Assessing the environmental fate of chemicals of emerging concern: a case study of the polybrominated diphenyl ethers

It is suggested that assessments of chemicals of emerging concern can be rationally structured around a multistage process in which fate and risk are evaluated with increasing accuracy as new data become available. An initial tentative and approximate assessment of fate and risk can identify key data gaps and justify and direct further investigations, which progressively improve the reliability of the assessment. This approach is demonstrated for a class of chemicals, the polybrominated diphenyl ethers (PBDEs), which is of increasing concern, but about which there is presently a lack of comprehensive data on properties, sources, fate and effects. Specifically, 20 PBDE congeners are investigated using the suggested approach and research needs are identified.     

The potential use of ultrasound-assisted bleaching in removing heavy metals and pigments from soybean oil using kinetic,thermodynamic and equilibrium modeling

Environmental Science and Pollution Research - In this research, the sorption behavior (kinetic, isotherm, and thermodynamic modeling) of heavy metals (Cu (II) and Fe (II)) and pigments (carotenoid...     

Sorption-desorption of cadmium in aqueous palygorskite, sepiolite, and calcite suspensions: isotherm hysteresis

Sorption isotherms have been widely used to assess the heavy metal retention characteristics of soil particles. Desorption behavior of the retained metals, however, usually differ from that of sorption, leading to a lack of coincidence in the experimentally obtained sorption and desorption isotherms. In this study, we examine the nonsingularity of cadmium (Cd) sorption–desorption isotherms, to check the possible hysteresis and reversibility phenomena, in aqueous palygorskite, sepiolite and calcite systems. Sorption of Cd was carried out using a 24-h batch equilibration experiment with eight different Cd solution concentrations, equivalent to 20–100% of maximum sorption capacity of each mineral. Immediately after sorption, desorption took place using successive dilution method with five consecutive desorption steps. Both Cd sorption and desorption data were adequately described by Freundlich equation (0.81 < r² < 0.99). The sorption and desorption reactions, however, did not provide the same isotherms, indicating that hysteresis occurred in Cd sorption–desorption processes. The extent of hysteresis was quantified based on the differences obtained from sorption and desorption isotherms regarding the amount of Cd sorbed, the Freundlich exponent, and the Cd distribution coefficient. The results revealed that, sepiolite possessed the most hysteretic behavior among the minerals studied. Calcite showed much smaller hysteresis compared to the other two silicate clays at low Cd surface load, but its hysteresis indices significantly increased, and exceeded that of palygorskite, as the amount of Cd in the systems increased. The average amount of Cd released after five desorption steps, was 13.8%, 2.2% and 3.6% for the palygorskite, sepiolite and calcite, respectively, indicating that a large portion of Cd was irreversibly retained by the minerals.     

Source apportionment and deposition of dustfall-bound trace elements around Tabriz,Iran

Environmental Science and Pollution Research - The monthly and spatial variations of atmospheric dustfall (DF) and their elemental components were determined. The DF sampling was performed using...     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

Inhibition of metamorphosis in tadpoles of Xenopus laevis exposed to polybrominated diphenyl ethers (PBDEs)

Tadpoles of the African clawed frog, Xenopus laevis were exposed, beginning at stage 50, to a commercial pentabromodiphenyl ether mixture (DE-71) through the diet. Subsequent experiments were conducted using a single intraperitoneal injection at stage 58 with limited quantities of two purified brominated diphenyl ether (BDE) congeners, BDE47 and BDE99 and DE-71 to determine the relative potency of these BDE congeners within the commercial mixture. Significant inhibition of tail resorption, delayed metamorphosis and impacts on skin pigmentation were observed in Xenopus exposed to DE-71 in the diet at nominal doses of 1000 and 5000 microgg(-1) of food. The estimated time required for 50% of the tadpoles to complete metamorphosis was significantly lengthened in Xenopus exposed to a dietary concentration of 1 microg DE-71 per gram of food. Analysis of PBDEs (sum of 32 congeners) in Xenopus from the treatment with 5000 microgg(-1) of DE-71 indicated that the frogs accumulated an average of 1030 microgg(-1) (wet weight) of PBDEs. In the intraperitoneal injection trials, similar inhibitory responses were observed in Xenopus injected with DE-71 at a nominal dose of 60 microg per tadpole, or injected with BDE47 at a nominal dose of 100 microg per tadpole. No responses were observed in Xenopus injected with BDE99 at doses up to 100 microg per tadpole. Complete inhibition of metamorphosis was observed only in the highest DE-71 dietary treatment. The results of this study are consistent with a mechanism of action of PBDEs involving competitive inhibition of binding of thyroid hormones to transporter proteins, although the mechanism cannot be definitively determined from this study. The observed effects may have occurred through other mechanisms, including sublethal toxicity. The doses used in this study are greater than the levels of PBDEs to which anurans are exposed in the environment, so further studies are required to determine whether exposure to PBDEs at environmentally relevant concentrations can affect frog metamorphosis.     

Analysis and occurrence of emerging chlorinated and brominated flame retardants in surficial sediment of the Dalian coastal area in China

The concentrations and distributions of some typical chlorinated flame retardants (Dechlorane or Mirex, Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), Dechlorane 604 (Dec 604) and Dechlorane Plus (DP)) and brominated FRs (polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)) were analyzed in surficial sediment collected from the Dalian coastal area in northeast China. Dec 603, Dec 604, and BTBPE were below their respective limits of detection (LOD) in all sediment samples, while Dechlorane, Dec 602, DP, Σ13BDE (tri- to hepta-BDEs), BDE 209, and PBEB were identified in the ranges <0.015-39.9 ng g(-1) dry weight (dw), <0.011-0.156 ng g(-1) dw, 0.69-7.00 ng g(-1) dw, 0.017-1.33 ng g(-1) dw, 3.94-103 ng g(-1) dw, and <0.073-1.9 ng g(-1) dw, respectively. Relationships between these chlorinated and brominated FRs were analyzed using Pearson's correlation and principal component analysis (PCA). DP, Dechlorane, Σ13BDE, and BDE 209 showed significantly positive correlation (p<0.05), and these relationships showed excellent agreement with PCA results. The spatial trends for Dechlorane, DP, BDE 209, and Σ13BDE showed that high concentrations were found in the industrial zone and lower concentrations in residential and garden zones. The results imply that these FRs are originating from a common source, and support the view that direct input from the effluent of sewage outlets is a major source of these compounds in Dalian sediment.     

Fugacity approach to evaluate the sediment-water diffusion of polycyclic aromatic hydrocarbons

Diffusion is an important process for sediment-water exchange and plays a vital role in controlling water quality. Fugacity fraction (ff) was used to estimate the sediment-water diffusion of polycyclic aromatic hydrocarbons (PAHs) between seawater and surficial sediment. A total of 33 surface sediment and sea water samples were collected concurrently from the northeast coastal area in China and 25 PAHs were analyzed including the alkylated and chlorated PAHs. Fugacity fraction was calculated based on the PAH concentrations in water and sediment, octanol-water partition coefficient of PAHs, organic matter content in sediment, and density of sediment. The calculated results showed that ff increased with decreasing molecular weight of PAHs. The low molecular weight PAHs (2-3 rings) transferred from sediment to water and the sediment acted as a secondary source to the water. The medium molecular weight PAHs (4-5 rings) were close to the sediment-water equilibrium and the transfer tendency shifted between sediment and water. The high molecular weight PAHs (5-6 rings) transferred from water into sediment and the sediment acted as a sink. Soot carbon and the difference of PAH concentrations between sediment and water were found to be important factors affecting the sediment-water diffusion. This study provided new insight into the process of sediment-water diffusion, which has a great influence on the quality of water, especially in severely-polluted sediment areas.     

Mobility and efficacy of 2,4-D herbicide from slow-release delivery systems based on organo-zeolite and organo-bentonite complexes

This research aimed to develop slow-release formulations (SRFs) of 2,4-dichlorophenoxyacetic acid (2,4-D) using zeolite and bentonite minerals modified with cetyltrimethylammonium (CTMA) surfactant. Adsorption–desorption, greenhouse bioassay and column experiments were carried out to assess the potential of the SRFs to control weeds while reducing the herbicide leaching losses to deep layers of soil. The results showed that only 6.5 mmol 2,4-D kg^?1 was retained by Na-bent, and the herbicide was not adsorbed by Na-zeol at all. The surface modification with CTMA surfactant, however, improved the 2,4-D adsorption capacity of the zeolite and bentonite up to 207.5 and 415.8 mmol kg^?1, respectively. The synthesized organo-minerals slowly released the retained 2,4-D discharging 22 to 64% of the adsorbed 2,4-D to the solution phase within 7 days. The SRFs significantly (P = 0.05) reduced the herbicide mobility within the soil columns keeping a great portion of the herbicide active ingredient in the upper 5 cm soil layer. The SRFs were significantly (P = 0.05) as effective as the free technical herbicide in weed control without harming the ryegrass as the main plant. Therefore, the synthesized SRFs could be considered as useful tools for weed control in sustainable agriculture.     

Occurrence of triclosan in plasma of wild Atlantic bottlenose dolphins (Tursiops truncatus) and in their environment

The presence of triclosan, a widely-used antibacterial chemical, is currently unknown in higher trophic-level species such as marine mammals. Blood plasma collected from wild bottlenose dolphins (Tursiops truncatus) in Charleston, SC (CHS) (n = 13) and Indian River Lagoon, FL (IRL) (n = 13) in 2005 was analyzed for triclosan. Plasma concentrations in CHS dolphins ranged from 0.12 to 0.27 ng/g wet weight (mean 0.18 ng/g), with 31% of the sampled individuals having detectable triclosan. The mean IRL dolphin plasma concentrations were 0.072 ng/g wet weight (range 0.025–0.11 ng/g); 23% of the samples having detectable triclosan. In the CHS area, triclosan effluent values from two WWTP were both 190 ng/L and primary influents were 2800 ng/L and 3400 ng/L. Triclosan values in CHS estuarine surface water samples averaged 7.5 ng/L (n = 18) ranging from 4.9 to 14 ng/L. This is the first study to report bioaccumulation of anthropogenic triclosan in a marine mammal highlighting the need for further monitoring and assessment.