The effect of a reduction of nitrogen and phosphorus to eutrophic and mesotrophic conditions towards silver nanoparticle (AgNP) on freshwater green algae species

We investigated the sensitivity of algae towards silver nanoparticles with OECD test medium and lower nutrient concentrations under standard test conditions to improve comparability and to exclude any other confounding factor aside nutrient levels. Two unicellular freshwater microalgae Desmodesmus subspicatus and Raphidocelis subcapitata were chosen due to their status as standard test organisms for the algae growth inhibition test and the response to changes in nutrient supply was compared. The original medium was used as the reference (standard). For the other four media, the amount of either nitrogen or phosphorus in the medium was lowered from half (50%) to one-fourth (25 %) of that of the OECD guideline, resulting in the following media: 50% N, 25% N, 50% P and 25% P medium. As test substance, the OECD reference material NM-300K was used. For this reason, the characterization of AgNP was done using DLS and Absorption spectra (UV/vis). Actual silver concentrations and ionic silver concentrations were measured at the highest test concentration used (100 µg Ag L-1) in R. subcapitata treatments only to reduce the number of samples. All tests were run according to the OECD guideline 201 with sterilized 50 mL cell culture flask. Each medium was tested using the test conditions for culturing with 3 replicates. Test concentrations for both algae species were 0, 25, 50 and 100 µg Ag L-1 for OECD, 50% P and 25% P while for both N reductions, the silver concentrations were 0, 10, 25 and 100 µg Ag L-1. Samples for determining the algal density were taken at every 24 h.

Image analysis from TEM and AFM micrograph, Table S1, S2, S3, Figure S1, Figure S2

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shal- low seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (b100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods. We provide analytical evidence for the presence in the water column of a large fraction of seep derived ele- ments (e.g. approximately 50% of iron, over 80% of Mn, 100% of Cr, S and Zn) in the form of nano sized par- ticles (e.g. b100 nm) even at typical open ocean pHs. We launch in situ sampling protocols and sample preparation procedures for multi-method suitable to obtain accurate measurements on nanoparticles from environmental samples. Based on our results a first insight to the formation of natural nanoparticles at cold CO2 seeps is presented and the persistence of such nano-clusters in the surrounding seawater is stipulated.

Magnetic extracts of three gravity cores located at the Ceará Rise, the Mid-Atlantic Ridge and the Sierra Leone Rise

The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.