotoxicity in male Sprague-Dawley rat pups

This study investigated whether perinatal exposure to diuron [3-(3,4-dichlorophenyl)-1-1-dimethylurea] might exert adverse effects on rat lymphoid organs. Pregnant Sprague-Dawley (SD) rats were exposed to diuron at 500, 750 or 1250 ppm in the diet from gestational days (GD) 12-21 and during lactation. At postnatal day (PND) 42, male pups were euthanized and thymus, spleen, mesenteric lymph node and femur were collected for histopathological analysis. Food consumption and body weight gain were significantly reduced in dams exposed to 1250 ppm during gestation period. Also, Diuron at 750 and 1250 ppm produced: (1) increased relative spleen weight associated histologically with severe congestion in red pulp, (2) enhanced extramedullary hematopoiesis and hemosiderosis as well as (3) depletion of lymphoid follicles in white pulp. Flow cytometric analysis revealed a significant reduction in B lymphocytes (CD45RA+) in male pups but T lymphocytes (CD4+, CD8+ and CD4+/CD8+) were not markedly affected. Thus, data suggest that Diuron-induced maternal toxicity in dams exposed to high dose and perinatal exposure to this herbicide produced spleen toxicity as evidenced by a reduction in B lymphocyte number in male SD pups.     

Agricultural pesticide residues of farm runoff in the Okanagan Valley, British Columbia, Canada

The objectives of this study were to determine environmental occurrence and concentrations of selected currently-used-pesticides and some transformation products in agricultural farms in the Okanagan Valley (OKV), and to conduct a simple risk assessment of environmental pesticides levels detected in OKV on non-target aquatic organisms. The OKV is the tree fruit country of the Province of British Columbia where considerable amount of pesticides are applied annually. Water, sediment and soil samples were collected at eleven sites in early June and late September following rainfall events and/or extended periods of irrigation from drainage ditches and/or from small streams. Undisturbed reference sites were also sampled. Study results showed that forty of the eighty chemicals analyzed, including organochlorine, nitrogen-containing and organophosphate pesticides commonly used for OKV crops, were detected in runoff and small stream water samples. Among which, endosulfan-sulfate was the most frequently detected chemical. Also, azinophos-methyl (0.699-25.5 ng/L), diazinon (0.088-214 ng/L) exceeded, and α-, β- endosulfan, endosulfan sulphate approached the guidelines for the protection of aquatic life.     

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.     

Metal stress and decreased tree growth in response to biosolids application in greenhouse seedlings and in situ Douglas-fir stands

To assess physiological impacts of biosolids on trees, metal contaminants and phytochelatins were measured in Douglas-fir stands amended with biosolids in 1982. A subsequent greenhouse study compared these same soils to soils amended with fresh wastewater treatment plant biosolids. Biosolids-amended field soils had significantly higher organic matter, lower pH, and elevated metals even after 25 years. In the field study, no beneficial growth effects were detected in biosolids-amended stands and in the greenhouse study both fresh and historic biosolids amendments resulted in lower seedling growth rates. Phytochelatins - bioindicators of intracellular metal stress - were elevated in foliage of biosolids-amended stands, and significantly higher in roots of seedlings grown with fresh biosolids. These results demonstrate that biosolids amendments have short- and long-term negative effects that may counteract the expected tree growth benefits.     

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

Monitoring of hexabromocyclododecane diastereomers in fish from European freshwaters and estuaries

Background and aims  

Hexabromocyclododecane (HBCD) is a brominated flame retardant used mainly in polystyrene foam as well as in textile applications. In recent years, measures were taken to reduce HBCD emissions during its production and use. To evaluate the efficacy of these measures, a monitoring project was initiated with fish as bioaccumulation indicators.