Colloidal stability of nanoparticles derived from simulated cloud-processed mineral dusts

Laboratory simulation of cloud processing of three model dust types with distinct Fe-content (Moroccan dust, Libyan dust and Etna ash) and reference goethite and ferrihydrite were conducted in order to gain a better understanding of natural nanomaterial inputs and their environmental fate and bioavailability. The resulting nanoparticles (NPs) were characterised for Fe dissolution kinetics, aggregation/size distribution, micromorphology and colloidal stability of particle suspensions using a multi-method approach. We demonstrated that the: (i) acid-leachable Fe concentration was highest in volcanic ash (1 m Mg(-1) dust) and was followed by Libyan and Moroccan dust with an order of magnitude lower levels; (ii) acid leached Fe concentration in the<20 nm fraction was similar in samples processed in the dark with those under artificial sunlight, but average hydrodynamic diameter of NPs after cloud-processing (pH~6) was larger in the former; iii) NPs formed at pH~6 were smaller and less poly-disperse than those at low pH, whilst unaltered zeta potentials indicated colloidal instability; iv) relative Fe percentage in the finer particles derived from cloud processing does not reflect Fe content of unprocessed dusts (e.g. volcanic ash>Libyan dust). The common occurrence of Fe-rich "natural nanoparticles" in atmospheric dust derived materials may indicate their more ubiquitous presence in the marine environment than previously thought.

Chemical interaction of atmospheric mineral dust-derived nanoparticles with natural seawater — EPS and sunlight-mediated changes

Laboratory studies were conducted to investigate the interactions of nanoparticles (NPs) formed via simulated cloud processing of mineral dust with seawater under environmentally relevant conditions. The effect of sunlight and the presence of exopolymeric substances (EPS) were assessed on the: (1) colloidal stability of the nanoparticle aggregates (i.e. size distribution, zeta potential, polydispersity); (2) micromorphology and (3) Fe dissolution from particles. We have demonstrated that: (i) synthetic nano-ferrihydrite has distinct aggregation behaviour from NPs formed from mineral dusts in that the average hydrodynamic diameter remained unaltered upon dispersion in seawater (~1500 nm), whilst all dust derived NPs increased about three fold in aggregate size; (ii) relatively stable and monodisperse aggregates of NPs formed during simulated cloud processing of mineral dust become more polydisperse and unstable in contact with seawater; (iii) EPS forms stable aggregates with both the ferrihydrite and the dust derived NPs whose hydrodynamic diameter remains unchanged in seawater over 24h; (iv) dissolved Fe concentration from NPs, measured here as <3 kDa filter-fraction, is consistently >30% higher in seawater in the presence of EPS and the effect is even more pronounced in the absence of light; (v) micromorphology of nanoparticles from mineral dusts closely resemble that of synthetic ferrihydrite in MQ water, but in seawater with EPS they form less compact aggregates, highly variable in size, possibly due to EPS-mediated steric and electrostatic interactions. The larger scale implications on real systems of the EPS solubilising effect on Fe and other metals with the additional enhancement of colloidal stability of the resulting aggregates are discussed.

From plankton to top predators: bottom-up control of a marine food web across four trophic levels

1. Abundant mid-trophic pelagic fish often play a central role in marine ecosystems, both as links between zooplankton and top predators and as important fishery targets. In the North Sea, the lesser sandeel occupies this position, being the main prey of many bird, mammal and fish predators and the target of a major industrial fishery. However, since 2003, sandeel landings have decreased by > 50%, and many sandeel-dependent seabirds experienced breeding failures in 2004. 2. Despite the major economic implications, current understanding of the regulation of key constituents of this ecosystem is poor. Sandeel abundance may be regulated 'bottom-up' by food abundance, often thought to be under climatic control, or 'top-down' by natural or fishery predation. We tested predictions from these two hypotheses by combining unique long-term data sets (1973–2003) on seabird breeding productivity from the Isle of May, SE Scotland, and plankton and fish larvae from the Continuous Plankton Recorder survey. We also tested whether seabird breeding productivity was more tightly linked to sandeel biomass or quality (size) of individual fish. 3. The biomass of larval sandeels increased two- to threefold over the study period and was positively associated with proxies of the abundance of their plankton prey. Breeding productivity of four seabirds bringing multiple prey items to their offspring was positively related to sandeel larval biomass with a 1-year lag, indicating dependence on 1-year-old fish, but in one species bringing individual fish it was strongly associated with the size of adult sandeels. 4. These links are consistent with bottom-up ecosystem regulation and, with evidence from previous studies, indicate how climate-driven changes in plankton communities can affect top predators and potentially human fisheries through the dynamics of key mid-trophic fish. However, the failing recruitment to adult sandeel stocks and the exceptionally low seabird breeding productivity in 2004 were not associated with low sandeel larval biomass in 2003, so other mechanisms (e.g. predation, lack of suitable food after metamorphosis) must have been important in this case. Understanding ecosystem regulation is extremely important for predicting the fate of keystone species, such as sandeels, and their predators.

The Severn Estuary: Sediments, contaminants and biota. Occasional Publication of the Marine Biological Association 19

This report about the Severn Estuary provides an up to date appraisal of the following issues: Transport and fate of sediments; Transport, fate and trends in contaminants; Bioavailability of contaminants; Consequences for biota, and pinpoints the major knowledge gaps.