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Development of analytical methods for the characterization (particle size determination, identification, and quantification) of the micro- and nanoscale plastic debris in the environment is a quickly emerging field and has gained considerable attention, not only within the scientific community, but also on the part of policy makers and the general public. In this Trends paper, the importance of developing and further improving analytical methodologies for the detection and characterization of sub-20-μm-range microplastics and especially nanoplastics is highlighted. A short overview of analytical methodologies showing considerable promise for the detection and characterization of such micro- and nanoscale plastic debris is provided, with emphasis on recent developments in mass spectrometry (MS)-based analytical methods. Novel hyphenated techniques combining the strengths of different analytical methods, such as field flow fractionation and MS-based detection, may be a way to adequately address the smallest fractions in plastic debris analysis, making such approaches worthwhile to be further explored.

The impact of a silica coating on the degradation potential of nanoscale zerovalent iron (nZVI) particles toward a mixture of chlorinated ethylenes is presented. The newly employed stabilization method for nZVI, based on silica deposition from saturated sodium silicate water glass, produces nZVI particles with a similar reactivity as non-stabilized particles. Moreover the removal rate constant kM of trichloroethylene (0.1740 L g−1 d−1 Fe0) and cis-dichloroethylene (0.1045 L g−1 d−1Fe0) was significantly improved (almost by a factor of 2) for stabilized nZVI. X-ray photoelectron spectroscopy (XPS) and Wavelength Dispersive X-ray Fluorescence (WDXRF) analyzes revealed a high durability of silica coating and the coating left at least half of nZVI surface silica free for reaction for more than 5 weeks. The silica coating did not affect the surface composition of silica coated nZVI which was confirmed by the very similar distribution of degradation products and corrosion products (Fe3O4, FeOOH) as was found for non-coated nanoparticles. An enhanced reactivity supplemented with a stable corrosion properties indicates that silica coated nZVI has potential as an efficient remediation agent toward chlorinated ethylenes.

The reactivity and apparent corrosion rate of newly produced boron-alloyed microscale zerovalent iron (mZVI) particles toward a variety of chlorinated aliphatic hydrocarbons (CAHs) were assessed in laboratory-scale batch reactors. For comparison, commercially available nanoscale zerovalent irons (nZVIs) were also included in the study. Based on mass normalized ( k M ) pseudo first-order degradation rate constants, the reactivity of boron-alloyed mZVIs appeared to be one order of magnitude lower than most reactive nZVI. However, specific surface area normalized reaction rate constants ( k SA ) were 1–2 orders of magnitude higher than for nZVIs showing that boron-alloyed mZVIs can compete with nZVIs. The high reactivity of boron-alloyed mZVIs was attributed to (1) the prevented iron surface passivation during anaerobic corrosion due to the simultaneous iron and boron dissolution kinetics preventing the formation of insoluble oxidized iron species, (2) the involvement of boron in facilitating electron transfer by inducing β-elimination followed by hydrogenation to ethane and/or (3) involvement of boron in improved particle size reduction during milling process leading to increased active surface areas of the particles. Results of this study suggest that boron-alloyed mZVIs could be an efficient alternative to nZVIs for in situ groundwater remediation of different CAHs in terms of their reactivity and apparent corrosion rate.

The implementation and enforcement of product labeling obligation as required, for example, by the cosmetic product regulation, needs simple and precise validated analytical methods. This also applies to the analysis of nanoparticles in products such as cosmetics. However, the provision of such methods is often hampered by inaccurate sizing due to unwanted nanoparticle changes, interference of matrix components with sizing and interactions between nanoparticles and analytical instrumentation. It is, therefore, necessary to develop appropriate sample preparation methods that preserve NP properties and reduce or remove matrix compounds that interfere with sizing. Further, accurate particle size analysis of samples containing unknown and possibly multiple nanoparticulate constituents is needed. In this study, we evaluated three sample preparation methods to identify and quantify TiO2 nanoparticles in sunscreens. Specifically, we used a combination of ultracentrifugation and hexane washing, thermal destruction of the matrix, and surfactant assisted particle extraction. The method accuracy was assessed by two internal reference samples: pristine TiO2 nanoparticles (NM104) and similar TiO2 nanoparticles dispersed in a sunscreen matrix. The PSDs were determined using an asymmetrical flow field-flow fractionation hyphenated with multi-angle light scattering and inductively coupled plasma-mass spectroscopy. Particle sizing was based on size calibration of the particle retention time in the AF4. Computation of radius of gyration from MALS data was used as an orthogonal particle sizing approach to verify ideal elution and particle size data from the AF4 calibration. Among the three tested sample preparation methods surfactant assisted particle extraction revealed TiO2 nanoparticle recoveries of above 90% and no increase in particle size due to sample preparation was observed. Finally, the sample preparation methods were applied to two commercial sunscreen samples revealing the existence of TiO2-NP

In this study, an intra-laboratory assessment was carried out to establish the effectiveness of a method for the detection of TiO2 engineered nanoparticles (ENPs) present in sunscreen containing nano-scale TiO2 and a higher nanometer-range (approx. 200-500 nm) Ti02, as well as iron oxide particles. Three replicate measurements were performed on five separate days to generate the measurement uncertainties associated with the quantitative asymmetrical flow field-flow fractionation (AF4) measurement of the hydrodynamic radius r(h, mode1) (MALS), rh,,odei (ICP-MS), r(h, mode2) (ICP-MS), and calculated mass-based particle size distribution (d(10), d(50), d(90)). The validation study demonstrates that the analysis of TiO2 ENPs present in sunscreen by AF4 separation-multi detection produces quantitative data (mass-based particle size distribution) after applying the sample preparation method developed within the NanoDefine project with uncertainties based on the precision (u(IP)) of 3.9-8.8%. This method can, therefore, be considered as the method with a good precision. Finally, the bias data shows that the trueness of the method (u(t) = 5.5-52%) can only be taken as a proxy due to the lack of a sunscreen standard containing certified TiO2 ENPs.

International audience; Milled zerovalent iron (milled ZVI) particles have been recognized as a promising agent for groundwater remediation because of (1) their high reactivity with chlorinated aliphatic hydrocarbons, organochlorine pesticides, organic dyes, and a number of inorganic contaminants, and (2) a possible greater persistance than the more extensively investigated nanoscale zerovalent iron. We have used laboratory-scale batch degradation experiments to investigate the effect that hydrogeochemical conditions have on the corrosion of milled ZVI and on its ability to degrade trichloroethene (TCE). The observed pseudo first-order degradation rate constants indicated that the degradation of TCE by milled ZVI is affected by groundwater chemistry. The apparent corrosion rates of milled ZVI particles were of the same order of magnitude for hydrogeochemical conditions representative for two contaminated field sites (133–140 mmol kg− 1 day− 1, indicating a milled ZVI life-time of 128–135 days). Sulfate enhances milled ZVI reactivity by removing passivating iron oxides and hydroxides from the Fe0 surface, thus increasing the number of reactive sites available. The organic matter content of 1.69% in the aquifer material tends to suppress the formation of iron corrosion precipitates. Results from scanning electron microscopy, X-ray diffraction, and iron K-edge X-ray adsorption spectroscopy suggest that the corrosion mechanisms involve the partial dissolution of particles followed by the formation and surface precipitation of magnetite and/or maghemite. Numerical corrosion modeling revealed that fitting iron corrosion rates and hydrogen inhibitory terms to hydrogen and pH measurements in batch reactors can reduce the life-time of milled ZVI particles by a factor of 1.2 to 1.7.

The affinity between nanoscale zerovalent iron (nano-ZVI) and mineral surfaces hinders its mobility, and hence its delivery into contaminated aquifers. We have tested the hypothesis that the attachment of poly(acrylic acid)-coated nano-ZVI (PAA-nano-ZVI) to mineral surfaces could be limited by coating such surfaces with sodium (Na) humate prior to PAA-nano-ZVI injection. Na humate was expected to form a coating over favorable sites for PAA-nano-ZVI attachment and hence reduce the affinity of PAA-nano-ZVI for the collector surfaces through electrosteric repulsion between the two interpenetrating charged polymers. Column experiments demonstrated that a low concentration (10 mg/L) Na humate solution in synthetic water significantly improved the mobility of PAA-nano-ZVI within a standard sand medium. This effect was, however, reduced in more heterogeneous natural collector media from contaminated sites, as not an adequate amount of the collector sites favorable for PAA-nano-ZVI attachment within these media appear to have been screened by the Na humate. Na humate did not interact with the surfaces of acid-washed glass beads or standard Ottawa sand, which presented less surface heterogeneity. Important factors influencing the effectiveness of Na humate application in improving PAA-nano-ZVI mobility include the solution chemistry, the Na humate concentration, and the collector properties.

Microscale zerovalent iron (mZVI) reduces chlorinated aliphatic hydrocarbons (CAHs) to harmless compounds, but the sedimentation of the mZVI particles in the injection fluid limits the injectability of the particles during field applications. In this study, mZVI particles in suspension were stabilized by green polymer guar gum, which had a positive impact on mZVI stability, but decreased the reactivity of the particles towards CAHs by 1 to 8 times. Guar gum (GG) was found to adsorb onto the mZVI surface, inhibiting contact between the chlorinated compounds and the reactive iron surface. Indications were found for intermolecular hydrogen bonding between mZVI and the guar gum. Subsequent addition of commercially available enzymes resulted in the cleavage of the polysaccharide guar gum into lower molecular fragments, but not in improved reactivity. The reactivity recovery of guar gum coupled mZVI was recovered after intensive rinsing of the iron particles, removing the guar gum fragments from the particles. Overall, this study shows that CAHs can be treated efficiently by guar gum stabilized mZVI after reactivation by means of enzymatic breakdown and rinsing. (C) 2012 Elsevier B.V. All rights reserved.

Submicron-scale milled zerovalent iron (milled ZVI) particles produced by grinding macroscopic raw materials could provide a cost-effective alternative to nanoscale zerovalent iron (nZVI) particles for in situ degradation of chlorinated aliphatic hydrocarbons in groundwater. However, the aggregation and settling of bare milled ZVI particles from suspension presents a significant obstacle to their in situ application for groundwater remediation. In our investigations we reduced the rapid aggregation and settling rate of bare milled ZVI particles from suspension by stabilization with a "green" agar agar polymer. The transport potential of stabilized milled ZVI particle suspensions in a diverse array of natural heterogeneous porous media was evaluated in a series of well-controlled laboratory column experiments. The impact of agar agar on trichloroethene (TCE) removal by milled ZVI particles was assessed in laboratory-scale batch reactors. The use of agar agar significantly enhanced the transport of milled ZVI particles in all of the investigated porous media. Reactivity tests showed that the agar agar-stabilized milled ZVI particles were reactive towards TCE, but that their reactivity was an order of magnitude less than that of bare, non-stabilized milled ZVI particles. Our results suggest that milled ZVI particles could be used as an alternative to nZVI particles as their potential for emplacement into contaminated zone, their reactivity, and expected longevity are beneficial for in situ groundwater remediation.

A column study was performed under in situ conditions to evaluate to which extend the inactivation of the microscale zerovalent iron (mZVI) by guar gum occurs under continuous flow conditions. Five aquifer containing columns were set up under different conditions. Efficient removal of trichloroethene was observed for the column amended by mZVI. Stabilization of the mZVI with guar gum led to slightly reduced activity. More reduced reactivity was observed in the poisoned column containing guar gum stabilized mZVI. This confirms that soil microorganisms can degrade guar gum and that subsequent removal of the oligosaccharides by the groundwater flow (flushing effect) can reactivate the mZVI. After more than six months of continuous operation the columns were dismantled. DNA-based qPCR analysis revealed that mZVI does not significantly affect the bacterial community, while guar gum stabilized mZVI particles can even induce bacterial growth. Overall, this study suggests that the temporarily decreased mZVI reactivity due to guar gum, has a rather limited impact on the performance of in situ reactive zones. The presence of guar gum slightly reduced the reactivity of iron, but also slowed down the iron corrosion rate which prolongs the life time of reactive zone (C) 2013 Elsevier B.V. All rights reserved.

A standardized batch test procedure was developed and used to evaluate the reactivity of twelve newly designed microscale zerovalent iron (mZVI) particles and two biogenic iron sulfides towards a mixture of chlorinated aliphatic hydrocarbons (CAHs) and their breakdown products. For comparison, commercially available mZVIs, nanoscale zerovalent irons (nZVIs), iron sulfides (FeS) and granular zerovalent iron were also tested. Reactivity of the particles was based on observed (k(obs)) and mass normalized (k(M)) pseudo-first-order degradation rate constants, as well as specific surface area normalized reaction rate constants (k(SA)). Sorption characteristics of the particles were based on mass balance data. Among the new mZVIs, significant differences in reactivity were observed and the most reactive particles were identified. Based on k(M) data, nZVI degraded the examined contaminants one to two orders of magnitude faster than the mZVIs. k(M) values for biogenic iron sulfides were similar to the least reactive mZVIs. On the other hand, comparison of k(SA) data revealed that the reactivity of some newly designed mZVIs was similar to highly reactive nZVIs, and even up to one order of magnitude higher. k(SA) values for biogenic iron sulfides were one to two orders of magnitude lower than those reported for reactive mZVIs. (c) 2013 Elsevier B.V. All rights reserved.

Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content. 2013 Elsevier Ltd. All rights reserved.