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Systematic development of extraction methods for quantitative microplastics analysis in soils using metal-doped plastics Full text
2022
Tophinke, Alissa H. | Joshi, Akshay | Baier, Urs | Hufenus, Rudolf | Mitrano, Denise M.
The inconsistency of available methods and the lack of harmonization in current microplastics (MPs) analysis in soils demand approaches for extraction and quantification which can be utilized across a wide variety of soil types. To enable robust and accurate assessment of extraction workflows, PET MPs with an inorganic tracer (Indium, 0.2% wt) were spiked into individual soil subgroups and standard soils with varying compositions. Due to the selectivity of the metal tracer, MPs recovery rates could be quickly and quantitatively assessed using ICP-MS. The evaluation of different methods specifically adapted to the soil properties were assessed by isolating MPs from complex soil matrices by systematically investigating specific subgroups (sand, silt, clay, non-lignified and lignified organic matter) before applying the workflow to standard soils. Removal of recalcitrant organic matter is one of the major hurdles in isolating MPs for further size and chemical characterization, requiring novel approaches to remove lignocellulosic structures. Therefore, a new biotechnological method (3-F-Ultra) was developed which mimics natural degradation processes occurring in aerobic (Fenton) and anaerobic fungi (CAZymes). Finally, a Nile Red staining protocol was developed to evaluate the suitability of the workflow for non-metal-doped MPs, which requires a filter with minimal background residues for further chemical identification, e.g. by μFTIR spectroscopy. Image analysis was performed using a Deep Learning tool, allowing for discrimination between the number of residues in bright-field and MPs counted in fluorescence mode to calculate a Filter Clearness Index (FCI). To validate the workflow, three well-characterized standard soils were analyzed applying the final method, with recoveries of 88% for MPs fragments and 74% for MPs fibers with an average FCI of 0.75. Collectively, this workflow improves our current understanding of how to adapt extraction protocols according to the target soil composition, allowing for improved MPs analysis in environmental sampling campaigns.
Show more [+] Less [-]Microplastic ingestion by quagga mussels, Dreissena bugensis, and its effects on physiological processes Full text
2020
Pedersen, Adam F. | Gopalakrishnan, Kishore | Boegehold, Anna G. | Peraino, Nicholas J. | Westrick, Judy A. | Kashian, Donna R.
The impacts of microplastic particulates in benthic freshwater organisms have been largely unexplored despite abundant plastic accumulation in the sediments of these systems. We investigated the uptake of plastic particles by benthic filter feeding quagga mussels (Dreissena bugensis) and associated toxicity exhibited through impacts on mortality, filtration rate, reproduction and oxygen consumption. Matrix Assisted Laser Desorption/Ionization Imaging Mass Spectrometry (MALDI-IMS) technology was used to assess the microplastic inclusion. For this purpose, quagga mussels were exposed to four treatments ranging from 0.0 to 0.8 g/L of a high density fluorescent red polyethylene powder in the size range of 10–45 μm for 24-h, and the targeted endpoints were quantified. Identification of several micrograms of microplastics in the digestive tract suggests rapid clearance from the water column by filtering. At the higher concentrations, about 95% of the microplastics ingested remained in the mussels after 24-h. Microplastics were found in the gills which correlated with decreasing filtration rate at higher microplastic concentrations. Despite large-scale ingestion, plastic exposure did not affect survivorship, reproduction rates, or oxygen consumption in the period examined. MALDI-IMS identified unique mass spectra that correlated with microplastic inclusion. This research suggests that microplastics can impair feeding through decreased filtration rates of filter feeding organisms, potentially resulting in a reduction of overall fitness over time and that MALDI-IMS may have the potential to identify microplastics and changes in tissue at the borders of plastic inclusion.
Show more [+] Less [-]Downward transport of naturally-aged light microplastics in natural loamy sand and the implication to the dissemination of antibiotic resistance genes Full text
2020
Yan, Xinyu | Yang, Xinyao | Tang, Zhang | Fu, Jingjing | Chen, Fangmin | Zhao, Ying | Ruan, Lili | Yang, Yuesuo
Current understanding on the fate and behavior of microplastics (MPs) in complex soil media remains inadequate. We characterized the aging and hetero-aggregation of a MP sampled in farmland soil, and explored its vertical downward transport in natural loamy sand. The MP was identified with FTIR spectrum as polypropylene, a plastic lighter than water. FTIR spectrum combined with SEM imaging confirmed the MP was highly aged, generating colloidal plastic fibers and carbonyl groups. SEM imaging coupled with EDX analysis suggested hetero-aggregation of the MP with soil minerals. Soil leaching tests performed with the clean MP (without soil minerals) (CMP), the raw MP (RMP) (with soil minerals), and the RMP with humic acid (HA) (RMP + HA) demonstrated that the mobility was insignificant for the CMP, moderate for the RMP and highest for the RMP + HA, resulting in a maximal downward traveling distance of 0 cm, 3–4 cm, and 9–10 cm, respectively. Correlation between the maximal traveling distance and zeta potential of the CMP, RMP, and RMP + HA confirmed surface charge as a dominant control on the MP mobility; while the increasing density of the MP, due to hetero-aggregation with soil minerals, was identified as a driving mechanism for its downward transport, despite its intrinsic density lower than water. Occurrence of only the lower-sized rod-shaped plastic fibers at the maximal traveling distance suggested the natural aging, a process leading to plastic vibration and fragmentation, was conducive to plastic translocation. The three explored classes of antibiotic resistance genes (ARGs) (tetracycline, beta-lactam and sulfonamide) were all detected in the plastic surface, suggesting the MP may function as a potential pathway for the dissemination of ARGs to the deeper soil layer. These findings are important to understand the concentration distribution of both the MPs and ARGs in agriculture impacted soils, a natural reservoir of both emerging contaminants.
Show more [+] Less [-]Muscle melanisation of southern sand flathead (Platycephalus bassensis) in the Tamar Estuary, Tasmania, Australia Full text
2020
Stocker, Clayton W. | Haddy, James | Lyle, Jeremy | Nowak, Barbara F.
Tasmanian recreational fishers have reported the presence of dark pigmentations in the usually white fillets of southern sand flathead (Platycephalus bassensis), a phenomenon known as muscle melanisation. Based on histology, it is suggested that eumelanin and pheomelanin are involved in the occurrence of the phenomenon. A gross melanisation scoring system was validated through a comparison with an image analysis technique, that quantified the percentage surface area of the fillets affected by muscle melanisation. The occurrence of muscle melanisation was most severe in fish inhabiting Deceitful Cove, Tamar Estuary. This indicated that muscle melanisation in P. bassensis may be caused by yet to be identified site specific factors. No significant relationships were evident between the percentage surface area of melanised muscle with condition index, age, sex, maturation stage, fish weight, fish length and size of melano-macrophage centres in the liver or spleen. Overall, this study has provided critical information that will frame the direction and focus of future P. bassensis muscle melanisation research.
Show more [+] Less [-]Athabasca oil sands region snow contains efficient micron and nano-sized ice nucleating particles Full text
2019
The Athabasca Oil Sands Region (AOSR) in Alberta, Canada, is an important source of atmospheric pollutants, such as aerosols, that have repercussions on both the climate and human health. We show that the mean freezing temperature of snow-borne particles from AOSR was elevated (−7.1 ± 1.8 °C), higher than mineral dust which freezes at ∼ −15 °C and is recognized as one of the most relevant ice nuclei globally. Ice nucleation of nanosized snow samples indicated an elevated freezing ability (−11.6 ± 2.0 °C), which was statistically much higher than snow-borne particles from downtown Montreal. AOSR snow had a higher concentration (∼2 orders of magnitude) of >100 nm particles than Montreal. Triple quadrupole ICP-(QQQ)-MS/MS analysis of AOSR and Montreal snow demonstrated that most concentrations of metals, including those identified as emerging nanoparticulate contaminants, were much more elevated in AOSR in contrast to Montreal: 34.1, 34.1, 16.6, 5.8, 0.3, 0.1, and 9.4 mg/m³ for Cr, Ni, Cu, As, Se, Cd, and Pb respectively, in AOSR and 1.3, 0.3, 2.0, <0.03, 0.1, 0.03, and 1.2 mg/m³ in Montreal snow. High-resolution Scanning Transmission Electron Microscopy/Energy-dispersive X-ray Spectroscopy (STEM-EDS) imaging provided evidence for various anthropogenic nano-materials, including carbon nanotubes resembling structures, in AOSR snow up to 7–25 km away from major oil sands upgrading facilities. In summary, particles characterized as coming from oil sands are more efficient at ice nucleation. We discuss the potential impacts of AOSR emissions on atmospheric and microphysical processes (ice nucleation and precipitation) both locally and regionally.
Show more [+] Less [-]Zinc and lead encapsulated in amorphous ferric cements within hardpans in situ formed from sulfidic Cu-Pb-Zn tailings Full text
2019
Liu, Yunjia | Wu, Songlin | Southam, Gordon | Nguyen, Tuan A.H. | Kopittke, Peter M. | Paterson, David J. | Huang, Longbin
Hardpans are massively indurated layers formed at the top layer of sulfidic tailings dams, which develop cementation structures and result in heavy metal immobilization. However, the micro-structural and complex forms of the cementing materials are not fully understood, as well as the mechanisms by which Zn and Pb are stabilized in the hardpans. The present study deployed synchrotron-based X-ray fluorescence microscopy (XFM) to have characterized the cementing structures, examined the distribution of Fe, Zn and Pb, and obtained laterally-resolved speciation of Zn within the hardpans using fluorescence X-ray absorption near-edge structure (XANES) imaging. The XFM analyses revealed that the Fe-rich cement layers consisted of Fe (oxyhydr)oxides coupled with amorphous Si materials, immobilizing Zn and Pb. Through laterally-resolved XANES imaging analyses, Zn-ferrihydrite-like precipitates were predicted to account for >76% of the total Zn within the Fe-rich cement layers. In contrast, outside of the cement layers, 9–63% of the Zn was estimated as labile ZnSO4.7H2O, with the remainder in the form of Zn-sulfide. These findings demonstrated that the Fe-rich cement layers were critical in immobilizing Zn and Pb within hardpans via mineral passivation and encapsulation, as the basis for long-term geochemical stability in the hardpan layer of sulfidic mine tailings.
Show more [+] Less [-]Location and speciation of gadolinium and yttrium in roots of Zea mays by LA-ICP-MS and ToF-SIMS Full text
2016
Saatz, Jessica | Stryhanyuk, Hryhoriy | Vetterlein, Doris | Musat, Niculina | Otto, Matthias | Reemtsma, Thorsten | Richnow, Hans H. | Daus, Birgit
Increasing production of rare earth elements (REE) might lead to future contamination of the environment. REE have been shown to accumulate in high concentrations in roots of plants. Plant experiments with Zea mays exposed to a nutrient solution containing gadolinium (Gd) or yttrium (Y) with 10 mg L−1 Gd or Y were carried out to investigate this accumulation behaviour. Total concentrations of 3.17 g kg−1 and 8.43 g kg−1 of Gd and Y were measured in treated plant roots. Using a novel combination of laser ablation mass spectrometry and time-of-flight secondary ion mass spectrometry, imaging of location and concentration of Gd and Y was carried out in root thin sections of treated roots. Single spots of elevated REE concentration were found at the epidermis, while inside the cortex, weak signals of Gd+ and Y+ were aligning with the root cell structures. The composition of Gd-containing secondary ions proves an REE-oxide phase accumulated at the epidermis, limiting REE availability for further uptake.
Show more [+] Less [-]Unmanned aerial vehicles for the assessment and monitoring of environmental contamination: An example from coal ash spills Full text
2016
Messinger, Max | Silman, Miles
Unmanned aerial vehicles (UAVs) offer new opportunities to monitor pollution and provide valuable information to support remediation. Their low-cost, ease of use, and rapid deployment capability make them ideal for environmental emergency response. Here we present a UAV-based study of the third largest coal ash spill in the United States. Coal ash from coal combustion is a toxic industrial waste material present worldwide. Typically stored in settling ponds in close proximity to waterways, coal ash poses significant risk to the environment and drinking water supplies from both chronic contamination of surface and ground water and catastrophic pond failure. We sought to provide an independent estimate of the volume of coal ash and contaminated water lost during the rupture of the primary coal ash pond at the Dan River Steam Station in Eden, NC, USA and to demonstrate the feasibility of using UAVs to rapidly respond to and measure the volume of spills from ponds or containers that are open to the air. Using structure-from-motion (SfM) imagery analysis techniques, we reconstructed the 3D structure of the pond bottom after the spill, used historical imagery to estimate the pre-spill waterline, and calculated the volume of material lost. We estimated a loss of 66,245 ± 5678 m3 of ash and contaminated water. The technique used here allows rapid response to environmental emergencies and quantification of their impacts at low cost, and these capabilities will make UAVs a central tool in environmental planning, monitoring, and disaster response.
Show more [+] Less [-]High-resolution imaging of labile phosphorus and its relationship with iron redox state in lake sediments Full text
2016
Gao, Yulu | Liang, Tao | Tian, Shuhan | Wang, Lingqing | Holm, Peter E. | Bruun Hansen, Hans Christian
A thorough understanding of the labile status and dynamics of phosphorus (P) and iron (Fe) across the sediment-water interface (SWI) is essential for managing internal P release in eutrophic lakes. Fe-coupled inactivation of P in sediments is an important factor which affects internal P release in freshwater lakes. In this study, two in-situ high-resolution diffusive gradients in thin films (DGT) techniques, Zr-Oxide DGT and ZrO-Chelex DGT, were used to investigate the release characteristics of P from sediments in a large freshwater lake (Dongting Lake, China; area of 2691 km2) experiencing a regional summer algal bloom. Two-dimensional distributions of labile P in sediments were imaged with the Zr-Oxide DGT without destruction of the original structure of the sediment layer at four sites of the lake. The concentration of DGT-labile P in the sediments, ranging from 0.007 to 0.206 mg L−1, was highly heterogeneous across the profiles. The values of apparent diffusion flux (Fd) and release flux (Fr) of P varied between −0.027–0.197 mg m−2 d−1 and 0.037–0.332 mg m−2 d−1, respectively. Labile P showed a high and positive correlation (p < 0.01) with labile Fe(II) in the profiles, providing high-resolution evidence for the key role of Fe-redox cycling in labile P variation in sediments.
Show more [+] Less [-]Spatial scales of pollution from variable resolution satellite imaging Full text
2013
Chudnovsky, Alexandra A. | Kostinski, Alex | Lyapustin, Alexei | Koutrakis, Petros
The Moderate Resolution Imaging Spectroradiometer (MODIS) provides daily global coverage, but the 10 km resolution of its aerosol optical depth (AOD) product is not adequate for studying spatial variability of aerosols in urban areas. Recently, a new Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm was developed for MODIS which provides AOD at 1 km resolution. Using MAIAC data, the relationship between MAIAC AOD and PM2.5 as measured by the EPA ground monitoring stations was investigated at varying spatial scales. Our analysis suggested that the correlation between PM2.5 and AOD decreased significantly as AOD resolution was degraded. This is so despite the intrinsic mismatch between PM2.5 ground level measurements and AOD vertically integrated measurements. Furthermore, the fine resolution results indicated spatial variability in particle concentration at a sub-10 km scale. Finally, this spatial variability of AOD within the urban domain was shown to depend on PM2.5 levels and wind speed.
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