Challenges in Exposure Modeling of Nanoparticles in Aquatic Environments

Managing the potential environmental risks of nanoparticles requires methods to link nanoparticle properties with macro-scale risks. This study outlines challenges in exposure modeling of nanoparticles in aquatic environments, such as the role of natural organic matter, natural colloids, fractal dimensions of agglomerates, coatings and doping of particles, and uncertainties regarding nanoparticle emissions to aquatic environments. The pros and cons of the exposure indicators mass concentration, particle number concentration, and surface area are discussed. By applying colloid chemistry kinetic equations describing particle agglomeration and sedimentation for the case of titanium dioxide nanoparticles, a limited exposure assessment including some of the factors mentioned is conducted with particle number concentration as the exposure indicator. The results of the modeling indicate that sedimentation, shear flows, and settling are of less importance with regard to particle number based predicted environmental concentrations. The inflow of nanoparticles to the water compartment had a significant impact in the model, and the collision efficiency (which is affected by natural organic matter) was shown to greatly affect model output. Implications for exposure modeling, regulation and science are discussed. A broad spectrum of scientific disciplines must be engaged in the development of exposure models where nano-level properties are linked to macro-scale risk

Fractionation of iron species and iron isotopes in the Baltic Sea euphotic zone

To indentify sources and transport mechanisms of iron in a coastal marine environment, we conducted measurements of the physiochemical speciation of Fe in the euphotic zone at three different locations in the Baltic Sea. In addition to sampling across a salinity gradient, we conducted this study over the spring and summer season. Moving from the riverine input characterized low salinity Bothnian Sea, via the Landsort Deep near Stockholm, towards the Gotland Deep in the Baltic Proper, total Fe concentrations averaged 114, 44, and 15 nM, respectively. At all three locations, a decrease in total Fe of 80–90% from early spring to summer was observed. Particulate Fe (PFe) was the dominating phase at all stations and accounted for 75–85% of the total Fe pool on average. The Fe isotope composition (δ 56Fe) of the PFe showed constant positive values in the Bothnian Sea surface waters (+0.08 to +0.20‰). Enrichment of heavy Fe in the Bothnian Sea PFe is possibly associated to input of aggregated land derived Fe-oxyhydroxides and oxidation of dissolved Fe(II). At the Landsort Deep the isotopic fractionation of PFe changed between −0.08‰ to +0.28‰ over the sampling period. The negative values in early spring indicate transport of PFe from the oxic-anoxic boundary at ∼80 m depth. The average colloidal iron fraction (CFe) showed decreasing concentrations along the salinity gradient; Bothnian Sea 15 nM; Landsort Deep 1 nM, and Gotland Deep 0.5 nM. Field Flow Fractionation data indicate that the main colloidal carrier phase for Fe in the Baltic Sea is a carbon-rich fulvic acid associated compound, likely of riverine origin. A strong positive correlation between PFe and chl-a indicates that cycling of suspended Fe is at least partially controlled by primary production. However, this relationship may not be dominated by active uptake of Fe into phytoplankton, but instead may reflect scavenging and removal of PFe during phytoplankton sedimentation

Influence of trace metal release from volcanic ash on growth of Thalassiosira pseudonana and Emiliania huxleyi

Recent studies demonstrate that volcanic ash has the potential to increase phytoplankton biomass in the open ocean. However, besides fertilizing trace metals such as Fe, volcanic ash contains a variety of potentially toxic metals such as Cd, Cu, Pb, and Zn. Especially in coastal regions closer to the volcanic eruption, where ash depositions can be very high, toxic effects are possible. Here we present the first results of laboratory experiments, showing that trace metal release from different volcanic materials can have both fertilizing and toxic effects on marine phytoplankton in natural coastal seawater. The diatom Thalassiosira pseudonana generally showed higher growth rates in seawater that was in short contact with volcanic ash compared to the controls without ash addition. In contrast to that, the addition of volcanic ash had either no effect or significantly decreased the growth rate of the coccolithophoride Emiliania huxleyi. It was not possible to attribute the effects to single trace metals, however, our results suggest that Mn plays an important role in regulating the antagonistic and synergistic effects of the different trace metals. This study shows that volcanic ash can lead to changes in the phytoplankton species composition in the high fall-out area of the surface ocean. Highlights: ► We tested the effect of volcanic ash on growth of T. pseudonana and E. huxleyi ► Volcanic ash increased growth of T. pseudonana but not of E. huxleyi ► Mn seems important to regulate the effects of different trace metals from the ash ► Volcanic eruptions have the potential to change phytoplankton community structure

Size dependence of silver nanoparticle removal in a wastewater treatment plant mesocosm measured by FAST single particle ICP-MS

The quantities of engineered nanoparticles (NP) released to the environment are often influenced by their fate in waste water treatment plants (WWTP). Here, 40 nm silver NP (AgNP) were spiked into a mesocosm simulating the process used at a major municipal WWTP. The evolution of the mass distributions and number concentrations were followed by fast acquisition speed technique single particle inductively coupled mass spectrometry (FAST spICP-MS) using a high-resolution ICP-MS. It was thus possible to detect smaller Ag containing NP than hitherto possible in similar studies. These small particles (ca. 5-10 nm in corresponding metallic Ag equivalent spherical diameter) were possibly dissolved Ag+ precipitated as Ag2S particles. They were detected immediately upon spiking and were stable with respect to aggregation and thus much less removed by the WWTP process compared to the 40 nm AgNP. The results also suggested that any transformation of the latter AgNP occurred without dissolution. Most of these larger AgNP were probably removed by aggregation with large floc particles and subsequent sedimentation with the suspended particulate matter in the simulated WWTP process. The results have implications for differentiating the fate of nanoparticles as a function of size and demonstrate how spICP-MS can reveal such size-dependent fate dynamics

Iron biogeochemistry across marine systems progress from the past decade

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

Microplastics in sub-surface waters of the Arctic Central Basin

© 2018 Elsevier Ltd Polar oceans, though remote in location, are not immune to the accumulation of plastic debris. The present study, investigated for the first time, the abundance, distribution and composition of microplastics in sub-surface waters of the Arctic Central Basin. Microplastic sampling was carried out using the bow water system of icebreaker Oden (single depth: 8.5 m) and CTD rosette sampler (multiple depths: 8–4369 m). Potential microplastics were isolated and analysed using Fourier Transform Infrared Spectroscopy (FT-IR). Bow water sampling revealed that the median microplastic abundance in near surface waters of the Polar Mixed Layer (PML) was 0.7 particles m −3 . Regarding the vertical distribution of microplastics in the ACB, microplastic abundance (particles m −3 ) in the different water masses was as follows: Polar Mixed Layer (0–375) > Deep and bottom waters (0–104) > Atlantic water (0–95) > Halocline i.e. Atlantic or Pacific (0–83)

Factors influencing organic carbon recycling and burial in Skagerrak sediments

Different factors influencing recycling and burial rates of organic carbon (OC) were investigated in the continental margin sediments of the Skagerrak (NE North Sea). Two different areas, one in the southern and one in the northeastern part of the Skagerrak were visited shortly after a spring bloom (March 1999) and in late summer (August 2000). Results suggested that: (1) Organic carbon oxidation rates (Cox) (2.2–18 mmol C m-2d-11) were generally larger than the O2 uptake rates (1.9 –25 mmol m-2d-1). Both rates were measured in situ using a benthic lander. A mean apparent respiration ratio (Cox:O2corr) of 1.3±0.5 was found, indicating some long-term burial of reduced inorganic substances in these sediments. Measured O2 fluxes increased linearly with increasing Cox rates during the late summer cruise but not on the early spring cruise, indicating a temporal uncoupling of anaerobic mineralization and reoxidation of reduced substances. (2) Dissolved organic carbon (DOC) fluxes (0.2–1.0 mmol C m-2d-1) constituted 3–10% of the Cox rates and were positively correlated with the latter, implying that net DOC production rates were proportional to the overall sediment OC remineralization rates. (3) Chlorophyll a (Chl-a) concentrations in the sediment were significantly higher in early spring compared to late summer. The measured Cox rates, but not O2 fluxes, showed a strong positive correlation with the Chl-a inventories in the top 3 cm of the sediment. (4) Although no relationship was found between the benthic fluxes and the macrofaunal biomass in the chambers, total in situ measured dissolved inorganic carbon (CT) fluxes were 1–5.4 times higher than diffusive mediated CT fluxes, indicating that macrofauna have a significant impact on benthic exchange rates of OC remineralization products in Skagerrak sediments. (5) OC burial fluxes were generally higher in northeastern Skagerrak than in the southern part. The same pattern was observed for burial efficiencies, with annual means of ~62% and ~43% for the two areas respectively. (6) On a basin-wide scale, there was a significant positive linear correlation between the burial efficiencies and sediment accumulation rates. (7) The calculated particulate organic carbon (POC) deposition, from benthic flux and burial measurements, was only 24 –78% of the sediment trap measured POC deposition, indicating a strong near-bottom lateral transport and resuspension of POC. (8) A larger fraction of the laterally advected material of lower quality seemed to settle in the northeastern Skagerrak rather than in the southern Skagerrak. (9) Skagerrak sediments, especially in the northeastern part, act as an efficient net sink for organic carbon, even in a global continental margin context

Are We Speaking the Same Language? Recommendations for a Definition and Categorization Framework for Plastic Debris

The accumulation of plastic litter in natural environments is a global issue. Concerns over potential negative impacts on the economy, wildlife, and human health provide strong incentives for improving the sustainable use of plastics. Despite the many voices raised on the issue, we lack a consensus on how to define and categorize plastic debris. This is evident for microplastics, where inconsistent size classes are used and where the materials to be included are under debate. While this is inherent in an emerging research field, an ambiguous terminology results in confusion and miscommunication that may compromise progress in research and mitigation measures. Therefore, we need to be explicit on what exactly we consider plastic debris. Thus, we critically discuss the advantages and disadvantages of a unified terminology, propose a definition and categorization framework, and highlight areas of uncertainty. Going beyond size classes, our framework includes physicochemical properties (polymer composition, solid state, solubility) as defining criteria and size, shape, color, and origin as classifiers for categorization. Acknowledging the rapid evolution of our knowledge on plastic pollution, our framework will promote consensus building within the scientific and regulatory community based on a solid scientific foundation

Plutonium in groundwater at the 100K-Area of the U.S. DOE Hanford Site

Author Posting. © The Authors, 2004. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Journal of Contaminant Hydrology 76 (2005): 167-189, doi:10.1016/j.jconhyd.2004.08.004.We examined the concentration, size distribution, redox state and isotopic composition of plutonium (Pu) in groundwater at the 100K-Area at the US Department of Energys (DOE) Hanford Site. Total concentrations of Pu isotopes were extremely low (10-4 to 10-6 pCi/kg, ≈ 104 to 106 atoms/kg), but measurable for the first time in the 100K-Area wells using mass spectrometric analyses that are much more sensitive than alpha spectroscopy methods used previously. Size fractionation data from two wells suggests that 7-29% of the Pu is associated with colloids, operationally defined here as particles between 1 kDa 0.2 μm in size. These colloids were collected using a 1 kDa cross-flow ultrafiltration system developed specifically for groundwater actinide studies to include careful controls both in the field and during processing to ensure in-situ geochemical conditions are maintained and size separations can be well characterized. Pu in this colloidal fraction was exclusively in the more reduced Pu(III/IV) form, consistent with the higher affinity of Pu for particle surfaces in the lower oxidation states. While the overall concentrations of Pu were low, the Pu isotopic composition suggests at least two local sources of groundwater Pu, namely local Hanford reactor operations at the 100K-Area, and spent nuclear fuel from the N reactor, which was stored in concrete pools at this site. Differences between this site and the Savannah River Site (SRS) are noted, since groundwater Pu at the F-Area seepage basin at SRS has been found using these same 2 methods, to be characterized by much lower colloidal abundances and higher oxidation states. This difference is not directly attributable to groundwater redox potential or geochemical conditions, but rather the physical-chemical difference in Pu sources, which at SRS appear to be dominated downstream from the seepage basins by decay of 244Cm, resulting in more oxidized forms of 240Pu. There is no clear evidence for colloid facilitated transport of Pu in groundwater at this site, since downstream wells have both an order of magnitude lower concentrations of Pu, but also a lower fractional colloidal distribution.This research was supported under Grant No. DOE DE-FG07-96ER14733 and DE-FG02-03ER63659, Environmental Management Science Program, Office of Science and Technology, Office of Environmental Management, US Department of Energy. The preparation of the manuscript was also supported by China Natural Science Foundation (#49825162)