Microplastics have the potential to uptake and release persistent organic pollutants (POPs); however, subsequent transfer to marine organisms is poorly understood. Some models estimating transfer of ...sorbed contaminants to organisms neglect the role of gut surfactants under differing physiological conditions in the gut (varying pH and temperature), examined here. We investigated the potential for polyvinylchloride (PVC) and polyethylene (PE) to sorb and desorb (14)C-DDT, (14)C-phenanthrene (Phe), (14)C-perfluorooctanoic acid (PFOA) and (14)C-di-2-ethylhexyl phthalate (DEHP). Desorption rates of POPs were quantified in seawater and under simulated gut conditions. Influence of pH and temperature was examined in order to represent cold and warm blooded organisms. Desorption rates were faster with gut surfactant, with a further substantial increase under conditions simulating warm blooded organisms. Desorption under gut conditions could be up to 30 times greater than in seawater alone. Of the POP/plastic combinations examined Phe with PE gave the highest potential for transport to organisms.
•Cosmetic products are potentially important sources of microplastics in the marine environment.•Here we characterised and quantified plastic microbeads extracted from cosmetics.•Extracted microbeads ...were polyethylene with mean diameters of between 164 and 327μm.•Between 4594 and 94,500 microbeads could be released from an exfoliant in a single use.•Extracted microbeads were able to sorb both Phe and DDT.
Cosmetic products, such as facial scrubs, have been identified as potentially important primary sources of microplastics to the marine environment. This study characterises, quantifies and then investigates the sorptive properties of plastic microbeads that are used as exfoliants in cosmetics. Polyethylene microbeads were extracted from several products, and shown to have a wide size range (mean diameters between 164 and 327μm). We estimated that between 4594 and 94,500 microbeads could be released in a single use. To examine the potential for microbeads to accumulate and transport chemicals they were exposed to a binary mixture of 3H-phenanthrene and 14C-DDT in seawater. The potential for transport of sorbed chemicals by microbeads was broadly similar to that of polythene (PE) particles used in previous sorption studies. In conclusion, cosmetic exfoliants are a potentially important, yet preventable source of microplastic contamination in the marine environment.
Microplastics represent an increasing source of anthropogenic contamination in aquatic environments, where they may also act as scavengers and transporters of persistent organic pollutants. As ...estuaries are amongst the most productive aquatic systems, it is important to understand sorption behaviour and transport of persistent organic pollutants (POPs) by microplastics along estuarine gradients. The effects of salinity sorption equilibrium kinetics on the distribution coefficients (Kd) of phenanthrene (Phe) and 4,4′-DDT, onto polyvinyl chloride (PVC) and onto polyethylene (PE) were therefore investigated. A salinity gradient representing freshwater, estuarine and marine conditions, with salinities corresponding to 0 (MilliQ water, 690 μS/cm), 8.8, 17.5, 26.3 and 35 was used. Salinity had no significant effect on the time required to reach equilibrium onto PVC or PE and neither did it affect desorption rates of contaminants from plastics. Although salinity had no effect on sorption capacity of Phe onto plastics, a slight decrease in sorption capacity was observed for DDT with salinity. Salinity had little effect on sorption behaviour and POP/plastic combination was shown to be a more important factor. Transport of Phe and DDT from riverine to brackish and marine waters by plastic is therefore likely to be much more dependent on the aqueous POP concentration than on salinity. The physical characteristics of the polymer and local environmental conditions (e.g. plastic density, particle residence time in estuaries) will affect the physical transport of contaminated plastics. A transport model of POPs by microplastics under estuarine conditions is proposed. Transport of Phe and DDT by PVC and PE from fresh and brackish water toward fully marine conditions was the most likely net direction for contaminant transport and followed the order: Phe-PE >> DDT-PVC = DDT-PE >> Phe-PVC.
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•Salinity effect was investigated on sorption/desorption of POPs onto microplastics.•Little effect on sorption and no effect on their desorption rates was observed.•Transport of POPs will largely depend on their concentration in each compartment.•A transport model of POPs onto microplastics was proposed.•Transport followed the order: Phe-PE >> DDT-PVC = DDT-PE >> Phe-PVC.
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► Organic pollutants are present as complex mixtures in the marine environment. ► The competitive sorption of phenanthrene and DDT in a bi-solute system was investigated onto PVC and ...PE. ► DDT outcompeted phenanthrene for sorption onto plastic. ► DDT also appeared to have a negative effect on the sorption of phenanthrene onto plastic when added at high concentration.
Plastics are known to sorb persistent organic pollutants from seawater. However, studies to quantify sorption rates have only considered the affinity of chemicals in isolation, unlike the conditions in the environment where contaminants are present as complex mixtures. Here we examine whether phenanthrene and 4,4′-DDT, in a mixture, compete for sorption sites onto PVC with no added additives (unplasticised PVC or uPVC) and Ultra-High Molecular Weight polyethylene. Interactions were investigated by exposing particles of uPVC and UHMW PE to mixtures of 3H and 14C radiolabelled Phe and DDT. Changes in sorption capacity were modelled by applying a Freundlich binding sorption isotherms. An Extended Langmuir Model and an Interaction Factor Model were also applied to predict equilibrium concentrations of pollutants onto plastic. This study showed that in a bi-solute system, DDT exhibited no significantly different sorption behaviour than in single solute systems. However, DDT did appear to interfere with the sorption of Phe onto plastic, indicating an antagonistic effect.
It has been hypothesised that, if ingested, plastic debris could act as vector for the transfer of chemical contaminants from seawater to organisms, yet modelling suggest that, in the natural ...environment, chemical transfer would be negligible compared to other routes of uptake. However, to date, the models have not incorporated consideration of the role of gut surfactants, or the influence of pH or temperature on desorption, whilst experimental work has shown that these factors can enhance desorption of sorbed contaminants several fold. Here, we modelled the transfer of sorbed organic contaminants dichlorodiphenyltrichloroethane (DDT), phenanthrene (Phe) and bis-2-ethylhexyl phthalate (DEHP) from microscopic particles of polyvinylchloride (PVC) and polyethylene (PE) to a benthic invertebrate, a fish and a seabird using a one-compartment model OMEGA (Optimal Modelling for EcotoxicoloGical Applications) with different conditions of pH, temperature and gut surfactants. Environmental concentrations of contaminants at the bottom and the top of published ranges were considered, in combination with ingestion of either 1 or 5% by weight of plastic. For all organisms, the combined intake from food and water was the main route of exposure for Phe, DEHP and DDT with a negligible input from plastic. For the benthic invertebrate, predictions including the presence of contaminated plastic resulted in very small increases in the internal concentrations of DDT and DEHP, while the net change in the transfer of Phe was negligible. While there may be scenarios in which the presence of plastic makes a more important contribution, our modelling study suggests that ingestion of microplastic does not provide a quantitatively important additional pathway for the transfer of adsorbed chemicals from seawater to biota via the gut.
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•Transfer of sorbed organic contaminants from microplastics was modelled to marine life using a one-compartment model OMEGA.•Cint increased when contribution of uptake via plastic relative to other uptake routes was larger than elimination routes.•Intake from food and water was the main route of exposure for Phe, DEHP and DDT with a negligible input from plastic.•Contaminated microplastics had a negligible impact on transfer to biota under both relevant and worst case scenarios.
Combined intake from food and water was the main route of exposure for DEHP, DDT and Phe to the organisms under investigation with a negligible input from plastic.
Asphaltene structure is one of the most controversial topics in petroleum chemistry. The controversy is centered on the organization of aromatic cores within asphaltene molecules (single aromatic ...core, island and multiple aromatic core, archipelago) and specifically the inconsistency between the island model and the composition of the products derived from asphaltene pyrolysis/thermal cracking. Such products are consistent with the coexistence of island and archipelago asphaltene structural motifs. However, the archipelago model continues to lack the widespread acceptance of the petroleum community, in part due to mass spectrometry results in support of the island model. In the first and second part of this series, we demonstrated that the disproportionally high atmospheric pressure photoionization (APPI) ionization efficiency (monomer ion yield) of island species is due to weak nanoaggregation of large aromatic cores which do not extensively aggregate in toluene, whereas more archipelago-dominant fractions were shown to have low monomer ion yield due to a greater propensity for aggregation. The discrepancy leads to bias toward the selective ionization of island compounds and thus the erroneous mass spectrometry support of the predominance of the island structural model. A separation method based on aggregation trends and therefore the efficiency of monomeric ion production is critical to access archipelago structures. In the work presented herein, we demonstrate that dominance of island or archipelago structural motif is sample dependent. We present the positive-ion APPI Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) characterization of asphaltenes and asphaltene extrography fractions derived from Wyoming Deposit (island dominant) and Athabasca Bitumen (archipelago dominant) C7 asphaltenes. Wyoming Deposit asphaltenes resemble the “classical” island-type asphaltene structure: they exhibit a high concentration of highly aromatic/alkyl-deficient species with a compositional space close to the polycyclic aromatic hydrocarbon (PAH) limit. Fragmentation results from infrared multiphoton dissociation (IRMPD) confirm that island is the dominant structural motif in Wyoming Deposit C7 asphaltenes; the predominant fragmentation pathway for all extrography fractions consists of loss of CH2 units (or dealkylation), without significant loss of aromaticity. Conversely, Athabasca Bitumen C7 asphaltenes exhibit an “atypical” molecular composition. More than 40 wt % of the sample is extracted in the latest extrography fractions, which are composed of difficult-to-ionize species, a fraction of which exhibit atypically low double bond equivalent (DBE = 5–12) and extended homologous series with carbon numbers up to 60. The fragmentation behavior of all Athabasca Bitumen-derived fractions demonstrates a predominant contribution of archipelago motifs. Our results suggest that the Yen-Mullins molecular definition of asphaltenes cannot be used to describe all asphaltene samples. Island and archipelago structural motifs coexist, and extrography separation reveals a structural continuum that is enriched with archipelago motifs as a function of increasing molecular weight and polarity. The ratio island/archipelago is sample dependent, and its accurate quantification should significantly improve the economic value of asphaltene-enriched feedstocks by prediction of yields and optimal conditions for upgrading processes.
Advances in high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) enable molecular-level characterization of ultracomplex asphaltene samples. Such analyses most ...often reveal compounds that are highly aromatic but alkyl-deficient in nature and, thus, support the classical “island” model of asphaltene architecture. However, recent works that combine chromatographic separations with mass spectrometry for the analysis of crude oils have shown that differences in ionization may greatly affect the analysis of complex mixtures (known as the matrix effect). Simply, compounds that ionize with greater efficiency are preferentially observed and mask the detection of poorly ionized compounds. Asphaltenes are not immune to this phenomenon. In the first of this series (10.1021/acs.energyfuels.7b02873), it was demonstrated that asphaltenes generated by different precipitants showed greatly varied monomer ion yields (ionization efficiencies). This work focuses on the development of an extrography fractionation method that selectively targets the removal of asphaltene species that exhibit high monomer ion yields and, thus, restrict mass spectral characterization of less efficiently ionized species. Silica gel was used as the stationary phase, and a unique solvent series separated asphaltenes based on their interaction with the silica surface, which was later determined to depend heavily upon the structure as well as monomer ion yield. The first two solvents (acetone and acetonitrile) isolated compounds that most efficiently produce monomeric asphaltene ions and, thus, cause bias in mass spectrometric analyses of whole asphaltenes. A solvent polarity gradient was then used, with n-heptane, toluene, tetrahydrofuran, and methanol, to separate remnant asphaltene compounds on the basis of polarity and structure. Our results demonstrate that mass spectrometry of whole asphaltenes does not reveal the complete molecular composition but rather preferentially exposes highly aromatic, alkyl-deficient, island-type structures. Early eluting fractions are shown to resemble the composition of the whole asphaltene and are enriched in island structures, whereas the analysis of later-eluting fractions reveals archipelago structural motifs as well as species with atypical asphaltene molecular compositions. We also demonstrate that, as molecular weight increases, the asphaltenes exhibit increased contributions of archipelago structural motifs. Higher mass ions (m/z > 550), even from asphaltene fractions enriched in island structures, exhibit fragmentation pathways that originate from archipelago structures. Thus, positive-ion atmospheric pressure photoionization (APPI) FT-ICR MS provides molecular-level data that suggest that the island model is not the dominant structure of asphaltenes. It coexists with abundant archipelago structures, and the ratios of each are sample-dependent.
Plastic debris litters marine and terrestrial habitats worldwide. It is ingested by numerous species of animals, causing deleterious physical effects. High concentrations of hydrophobic organic ...contaminants have also been measured on plastic debris collected from the environment, but the fate of these contaminants is poorly understood. Here, we examine the uptake and subsequent release of phenanthrene by three plastics. Equilibrium distribution coefficients for sorption of phenanthrene from seawater onto the plastics varied by more than an order of magnitude (polyethylene ≫ polypropylene > polyvinyl chloride (PVC)). In all cases, sorption to plastics greatly exceeded sorption to two natural sediments. Desorption rates of phenanthrene from the plastics or sediments back into solution spanned several orders of magnitude. As expected, desorption occurred more rapidly from the sediments than from the plastics. Using the equilibrium partitioning method, the effects of adding very small quantities of plastic with sorbed phenanthrene to sediment inhabited by the lugworm (Arenicola marina) were evaluated. We estimate that the addition of as little as 1 μg of contaminated polyethylene to a gram of sediment would give a significant increase in phenanthrene accumulation by A. marina. Thus, plastics may be important agents in the transport of hydrophobic contaminants to sediment-dwelling organisms.
Domesticated plants display diverse phenotypic traits. However, the influence of breeding effort on this phenotypic diversity remains unknown. Here, we demonstrate that a single nucleotide deletion ...in the homeobox motif of BIPINNATA, a BEL-LIKE HOMEODOMAIN gene, led to a highly complex leaf phenotype in an heirloom tomato (Solanum lycopersicum), Silvery Fir Tree (SiFT), which is used as a landscaping and ornamental plant. A comparative gene network analysis revealed that repression of SOLANIFOLIA, the ortholog of WUSCHEL RELATED HOMEOBOX 1, caused the narrow leaflet phenotype seen in SiFT. Comparative genomics indicated that the bip mutation in SiFT likely arose de novo and is unique to SiFT and not introgressed from other tomato genomes. These results provide new insights into the natural variation in phenotypic traits introduced into crops during improvement processes after domestication and establish homeobox genes as evolutionary hotspots.
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•Two HOMEOBOX genes are responsible for the leaf shape in an heirloom tomato, SiFT•BIP regulates leaf complexity; SlWOX1 regulates leaflet width and vascular density•SlWOX1 is mutated in the classical tomato mutant, solanifolia•The bip mutation in SiFT arose de novo during the breeding process
Nakayama et al. identify two HOMEOBOX genes responsible for leaf form diversification in an ornamental heirloom tomato. Those genes regulate leaf complexity, leaflet width, and vascular density. New morphological traits can be introduced into a crop during the ongoing improvement processes after domestication.
to mg l, Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic
contaminants, including polychlorinated biphenyls (PCBs), ...polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine
pesticides (2,2′-bis(, to µg g, and were correlated with the level of economic development., chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A,
at concentrations from sub ng g, . Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations
of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns.
Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants
than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning
and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated
that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives
and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal
sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena
dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations
in leachates from municipal waste disposal sites in tropical Asia ranged from sub µg l
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