Sampling and characterising groundwater nanoparticles in sub-oxic environments

Characterising nanoparticles is important for understanding physiochemical and biogeochemical processes occurring within groundwater bodies e.g. those impacted by the migration of leachates from waste storage sites as well as monitoring the use of engineered nanotechnology for pollution attenuation. While characterising nano-scale particles (both natural and engineered) within sub-oxic environments is a challenging task, it is critical for understanding pollution attenuation and migration within a number of different environments. The overall aim of this study was to develop a robust sampling and analytical methodology for characterising nanoparticles in sub-oxic environments using a range of complementary methods. This study has successfully sampled and characterised nano-scale particulate material in sub-oxic groundwaters within an alluvial floodplain aquifer impacted by a landfull plume. The integrity of the sample was maintained throughout the field and laboratory work to ensure that only nanoparticles representative of the sub-oxic environment were characterised. Nanoparticles from two pairs of nested boreholes were characterised by a number of state-of-the-art methods; atomic force microscopy (AFM), scanning electron microscopy (SEM), scanning transmisson electron microscopy (TEM) and field flow fractionation (FFF), to explore particle size distributions, morphology and surface chemistry. It is important to characterise nanoparticles in environmental contexts using multiple techniques as each method has its own benefits and limitations (Lead and Wilkinson 2006). As far as the authors are aware this is the first such study in the UK to isolate and characterise sub-oxic groundwater nanoparticles using these complimentary techniques. Groundwaters were found to have abundant iron and organic nanoparticles with diameters <30 nm. AFM results showed spherical nanoparticles with average diameters of ca 10 nm, while FFF with UV absorbance (254 nm) results indicated that smaller fulvic-like nanoparticles were present with average hydrodynamic diameters of ca. 1.5 nm. FFF with UV absorbance detection at 575 nm showed that another population of organic rich nanoparticles was present with larger hydrodynamic diameters (ca. 3 nm) in the groundwater at nest 26, but were not present in nest 28. These larger organic nanoparticles perhaps represent co-aggregated humic-like particles or another distinct type of organic matter. Scanning TEM analysis with energy-dispersive X-ray diffraction showed that Ca rich nanoparticles were present within the groundwater at a number of sites, and that P was associated with the surface of Fe rich particles in nest 28. Aeration of sub-oxic samples resulted in a dramatic shift in the nanoparticle size distribution. This was a result of the aggregation of smaller nanoparticles to form larger agglomerations with diameters typically >50-100 nm. This is analogous to processes that occur during groundwater aeration for water treatment, and mixing of anaerobic and aerobic environmental waters, e.g. during rapid recharge events, flooding, hyporheic zone mixing, waste water treatment and waste water inputs to surface waters. The techniques developed in this study have potential wider applications for understanding the occurrence and fate of natural and anthropogenic (engineered) nanoparticles in sub-oxic conditions, such as the fate of nanoparticles injected for pollution attenuation, those found below landfill sites, within waste water treatment works and the hyporheic zone which are all important redox hot-spots for pollution attenuation and biological activity

The critical importance of defined media conditions in Daphnia magna nanotoxicity studies

AbstractDue to the widespread use of silver nanoparticles (AgNPs), the likelihood of them entering the environment has increased and they are known to be potentially toxic. Currently, there is little information on the dynamic changes of AgNPs in ecotoxicity exposure media and how this may affect toxicity. Here, the colloidal stability of three different sizes of citrate-stabilized AgNPs was assessed in standard strength OECD ISO exposure media, and in 2-fold (media2) and 10-fold (media10) dilutions by transmission electron microscopy (TEM) and atomic force microscopy (AFM) and these characteristics were related to their toxicity towards Daphnia magna. Aggregation in undiluted media (media1) was rapid, and after diluting the medium by a factor of 2 or 10, aggregation was reduced, with minimal aggregation over 24h occurring in media10. Acute toxicity measurements were performed using 7nm diameter particles in media1 and media10. In media10 the EC50 of the 7nm particles for D. magna neonates was calculated to be 7.46μgL−1 with upper and lower 95% confidence intervals of 6.84μgL−1 and 8.13μgL−1 respectively. For media1, an EC50 could not be calculated, the lowest observed adverse effect concentration (LOAEC) of 11.25μgL−1 indicating a significant reduction in toxicity compared to that in media10. The data suggest the increased dispersion of nanoparticles leads to enhanced toxicity, emphasising the importance of appropriate media composition to fully assess nanoparticle toxicity in aquatic ecotoxicity tests

Contribution of humic substances from different composts to the synthesis of humin in a tropical soil

The contribution of humic substances of different composts to the synthesis of humin in a tropical soil was evaluated. Increasing doses (0, 13, 26, 52, and 104 Mg ha-1) of five different composts consisting of agroinpowderrial residues were applied to a Red-Yellow Latosol. These composts were chemically characterized and 13C NMR determined and the quantity of the functional alkyl groups of humic acids applied to the soil as compost was estimated. Thirty days after application of the treatments, organic matter samples were collected for fractionation of humic acids (HA), fulvic acids (FA) and humin (HU), from which the ratios HA/FA and (HA + FA)/HU were calculated. The application of the composts based on castor cake resulted in the highest HU levels in the soil; alkyl groups of the HA fraction of the composts were predominant in the organic components added to the HU soil fraction.Avaliou-se a contribuição de substâncias húmicas provenientes de diferentes compostos orgânicos na síntese de humina em um solo tropical. Para isso, foram adicionadas doses crescentes (0, 13, 26, 52 e 104 Mg ha-1) de cinco diferentes compostos orgânicos formulados com resíduos orgânicos agroindustriais em um Latossolo Vermelho-Amarelo. As substâncias húmicas desses compostos foram caracterizadas quimicamente e por ressonância nuclear magnética do 13C, sendo estimados os quantitativos dos grupos funcionais alquil dos ácidos húmicos aplicados no solo via composto. Trinta dias após aplicação dos tratamentos, coletaram-se amostras de solo para fracionamento da matéria orgânica em ácidos húmicos (AH), ácidos fúlvicos (FA) e humina (HU), a partir dos quais foram calculadas as relações AH/FA e (AH + FA)/HU. A aplicação do composto à base de torta de mamona contribuiu para obtenção de teores mais elevados de HU no solo; a incorporação de componentes orgânicos à fração HU do solo foi regida pelo conteúdo de grupos alquil da fração AH dos compostos

Characterising nanoparticles in sub-oxic environments

Characterising nanoparticles in sub-oxic environments is important for understanding pollution transport and attenuation within a range of situations, e.g. in waste water treatment plants, hyporheic zones and within groundwater. It has been shown that multi-method approaches are essential in an environmental context for adequate characterisation [1]. In the last decade there has been a focus on the use of manufactured nanoparticles for contaminant attenuation and remediation of groundwater e.g. Elliot and Zhang [2], Reinsch et al. [3]. Obtaining a representative sample and maintaining the environmental redox status throughout the field and laboratory work is a real challenge when working in these environments. To date, very few studies have successfully sampled and characterised nanoparticles in sub-oxic environments, e.g. anaerobic groundwaters, using a range of state-of-the-art techniques

Characterizing colloidal material in natural waters

Sampling has inherent uncertainties when applied tothe sub-micron fraction of natural waters. Processes of aggregation, biological activity andchemical transformation potentially effect changesimmediately after a sample is taken from the waterbody and there is no suitable method of samplestabilization. The size distribution and associatedphysical and chemical parameters of colloids in theaquatic environment can be effectively stable overshort periods of time (about two days under idealconditions, but frequently much shorter timeintervals). To achieve accurate representations of thesize distribution and associated colloidalcharacteristics in situ techniques are required,although adequate approximations may be obtained undersome circumstances if separation is done immediatelyafter sampling. This paper reviews the currentlyavailable strategies for separation and analysis ofcolloids from natural waters (primarily filtration andcentrifugation) and discusses their uses andlimitations, as well as potential uses of promisingtechniques (voltammetry, gels, field-flowfractionation, SPLITT). For small colloids, thetechniques of voltammetry, dialysis, DET and DGT maybe used to obtain in situ information. Forlarger colloids it is more difficult to performmeasurements in situ and a combination of rapidfractionation procedures, including filtration,field-flow fractionation and SPLITT, may still berequired

Status dello Storno Sturnus vulgaris svernante in Liguria e impatto sulle attivit\ue0 antropiche.

The applicability of environmental scanning electron microscopy (ESEM; imaging of hydrated samples) and conventional high vacuum scanning electron microscopy (SEM; imaging of dried samples at high vacuum) for the observation of natural aquatic colloids and particles was explored and compared. Specific attention was given to the advantages and limitations of these two techniques when used to assess the sizes and morphologies of complex and heterogeneous environmental systems. The observation of specimens using SEM involved drying and coating, whereas ESEM permitted their examination in hydrated form without prior sample preparation or conductive coating. The two techniques provided significantly different micrographs of the same sample. SEM provided sharper images, lower resolution limits (10 nm or lower), but more densely packed particles, suggesting aggregation, and different morphological features than ESEM, suggesting artefacts due to drying. ESEM produced less easily visualised materials, more complex interpretation, slightly higher resolution limits (30–50 nm), but these limitations were more than compensated for by the fact that ESEM samples retained, at least to some extent, their morphological integrity. The results in this paper show that SEM and ESEM should be regarded as complementary techniques for the study of aquatic colloids and particles and that ESEM should be more widely applied to aquatic environmental systems than hitherto

Europium-Coordinated Gold Nanoparticles on Paper for the Colorimetric Detection of Arsenic(III, V) in Aqueous Solution

The europium-functionalized gold nanoparticle is developed as a sensor for highly sensitive and specific detection of the very low concentration of As^III and As^V ions in water and using the paper strip. The GNP-MMT@Eu nanosensor is synthesized by stepwise chemical conjugations of gold nanoparticle (GNP) with 2-mercapto-4-methyl-5-thiazoleacetic acid (MMT) followed by europium chloride (EuCl₃) in deionized (DI) water. GNP-MMT@Eu shows a visible color change in the presence of both As^III and As^V ions in an aqueous medium, because of arsenic-mediated aggregation through electrostatic attraction and covalent-type interaction that form an inner-sphere arsenic complex between nanoparticles, which is proportional to the concentration of arsenic. The fluorometric properties of the nanosensor are not significant, and thus, only colorimetric and spectroscopic methods that are very much selective for As^III and As^V ions are used with a detection limit of ≤10.0 ppb. GNP-MMT@Eu also shows excellent capabilities for regeneration and quantitative estimation of total dissolved arsenic in a real water sample, signifying the usefulness of the developed nanosensor for field-test applications such as arsenic level screening during the water quality monitoring process

Quantifying the dynamics of flow within a permeable bed using time-resolved endoscopic particle imaging velocimetry (EPIV)

This paper presents results of an experimental study investigating the mean and temporal evolution of flow within the pore space of a packed bed overlain by a free-surface flow. Data were collected by an endoscopic PIV (EPIV) technique. EPIV allows the instantaneous velocity field within the pore space to be quantified at a high spatio-temporal resolution, thus permitting investigation of the structure of turbulent subsurface flow produced by a high Reynolds number freestream flow (Re s in the range 9.8 × 103–9.7 × 104). Evolution of coherent flow structures within the pore space is shown to be driven by jet flow, with the interaction of this jet with the pore flow generating distinct coherent flow structures. The effects of freestream water depth, Reynolds and Froude numbers are investigated