Field-Flow Fractionation (FFF) is now recognised as a versatile pool of techniques allowing particle size or molar mass to be obtained in a wide variety of samples covering numerous applications in ...the fields of environment, materials or biology. In the same time, Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) has an indisputable place in the field of elemental detectors and the coupling between FFF and ICP-MS can be considered as an emerging technique capable to reach relevant physico-chemical information at sub-micrometre scale and trace element concentration level. This paper gives some key elements of FFF-based fractionation linking theory and practical analytical aspects, from injection and preconcentration to analysis. The different components of the coupling are described. Summary tables of the main operating conditions of FFF-ICP-MS coupling are presented and operating conditions such as carrier composition, flow and nebulizers are discussed. Special attention is given to the FFF-ICP-MS interface. Qualitative and quantitative analysis is also discussed. Applications in the fields of environment, bioanalysis and nanoparticles are presented in order to illustrate the potentialities of such coupling.
Standardized methods for the digestion of biota for microplastic analysis are currently lacking. Chemical methods can be effective, but can also cause damage to some polymers. Enzymatic methods are ...known to be gentler, but often laborious, expensive and time consuming. A novel tissue digestion method with pancreatic enzymes and a pH buffer (Tris) is here presented in a comparison to a commonly applied digestion protocol with potassium hydroxide. The novel protocol demonstrates a highly efficient removal of bivalve tissue (97.7 ± 0.2% dry weight loss) already over-night. Furthermore, it induces no impairment in terms of ability to correctly identify four pre-weathered plastic polymers and six textile fiber polymers by Fourier transform infrared spectroscopy after exposure. The high-throughput protocol requires minimal handling, is of low cost and does not pose risk to the performer or the environment. It is therefore suggested as a candidate for a standardized digestion protocol, enabling successful analysis of microplastics ingested by bivalves.
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•Presents a novel protocol for bivalve tissue digestion and microplastic extraction•No impact on pre-weathered polymers nor textile fibers was detected.•The enzymatic protocol is superior to KOH in terms of tissue digestion efficiency.•The developed protocol is suggested to fulfil requirements of a standardized method.
There is mounting evidence that tire wear particles can harm natural systems, but worldwide trends in car weight and car usage, mean emissions are set to increase. To control tire wear emissions and ...help understand fate and transport, detailed characterisation of the particles, and the relationship between road surface properties and emission profiles is needed. This study deployed a suite of experiments utilising the advanced road simulator of the Swedish National Road and Transport Research Institute to compare seasonal tire types from three brands. An extraction method was developed for a coarse (>30 µm) fraction of tire and road wear particles (TRWP), and a comprehensive physicochemical characterisation scheme applied to both TRWP and tire-tread, including microscopy, energy-dispersive X-ray spectroscopy and pyrolysis-GC/MS. Road simulator dusts and hand-picked TRWP showed differences in shape, numbers, and mass between tire types and brands, and between asphalt and cement concrete road surfaces. Contrary to accepted perceptions, tactile analyses revealed that firm-elastic TRWP comprised only a minor proportion of TRWP. Fragile and chemically distinct tire-road-derived particles, termed here sub-elastic TRWP, comprised 39–100% of TRWP. This finding raises urgent questions about overall TRWP classification and identification features, resistance to weathering, and environmental fate. At the same time, differences in TRWP generation between tire formulations, and road surfaces, show potential for controlling emissions to reduce global impacts.
Aqueous dispersions of titania nanoparticles are shown to yield collective diffusion coefficients in dynamic light-scattering measurements that depend nonlinearly on particle concentration under ...dilute conditions. From theory, one expects a linear dependence for monodisperse systems except for strongly interacting charged particles in low ionic strength media. Angularly resolved dynamic light-scattering measurements reveal that aggregates are present, which explains the collective diffusion coefficient tending to lower values in the dilute limit than the Stokes–Einstein diffusion coefficient of the nanoparticles. A simple theoretical model based on mixtures of charged nanoparticle spheres and small amounts of larger-sized neutral or weakly charged spheres, modeling the presence of aggregates, is applied and shown to yield predictions in qualitative accord with the experimental trends. In particular, the downward curvature of the collective diffusion coefficient on diluting the system arises in the model from nanoparticles being driven into close proximity to the larger particles by electrostatic interactions. Similar experimental trends observed in silica dispersions suggest that the behavior is not an isolated finding. This study clearly shows that a small number of larger aggregates dramatically change the measured value of the collective diffusion coefficient; thus, care must be exercised when characterizing nanoparticles with dynamic light scattering.
Iron chemistry measurements were conducted during summer 2007 at two distinct locations in the Baltic Sea (Gotland Deep and Landsort Deep) to evaluate the role of iron for cyanobacterial bloom ...development in these estuarine waters. Depth profiles of Fe(II) were measured by chemiluminescent flow injection analysis (CL-FIA). Up to 0.9 nmol Fe(II) L−1 were detected in light penetrated surface waters, which constitutes up to 20% to the dissolved Fe pool. This bioavailable iron source is a major contributor to the Fe requirements of Baltic Sea phytoplankton and apparently plays a major role for cyanobacterial bloom development during our study. Measured Fe(II) half life times in oxygenated water exceed predicted values and indicate organic Fe(II) complexation. Potential sources for Fe(II) ligands, including rainwater, are discussed. Fe(II) concentrations of up to 1.44 nmol L−1 were detected at water depths below the euphotic zone, but above the oxic anoxic interface. Mixed layer depths after strong wind events are not deep enough in summer time to penetrate the oxic-anoxic boundary layer. However, Fe(II) from anoxic bottom water may enter the sub-oxic zone via diapycnal mixing and diffusion.
We tested the effect of additions of organic matter of different quality (C:N ratio) and quantity on benthic fluxes of ammonium, nitrate, silicate, oxygen and dissolved inorganic carbon (DIC). ...Additions were made to intact sediment boxes, according to a 2-level factorial design, and the magnitude and temporal scale of the response were evaluated with Partial Least Square (PLS) regression analysis. Response patterns were followed over a 40 d period following the addition, but only fluxes of ammonium, nitrate, silicate and oxygen for the first 2 d after addition, and nitrate fluxes for the first 8 d after addition, could be used for predictive modelling. The results showed that the response of the microbial community to different qualities and quantities of organic matter may initially be related to its capacity to sequester organic matter, and in the long term, to its growth in response to the respective nutritional supply. The results also suggest that such an experimental approach can be a useful tool for classification of areas with potential risk of eutrophication.
Enrichments with five types of organic carbon, differing in nitrogen content and type of organic carbon, were made to a marine sediment in order to study effects on nitrogen fluxes. The enrichments ...used were Ulva lactuca, Ascophyllum nodosum, Zostera marina, Ceratium spp., lignin, and mixtures of U. lactuca and A. nodosum. Fluxes of ammonium, nitrate, and phosphate were measured in short-term (48 h) microcosm experiments, using a carbon enrichment loading similar to that at the sampling site. Changes in microbial community growth and structure due to three types enrichments were also detected using molecular methods in a microcosm experiment run for 4 days to allow for detection at DNA-level.
Ammonium fluxes changed from an efflux in the control to an influx for all enrichments apart from U. lactuca. The change was significantly related to the added material's C:N ratio when Ceratium spp. was excluded. All enrichments induced an influx of nitrate suggesting the formation of anoxic micro zones, but there was no relationship with C:N ratio. Instead, the magnitude of the nitrate influx is suggested to be related to the structure of the organic carbon, where enrichments containing a large pool of cellulose and lignin (Z. marina and lignin) gave rise to a lower influx, compared to algal material with more easily degraded organic matter like lipids and starch, which induced the highest influx of nitrate (Ceratium spp., U. lactuca, and A. nodosum). The occurrence of an ammonium influx together with increased nitrate influx and a lower efflux of phosphate in the enrichments suggests a growth of heterotrophic bacteria. This was also confirmed using molecular methods (PCR-DGGE) where the relative abundance of bacterial species in the enrichments increased.
The sum of ammonium and nitrate fluxes showed that total nitrogen removal was enhanced in all enrichments compared to the nonenriched control sediment, but in different ways. Ceratium spp. induced the highest removal followed by A. nodosum, U. lactuca, Z. marina, and lastly, by lignin. The same pattern was observed also in a second experiment. These results indicate that easily degradable organic carbon, together with a lower C:N ratio of the added material, will remove nitrogen from the water phase, making the recycling of nitrogen to the overlying water mass smaller.
Nanominerals and mineral nanoparticles from a mining-contaminated river system were examined to determine their potential to co-transport toxic trace metals. A recent large-scale dam removal project ...on the Clark Fork River in western Montana (USA) has released reservoir and upstream sediments contaminated with toxic trace metals (Pb, As, Cu and Zn), which had accumulated there as a consequence of more than a century and a half of mining activity proximal to the river’s headwaters near the cities of Butte and Anaconda. To isolate the high-density nanoparticle fractions from riverbed and bank sediments, a density separation with sodium polytungstate (2.8g/cm3) was employed prior to a standard nanoparticle extraction procedure. The stable, dispersed nanoparticulate fraction was then analyzed by analytical transmission electron microscopy (aTEM) and flow field-flow fractionation (FlFFF) coupled to both multi-angle laser light scattering (MALLS) and high-resolution, inductively coupled plasma mass spectrometry (HR-ICPMS). FlFFF analysis revealed a size distribution in the nano range and that the elution profiles of the trace metals matched most closely to that for Fe and Ti. aTEM confirmed these results as the majority of the Fe and Ti oxides analyzed were associated with one or more of the trace metals of interest. The main mineral phases hosting trace metals are goethite, ferrihydrite and brookite. This demonstrates that they are likely playing a significant role in dictating the transport and distribution of trace metals in this river system, which could affect the bioavailability and toxicity of these metals.
Based on an international workshop (Gothenburg, 14–16 May 2008), this review article aims to combine interdisciplinary knowledge from coastal and open ocean research on iron biogeochemistry. The ...major scientific findings of the past decade are structured into sections on natural and artificial iron fertilization, iron inputs into coastal and estuarine systems, colloidal iron and organic matter, and biological processes. Potential effects of global climate change, particularly ocean acidification, on iron biogeochemistry are discussed. The findings are synthesized into recommendations for future research areas.
Pore water metal profiles are important for identifying redox horizons and understanding trace metal geochemical cycling. The challenges of pore water sampling for trace metals are minimizing ...disturbance, especially at the sediment–water interface, and minimizing oxidation during sampling. We are investigating diffusional equilibration in thin films (DET) probes for obtaining pore water profiles. Our goal is to use probes for redox-sensitive trace metals U, Re and Mo, in addition to Mn and Fe, in coastal marine areas. Initial solution equilibration tests and laboratory core incubation experiments suggest that equilibration times for probes in sediments are approximately 24–48 h. Control tests suggest that the incubation does not alter the redox conditions in the pore waters. Pore water profiles from cores sampled by slicing, centrifuging and filtering (in a nitrogen atmosphere) and from probes are similar.
Two modifications on the gel probe design were tested to determine their impact. (1) PVC wedges were attached to the backs of probes to increase the contact between sediments and the probe surface and to reduce the risk of forming channels along the probe surface, which might allow vertical pore water transport. Lower Fe concentrations were measured from probes without PVC wedges, but other metal profiles were similar. (2) A modified face frame was removed from the front of a probe, to reduce disturbance of the sediments during insertion and to increase the contact between the sediments and probe surface. Probes with modified face frames did not have increasing U and Mo concentrations with depth, whereas two of the three probes without face frames did have increasing concentrations. Increasing U and Mo concentrations at depth may be reflecting the influence of irrigating burrows and their supply of oxygen to reduced sediments, which could oxidize previously reduced metals. The distribution of burrows is heterogeneous and resulting profiles would also be expected to be heterogeneous in their response.
Differences between probe profiles and sliced/centrifuged profiles are examined to gain insight into possible sampling artifacts. Peaks in the Re sliced/centrifuged profiles suggest a large Re flux to the overlying waters, which is neither calculated from probe profiles nor measured in benthic chamber samples. It is possible that heterogeneity at the sampling site in Buzzards Bay resulted in these differences; however, it is also possible that centrifugation releases Re from pore structures that would not be measured with less intrusive sampling methods, such as gel probes or benthic chambers.
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