Currently there are few ideal methods for the characterization of nanoparticles in complex, environmental samples, leading to significant gaps in toxicity and exposure assessments of nanomaterials. Single particle-inductively coupled plasma-mass spectrometry (spICP-MS) is an emerging technique that can both size and count metal-containing nanoparticles. A major benefit of the spICP-MS method is its ability to characterize nanoparticles at concentrations relevant to the environment. This paper presents a practical guide on how to count and size nanoparticles using spICP-MS. Different methods are investigated for measuring transport efficiency (i.e. nebulization efficiency), an important term in the spICP-MS calculations. In addition, an alternative protocol is provided for determining particle size that broadens the applicability of the technique to all types of inorganic nanoparticles. Initial comparison, using well-characterized, monodisperse silver nanoparticles, showed the importance of having an accurate transport efficiency value when determining particle number concentration and, if using the newly presented protocol, particle size. Ultimately, the goal of this paper is to provide improvements to nanometrology by further developing this technique for the characterization of metal-containing nanoparticles.

Sizing engineered nanoparticles in simple, laboratory systems is now a robust field of science; however, application of available techniques to more complex, natural systems is hindered by numerous challenges including low nanoparticle number concentrations, polydispersity from aggregation and/or dissolution, and interference from other incidental particulates. A new emerging technique, single particle inductively coupled plasma-mass spectrometry (spICPMS), has the potential to address many of these analytical challenges when sizing inorganic nanoparticles in environmental matrices. However, to date, there is little beyond the initial feasibility studies that investigates the performance characteristics and validation of spICPMS as a nanoparticle sizing technique. This study compares sizing of four silver nanoparticle dispersions (nominal diameters of 40, 60, 80, and 100 nm) by spICPMS to four established sizing techniques: dynamic light scattering, differential centrifugal sedimentation, nanoparticle tracking analysis, and TEM. Results show that spICPMS is able to size silver nanoparticles, across different sizes and particle number concentrations, with accuracy similar to the other commercially available techniques. Furthermore, a novel approach to evaluating particle coincidence is presented. In addition, spICPMS size measurements were successfully performed on nanoparticles suspended in algal growth media at low concentrations. Overall, while further development of the technique is needed, spICPMS yields important advantages over other techniques when sizing nanoparticles in environmentally relevant media.

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Many sediment quality assessment frameworks incorporate contaminant bioavailability as a critical factor regulating toxicity in aquatic ecosystems. However, current approaches do not always adequately predict metal bioavailability to organisms living in the oxidized sediment surface layers. The deployment of the diffusive gradients in thin films (DGT) probes in sediments allows labile metals present in pore waters and weakly bound to the particulate phase to be assessed in a time-integrated manner in situ. In this study, relationships between DGT-labile metal fluxes within 5 mm of the sediment-water interface and lethal and sublethal effects to the amphipod Melita plumulosa were assessed in a range of contaminated estuarine sediments during 10-day laboratory-based bioassays. To account for differing toxicities of metals, DGT fluxes were normalized to water (WQG) or sediment quality guidelines or toxicity thresholds specific for the amphipod. The better dose-response relationship appeared to be the one based on WQG-normalized DGT fluxes, which successfully predicted toxicity despite the wide range of metals and large variations in sediment properties. The study indicated that the labile fraction of metals measured by DGT is useful for predicting metal toxicity to benthic invertebrates, supporting the applicability of this technique as a rapid monitoring tool for sediments quality assessments.

Many regulatory frameworks for sediment quality assessment include consideration of contaminant bioavailability. However, the "snap-shots" of metal bioavailability provided by analyses of porewaters or acid-volatile sulfide-simultaneously extractable metal (AVS-SEM) relationships do not always contribute sufficient information. The use of inappropriate or inadequate information for assessing metal bioavailability in sediments may result in incorrect assessment decisions. The technique of diffusive gradients in thin films (DGT) enables the in situ measurement of metal concentrations in waters and fluxes from sediment porewaters. We utilized the DGT technique to interpret the bioavailability of copper to the benthic bivalve Tellina deltoidalis in sediments of varying properties contaminated with copper-based antifouling paint particles. For a concentration series of copper-paint contaminated sandy, silty-sand, and silty sediment types, DGT-probes were used to measure copper fluxes to the overlying water, at the sediment-water interface, and in deeper sediments. The overlying water copper concentrations and DGT-Cu fluxes were shown to provide excellent exposure concentration-response relationships in relation to lethal effects occurring to the copper-sensitive benthic bivalve, T. deltoidalis. The study demonstrates the strength of the DGT technique, which we expect will become frequently used for assessing metal bioavailability in sediments.

Determining transport efficiency for the purpose of counting and sizing nanoparticles via single particle inductively coupled plasma mass spectrometry. Anal. Chem., 83, 9361-9369. Two errors occur in equation 3, which is also presented as part of Figure 1. As published, equation 3 is The corrected equation should be The signal intensity arising from the nanoparticle (I p-I Bgd) should be divided by the ionization efficiency, not multiplied. For the particles examined in this study (Au, Ag) we

. (2015). Metal fluxes from porewaters and labile sediment phases for predicting metal exposure and bioaccumulation in benthic invertebrates. Environmental Science and Technology (Washington), 49 (24), 14204-14212. Metal fluxes from porewaters and labile sediment phases for predicting metal exposure and bioaccumulation in benthic invertebrates AbstractThe use of diffusive gradients in thin films (DGT) for predicting metal bioavailability was investigated by exposing the bivalve Tellina deltoidalis to an identical series of metal-contaminated sediments deployed simultaneously in the field and laboratory. To understand the differences in metal exposure occurring between laboratory and field-based bioassays, changes in metal fluxes to DGT probes in sediments, and metal concentrations and partitioning to porewaters and overlying waters were investigated. DGT-metal fluxes (Cu, Pb and Zn) were lower in the overlying waters of most field-bioassays compared to the laboratory, causing differences in Pb and Zn bioaccumulation between bivalves exposed to laboratory and field conditions. Overall, DGT-metal fluxes provided predictions of metal bioaccumulation similar to those obtained using dilute-acid extractable metal measurements. This study demonstrates that, irrespective of the physicochemical properties of the sediment and type of exposure (laboratory or field), sediments pose a significant risk of bioaccumulation by T. deltoidalis when the Cu, Pb and Zn DGT flux exceeds 3.5, 1.3 and 156 µg/h/m2, respectively. The results presented here support the use of the DGT technique for sediment quality assessment and the hypothesis that DGT-metal fluxes may potentially be useful surrogates for the lability of metals for all exposure routes. * Corresponding author: Dianne JolleySchool of Chemistry, University of Wollongong, NSW 2522, Australia tel.: +61 2 4221 3516 E-mail address: djolley@uow.edu.au Rationale: Many sediment quality assessment frameworks consider the bioavailability of contaminants when evaluating the risk posed by contaminants to benthic communities. For metals, analyses of acidvolatile sulfide (AVS), simultaneously extracted metals (SEM) (dilute-acid extractable metals) and organic carbon (OC) are commonly used to assist in the bioavailability assessment. Although these approaches frequently provide useful information, they may result in inadequate predictions of risk of toxicity as they are based on a single measurement ('snapshots' temporally and spatially) that do not adequately reflect how the broader sediment properties (including particle size, iron and manganese oxyhydroxides etc) influence metal bioavailability. Diffusive gradients in thin films (DGT) is an in-situ technique which provides a timeintegrated measure of metal fluxes from the pore water and labile sediment phases, allowing the quantitative evaluation of the sediment metal 'release potential'. In this study, we assess the performance of the DGT technique to predict metal bioavailability by comparing DGT metal fluxes with metal bioaccumulati...

The biogeochemistry of acid mine drainage (AMD) derived from waste rock associated sulfide mineral oxidation is relatively well-characterized and linked to Acidithiobacillus spp.. However, little is understood about the microbial communities and sulfur cycling before AMD develops, a key component of its prevention. This study aimed to examine circum-neutral mining impacted water (MIW) communities and its laboratory enrichments for sulfur oxidizing bacteria (SoxBac). MIW in situ microbial communities differed in diversity, structure and relative abundance consistent with site specific variations in total aqueous sulfur concentrations (TotS; ~2–17 mM), pH (3.67–7.34), and oxygen (22–93% saturation). However, the sulfur oxidizer, Halothiobacillus spp. dominated seven of the nine total SoxBac enrichment communities (~76–100% relative abundance), spanning three of the four mines. The presence and relative abundance of the identified sixteen known and five unclassified Halothiobacillus spp. here, were the important clustering determinants across parent MIW and enrichment communities. Further, the presence of Halothiobacillus spp. was associated with driving the pH <4 in enrichment experiments, and the combination of specific Halothiobacillus spp. in the enrichments affected the observed acid to sulfate ratios indicating differential sulfur cycling. Halothiobacillus spp. also dominated the parent communities of the two acidic MIWs providing corroborating evidence for its active role in net acid generation within these waters. These results identify a putative indicator organism specific to mine tailings reservoirs and highlight the need for further study of tailings associated sulfur cycling for better mine management and environmental stewardship.