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Facile nanoplastics formation from macro and microplastics in aqueous media
2022
Peller, Julie R. | Mezyk, Stephen P. | Shidler, Sarah | Castleman, Joe | Kaiser, Scott | Faulkner, Richard F. | Pilgrim, Corey D. | Wilson, Antigone | Martens, Sydney | Horne, Gregory P.
The immense production of plastic polymers combined with their discordancy with nature has led to vast plastic waste contamination across the geosphere, from the oceans to freshwater reservoirs, wetlands, remote snowpacks, sediments, air and multiple other environments. These environmental pollutants include microplastics (MP), typically defined as small and fragmented plastics less than 5 mm in size, and nanoplastics (NP), particles smaller than a micrometer. The formation of micro and nanoplastics in aqueous media to date has been largely attributed to fragmentation of plastics by natural (i.e., abrasion, photolysis, biotic) or industrial processes. We present a novel method to create small microplastics (≲ 5 μm) and nanoplastics in water from a wide variety of plastic materials using a small volume of a solubilizer liquid, such as n-dodecane, in combination with vigorous mixing. When the suspensions or solutions are subjected to ultrasonic mixing, the particle sizes decrease. Small micro- and nanoparticles were made from commercial, real world and waste (aged) polyethylene, polystyrene, polycarbonate and polyethylene terephthalate, in addition to other plastic materials and were analyzed using dark field microscopy, Raman spectroscopy and particle size measurements. The presented method provides a new and simple way to create specific size distributions of micro- and nanoparticles, which will enable expanded research on these plastic particles in water, especially those made from real world and aged plastics. The ease of NP and small MP formation upon initial mixing simulates real world environments, thereby providing further insight into the behavior of plastics in natural settings.
Afficher plus [+] Moins [-]Traffic noise playback reduces the activity and feeding behaviour of free-living bats
2020
Finch, Domhnall | Schofield, Henry | Mathews, Fiona
Increasing levels of road noise are creating new anthropogenic soundscapes that may affect wildlife globally. Bats, which form about a third of all mammal species, are sensitive bioindicators, and may be particularly vulnerable because of their dependency on echolocation. Here we present the first controlled field experiment with free-living bats. Using a Before-After-Control-Impact phantom road experimental design, we examine the impacts of traffic noise on their activity and feeding behaviour. Disentangling the impacts of traffic noise from other co-varying exposures such as habitat quality, the experiment demonstrates a significant negative effect on the activity of each of the five, ecologically different, species (genus for Myotis spp.) examined. This suggests that the results are widely applicable. The negative effects are largely attributable to noise in the sonic spectrum, which elicited aversive responses in all bat species tested,whereas responses to ultrasoundwere restricted to a single species. Our findings demonstrate that traffic noise can affect bat activity at least 20m away from the noise source. For Pipistrellus pipistrellus and Pipistrellus pygmaeus, feeding behaviour, as well as overall activity, was negatively affected. Ecological Impact Assessments are therfore needed wherever there are significant increases in traffic flow, and not just when new roads are built. Further research is required to identify effective mitigation strategies, to delineate the zone of influence of road noise, and to assess whether there is any habituation over time.
Afficher plus [+] Moins [-]Prediction of organic contaminant uptake by plants: Modified partition-limited model based on a sequential ultrasonic extraction procedure
2019
Wu, Xiang | Zhu, Lizhong
Predicting the translocation of organic contaminants to plants is crucial to ensure the quality of agricultural goods and assess the risk of human exposure through the food web. In this study, the performance of a modified plant uptake model was evaluated considering a number of chemicals, such as polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs), with a range of physicochemical properties; different plant species (Ipomoea aquatica Forsk (swamp morning glory), Chrysanthemum coronarium L. (crown daisy), Zea mays L. (corn), Brassica rapa pekinensis (Chinese cabbage), Cucurbita moschata (pumpkin), Raphanus sativus L. (radish), Spinacia oleracea L. (spinach) and Capsicum annuum L. (pepper)); and different types of soil (paddy soil, laterite soil and black soil). The biases of predictions from a previously used partition-limited model were −76.4% to −99.9% relative to the measured concentrations. An overall transmission factor (αtf=0.39), calculated from a linear regression of the measured bioavailable fraction (Cbᵢₒ) and the total concentration in plants, was considered a crucial modification and was included in the modified model. Cbᵢₒ was found to better represent the chemical content available in soil for root uptake. The results from this study improve the accuracy of predictions for vegetation-uptake assessments by modifying the partition-limited model and then validating the modified model using comparisons between predicted data and measured values. The accuracy of the concentrations of organic contaminants in plants improved: when using the modified model, 89.5% of the predictions were within 40% of the actual value. The average bias was limited to 1.5%–30.5%. The model showed great potential to predict plant uptake using the bioavailable fraction concentration in soil.
Afficher plus [+] Moins [-]Potential transfer of organic pollutants from littoral plastics debris to the marine environment
2018
León, Víctor M. | García, Inés | González, Emilia | Samper, Raquel | Fernández-González, Verónica | Muniategui-Lorenzo, Soledad
Plastic polymers act as passive samplers in air system and concentrate hydrophobic organic contaminants by sorption or specific interactions, which can be transported to other systems such as the marine environment. In this study plastic debris was sampled in the surrounding area of a Mediterranean lagoon in order to determine the concentration of persistent and emerging organic contaminants. More specifically, desorption of 91 regulated and emerging organic contaminants (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, current-use pesticides, personal care products, other pesticides and plastic additives) was characterized for the first 24 h from different polymers to seawater and the remaining content of these contaminants was also extracted by ultrasonic extraction with methanol. All samples were analyzed by Stir Bar Sorptive Extraction coupled to GC/MS. A significant fraction of sorbed contaminants in polymers was desorbed in the first 24 h, particularly for triazines and organophosphorus pesticides due to their lower hydrophobicity than other considered analytes. The remaining contaminants contained in plastics can be also transferred to seawater, sediments or biota. Considering 24 h desorbed fraction plus the remaining methanol extracted fraction, the highest transfer levels corresponded to personal care products, plastic additives, current-use pesticides and PAHs. This is the first study to show the relevance of the transport of organic contaminants on plastic debris from littoral areas to the marine environment.
Afficher plus [+] Moins [-]Analysis of petroleum-contaminated soils by diffuse reflectance spectroscopy and sequential ultrasonic solvent extraction–gas chromatography
2014
Okparanma, Reuben N. | Coulon, Frederic | Mouazen, Abdul M.
In this study, we demonstrate that partial least-squares regression analysis with full cross-validation of spectral reflectance data estimates the amount of polycyclic aromatic hydrocarbons in petroleum-contaminated tropical rainforest soils. We applied the approach to 137 field-moist intact soil samples collected from three oil spill sites in Ogoniland in the Niger Delta province (5.317°N, 6.467°E), Nigeria. We used sequential ultrasonic solvent extraction–gas chromatography as the reference chemical method. We took soil diffuse reflectance spectra with a mobile fibre-optic visible and near-infrared spectrophotometer (350–2500 nm). Independent validation of combined data from studied sites showed reasonable prediction precision (root-mean-square error of prediction = 1.16–1.95 mg kg−1, ratio of prediction deviation = 1.86–3.12, and validation r2 = 0.77–0.89). This suggests that the methodology may be useful for rapid assessment of the spatial variability of polycyclic aromatic hydrocarbons in petroleum-contaminated soils in the Niger Delta to inform risk assessment and remediation.
Afficher plus [+] Moins [-]Fabrication of activated carbon supported modified with bimetallic-platin ruthenium nano sorbent for removal of azo dye from aqueous media using enhanced ultrasonic wave
2022
Herein, activated carbon supported modified with bimetallic-platin ruthenium nano sorbent (PtRu@AC) was synthesized by a thermal decomposition process and used in the removal of methylene blue (MB) from aqueous solutions. The synthesized nano sorbents were characterized by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS) spectroscopic techniques. The data obtained from characterization studies showed that PtRu@AC nano sorbent was highly crystalline and in a form of PtRu alloy with a monodispersed composition. The results indicated that the maximum adsorption capacity (qemax) for the removal of MB with PtRu@AC under optimum conditions was detected to be 1.788 mmol/g (569.4 mg/g). The experimental kinetic results of the study revealed that the adsorption of methylene blue was found to be more compatible with the false second-order model compared to some tested models. Calculations for thermodynamic functions including enthalpy change (ΔHo), entropy change (ΔSo), and Gibbs free energy change (ΔGo) values were performed to get an idea about the adsorption mechanism. As a result, the synthesized PtRu@AC nano adsorbent was detected as a highly effective adsorbent material in the removal of MB from aquatic mediums.
Afficher plus [+] Moins [-]Enhanced removal of per- and polyfluoroalkyl substances in complex matrices by polyDADMAC-coated regenerable granular activated carbon
2022
Ramos, Pia | Singh Kalra, Shashank | Johnson, Nicholas W. | Khor, Chia Miang | Borthakur, Annesh | Cranmer, Brian | Dooley, Gregory | Mohanty, Sanjay K. | Jassby, David | Blotevogel, Jens | Mahendra, Shaily
Granular activated carbon (GAC) has been used to remove per- and polyfluoroalkyl substances (PFASs) from industrial or AFFF-impacted waters, but its effectiveness can be low because adsorption of short-chained PFASs is ineffective and its sites are exhausted rapidly by co-contaminants. To increase adsorption of anionic PFASs on GAC by electrostatic attractions, we modified GAC's surface with the cationic polymer poly diallyldimethylammonium chloride (polyDADMAC) and tested its capacity in complex water matrices containing dissolved salts and humic acid. Amending with concentrations of polyDADMAC as low as 0.00025% enhanced GAC's adsorption capacity for PFASs, even in the presence of competing ions. This suggests that electrostatic interactions with polyDADMAC's quaternary ammonium functional groups helped bind organic and inorganic ions as well as the headgroup of short-chain PFASs, allowing more overall PFAS removal by GAC. Evaluating the effect of polymer dose is important because excessive addition can block pores and reduce overall PFAS removal rather than increase it. To decrease the waste associated with this adsorption strategy by making the adsorbent viable for more than one saturation cycle, a regeneration method is proposed which uses low-power ultrasound to enhance the desorption of PFASs from the polyDADMAC-GAC with minimum disruption to the adsorbent's structure. Re-modification with the polymer after sonication resulted in a negligible decrease in the sorbent's capacity over four saturation rounds. These results support consideration of polyDADMAC-modified GAC as an effective regenerable adsorbent for ex-situ concentration step of both short and long-chain PFASs from real waters with high concentrations of competing ions and low PFAS loads.
Afficher plus [+] Moins [-]Enhanced organic contaminants accumulation in crops: Mechanisms, interactions with engineered nanomaterials in soil
2018
Wu, Xiang | Wang, Wei | Zhu, Lizhong
The mechanism of enhanced accumulation of organic contaminants in crops with engineered nanomaterials (ENMs) were investigated by co-exposure of crops (Ipomoea aquatica Forsk (Swamp morning-glory), Cucumis sativus L. (cucumber), Zea mays L. (corn), Spinacia oleracea L. (spinach) and Cucurbita moschata (pumpkin))to a range of chemicals (polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenyl ether (PBDE)) and ENMs (TiO2, Ag, Al2O3, graphene, carbon nanotubes (CNTs)) in soil. Induced by 50 mg kg−1 graphene co-exposure, the increase range of BDE-209, BaP, p,p′-DDE, HCB, PYR, FLU, ANT, and PHEN in the plants were increased in the range of 7.51–36.42, 5.69–32.77, 7.09–59.43, 11.61–66.73, 4.58–57.71, 5.79–109.07, 12.85–109.76, and15.57–127.75 ng g−1, respectively. The contaminants in ENMs-spiked and control soils were separated into bioavailable, bound and residual fractions using a sequential ultrasonic extraction procedure (SUEP) to investigate the mechanism of the enhanced accumulation. The bioavailable fraction in spiked soils showed no significant difference (p > 0.05) from that in the control, while the bound fraction increased in equal proportion (p > 0.05) to the reduction in the residual fraction. These results implied that ENMs can competitively adsorbed the bound of organic contaminants from soil and co-transferred into crops, followed by a portion of the residual fraction transferred to the bound fraction to maintain the balance of different fractions in soils. The mass balance was all higher than 98.5%, indicating the portion of degraded contaminants was less than 1.5%. These findings could expand our knowledge about the organic contaminants accumulation enhancement in crops with ENMs.
Afficher plus [+] Moins [-]Molecular identification of polymers and anthropogenic particles extracted from oceanic water and fish stomach – A Raman micro-spectroscopy study
2018
Ghosal, Sutapa | Chen, Michael | Wagner, Jeff | Wang, Zhong-Min | Wall, Stephen
Pacific Ocean trawl samples, stomach contents of laboratory-raised fish as well as fish from the subtropical gyres were analyzed by Raman micro-spectroscopy (RMS) to identify polymer residues and any detectable persistent organic pollutants (POP). The goal was to access specific molecular information at the individual particle level in order to identify polymer debris in the natural environment. The identification process was aided by a laboratory generated automated fluorescence removal algorithm. Pacific Ocean trawl samples of plastic debris associated with fish collection sites were analyzed to determine the types of polymers commonly present. Subsequently, stomach contents of fish from these locations were analyzed for ingested polymer debris. Extraction of polymer debris from fish stomach using KOH versus ultrapure water were evaluated to determine the optimal method of extraction. Pulsed ultrasonic extraction in ultrapure water was determined to be the method of choice for extraction with minimal chemical intrusion. The Pacific Ocean trawl samples yielded primarily polyethylene (PE) and polypropylene (PP) particles >1 mm, PE being the most prevalent type. Additional microplastic residues (1 mm - 10 μm) extracted by filtration, included a polystyrene (PS) particle in addition to PE and PP. Flame retardant, deca-BDE was tentatively identified on some of the PP trawl particles. Polymer residues were also extracted from the stomachs of Atlantic and Pacific Ocean fish. Two types of polymer related debris were identified in the Atlantic Ocean fish: (1) polymer fragments and (2) fragments with combined polymer and fatty acid signatures. In terms of polymer fragments, only PE and PP were detected in the fish stomachs from both locations. A variety of particles were extracted from oceanic fish as potential plastic pieces based on optical examination. However, subsequent RMS examination identified them as various non-plastic fragments, highlighting the importance of chemical analysis in distinguishing between polymer and non-polymer residues.
Afficher plus [+] Moins [-]Enzymatic probe sonication for quick extraction of total bisphenols from animal-derived foods: Applicability to occurrence and exposure assessment
2022
Xiao, Zhiming | Wang, Shi | Suo, Decheng | Wang, Ruiguo | Huang, Yuan | Su, Xiaoou
A high demand exists in bisphenols (BPs) screening studies for quick, reliable and straightforward analytical methods that generate data faster and simultaneously. Herein, we describe a combination of enzymatic probe sonication (EPS) and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for quick extraction and simultaneous quantification of eight important BPs in animal-derived foods. Results obtained demonstrated that the ultrasonic probe power could not only enhance the enzymatic hydrolysis efficiency, but also accelerate the liquid-liquid extraction procedure. Under optimized EPS parameters, one sample could be exhaustively extracted within 120 s, as compared with 12 h needed for the conventional enzymatic extraction which is more suitable for high-throughput analysis. The method was successfully applied to analyze residual BPs in animal-derived foods collected from Beijing, China. Widespread occurrence of BPA, BPS, BPF, BPAF, BPP, and BPB were found, with detection frequencies of 65.2%, 42.4%, 33.7%, 29.4%, 28.3%, and 27.2%, respectively. The highest total concentration levels of BPs (sum of the eight BPs analyzed, ΣBPs) were found in chicken liver (mean 12.2 μg/kg), followed by swine liver (6.37 μg/kg), bovine muscle (3.24 μg/kg), egg (2.03 μg/kg), sheep muscle (2.03 μg/kg), chicken muscle (1.45 μg/kg), swine muscle (1.42 μg/kg), and milk (1.17 μg/kg). The estimated daily intake (EDI) of BPs, based on the mean and 95th percentile concentrations and daily food consumptions, was estimated to be 5.687 ng/kg bw/d and 22.71 ng/kg bw/d, respectively. The human health risk assessment in this work suggests that currently BPs do not pose significant risks to the consumers because the hazard index (HI) was <1.
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