Volker Nischwitz

The potential of asymmetric flow field-flow fractionation hyphenated to multiple detectors for the quantification and size estimation of silica nanoparticles in a food matrix

AbstractThis work represents a first systematic approach to the size-based elemental quantification and size estimation of metal(loid) oxide nanoparticles such as silica (SiO2) in a real food matrix using asymmetric flow field-flow fractionation coupled online with inductively coupled plasma mass spectrometry (ICP-MS) and multi-angle light scattering (MALS) and offline with transmission electron microscopy (TEM) with energy-dispersive X-ray analysis (EDAX). Coffee creamer was selected as the model sample since it is known to contain silica as well as metal oxides such as titania at the milligramme per kilogramme levels. Optimisation of sample preparation conditions such as matrix-to-solvent ratio, defatting with organic solvents and sonication time that may affect nanoparticle size and size distribution in suspensions was investigated. Special attention was paid to the selection of conditions that minimise particle transformation during sample preparation and analysis. The coffee creamer matrix components were found to stabilise food grade SiO2 particles in comparison with water suspensions whilst no significant effect of defatting using hexane was found. The use of sample preparation procedures that mimic food cooking in real life was also investigated regarding their effect on particle size and particle size distribution of silica nanoparticles in the investigated food matrix; no significant effect of the water temperature ranging from ambient temperature to 60xa0°C was observed. Field-flow fractionation coupled to inductively coupled plasma-mass spectrometry (FFF-ICP-MS) analysis of extracts of both unspiked coffee creamer and coffee creamer spiked with food grade silicon dioxide, using different approaches for size estimation, enabled determination of SiO2 size-based speciation. Element-specific detection by ICP-MS and post-FFF calibration with elemental calibration standards was used to determine the elemental composition of size fractions separated online by FFF. Quantitative data on mass balance is provided for the size-based speciation of the investigated inorganic nano-objects in the complex matrix. The combination of FFF with offline fractionation by filtration and with detection by ICP-MS and TEM/EDAX has been proven essential to provide reliable information of nanoparticle size in the complex food matrix.n FigureCharacterisation of silica nanoparticles in a coffee creamer matrix using FFF-based methodology

Field flow fractionation online with ICP-MS as novel approach for the quantification of fine particulate carbon in stream water samples and soil extracts

Reliable and efficient analytical techniques are required for quantitative size-resolved carbon determination of nanoparticles and colloids in complex sample matrices due to the key role of carbon in biological and environmental processes. Field flow fractionation (FFF) online with inductively coupled plasma mass spectrometry (ICP-MS) is a powerful technique for identification and quantification of particle bound metals, but has not been applied for quantitative determination of particulate carbon, yet, due to several challenges. Therefore, our study explores the potential of online particulate carbon detection by ICP-MS to overcome limitations of previously used UV detection or offline total organic carbon measurements. A novel organic carbon detector (OCD) was used as independent sensitive carbon detector to validate the ICP-MS results. Basic validation of organic carbon detection by offline quadrupole and sector-field ICP-MS was performed for fresh water samples using OCD as reference achieving recoveries of 107 ± 16% with Q-ICP-MS and 122 ± 22% with SF-ICP-MS. Limits of detection were 0.6 mg L−1 for Q-ICP-MS, 0.3 mg L−1 for SF-ICP-MS and 0.04 mg L−1 for OCD. The main focus was on comparison of FFF-ICP-MS and FFF-OCD for quantification of particulate carbon in fresh water samples, soil extracts as well as in bovine serum albumin (BSA) as candidate reference standard. Recoveries obtained by FFF-Q-ICP-MS with a flow-injection calibration approach were in a range from 90 to 113% for replicate analyses of fresh water samples compared to FFF-OCD and from 87 to 107% with an alternative post-channel calibration strategy.

Elemental Composition of Natural Nanoparticles and Fine Colloids in European Forest Stream Waters and Their Role as Phosphorus Carriers

Biogeochemical cycling of elements largely occurs in dissolved state, but many elements may also be bound to natural nanoparticles (NNP, 1-100 nm) and fine colloids (100-450 nm). We examined the hypothesis that the size and composition of stream water NNP and colloids vary systematically across Europe. To test this hypothesis, 96 stream water samples were simultaneously collected in 26 forested headwater catchments along two transects across Europe. Three size fractions (~1-20 nm, >20-60 nm, and >60 nm) of NNP and fine colloids were identified with Field Flow Fractionation coupled to inductively coupled plasma mass spectrometry and an organic carbon detector. The results showed that NNP and fine colloids constituted between 2 ± 5% (Si) and 53 ± 21% (Fe; mean ± SD) of total element concentrations, indicating a substantial contribution of particles to element transport in these European streams, especially for P and Fe. The particulate contents of Fe, Al, and organic C were correlated to their total element concentrations, but those of particulate Si, Mn, P, and Ca were not. The fine colloidal fractions >60 nm were dominated by clay minerals across all sites. The resulting element patterns of NNP <60 nm changed from North to South Europe from Fe- to Ca-dominated particles, along with associated changes in acidity, forest type, and dominant lithology. (Less)

First Comprehensive Study on Total Contents and Hot water Extractable Fraction of selected elements in 19 Medicinal Plants from Various Locations in Nyamira County, Kenya.

A large number of medicinal plants is traditionally known in Kenya and used for treatment of various diseases, for example diabetes, where metals are supposed to be involved in pathogenesis and therapy. Therefore, detailed investigation of the concentration of a large number of metals in medicinal plants is required for improved understanding and optimisation of the therapeutic role of metals and also to exclude potentially toxic effects. Our study focused on the determination of 30 selected elements in 19 medicinal plant species each collected from 3 sampling locations in Nyamira County, Kenya. The obtained comprehensive data set showed large variability and multivariate data analysis revealed that the differences in the elemental composition were stronger dependent on the plant species than on the sampling location. In addition, hot water extractions were performed to mimic the traditional preparation of medicine from the plants. It was found that the mean extraction efficiencies were below 20% except for B, Mg, P, K, Mn, Co, Ni, Cu, Zn, Rb, Mo, Cd and Tl, which are mostly essential elements apart from Cd and Tl. Sequential (ultra)filtration of the extracts was applied as novel approach for molecular size-fractionation of the extracted elemental species. The results indicate more than 50% low molecular weight species (<3kDa) for Mg, Mn, Co, Ni and Zn while predominantly larger size-fractions (>3kDa up to<5μm) were detected for V, Cu, Al and Fe.

Leaching of natural colloids from forest topsoils and their relevance for phosphorus mobility

The leaching of P from the upper 20cm of forest topsoils influences nutrient (re-)cycling and the redistribution of available phosphate and organic P forms. However, the effective leaching of colloids and associated P forms from forest topsoils was so far sparsely investigated. We demonstrated through irrigation experiments with undisturbed mesocosm soil columns, that significant proportions of P leached from acidic forest topsoils were associated with natural colloids. These colloids had a maximum size of 400nm. By means of Field-flow fractionation the leached soil colloids could be separated into three size fractions. The size and composition was comparable to colloids present in acidic forest streams known from literature. The composition of leached colloids of the three size classes was dominated by organic carbon. Furthermore, these colloids contained large concentrations of P which amounted between 12 and 91% of the totally leached P depending on the type of the forest soil. The fraction of other elements leached with colloids ranged between 1% and 25% (Fe: 1-25%; Corg: 3-17%; Al: <4%; Si, Ca, Mn: all <2%). The proportion of colloid-associated P decreased with increasing total P leaching. Leaching of total and colloid-associated P from the forest surface soil did not increase with increasing bulk soil P concentrations and were also not related to tree species. The present study highlighted that colloid-facilitated P leaching can be of higher relevance for the P leaching from forest surface soils than dissolved P and should not be neglected in soil water flux studies.

ICP-MS for the analysis at the nanoscale – a tutorial review

This tutorial review focuses on the use of ICP-MS based techniques for the analysis of metal-containing nanoparticles and colloids. Within the first part the capabilities of “stand alone” ICP-MS for the analysis of total metal contents and the suitability of stable isotopes for nanoparticle tracking (stable isotope labelling and naturally occurring variation in isotope ratios) are introduced (Chapter 3). Special focus was given on single particle ICP-MS (sp-ICP-MS) mode (Chapter 4). Upon a brief introduction into the theoretical concept, critical aspects such as calibration strategies, dwell time as well as ionic background were discussed and practical advice is given. References to current data assessment sheets are provided. Furthermore, a brief chapter on general sample preparation aspects is included within the first part (Chapter 2). The second part is dedicated to fractionation/separation systems, such as field-flow fractionation (FFF), hydrodynamic chromatography (HDC), high performance liquid chromatography (HPLC) and capillary electrophoresis (CE) coupled on-line with ICP-MS detection for metal-based nanoparticle and colloid analysis (Chapter 5). Each section starts with an introduction into the theoretical concept of the respective fractionation/separation system, followed by practical hints regarding method development (e.g. selection of appropriate carrier/mobile phase, membrane/stationary phase) as well as critical aspects and limitations. Particular attention is payed to laser ablation ICP-MS (LA-ICP-MS) for spatially resolved nanoparticle analysis. Each section concludes with selected application examples of the respective analytical technique from the most relevant fields of nanoparticle use or exposure (consumer products, food, medicine and environment), highlighting the performance of each technique in metal-based nanoparticle analysis. Chapter 6 is dedicated to aspects of quality assurance. Various critical points regarding method development and validation, mass balance, size calibration and quantification from the previous sections are revisited, discussed and practical advice is given. Finally, the authors provide some concluding remarks and future perspectives (Chapter 7). Furthermore, a flow-chart is included as a “hands-on” overview on all ICP-MS based techniques discussed within this tutorial review intended as a “method-decision tool” for users.

Extending the capabilities of field flow fractionation online with ICP-MS for the determination of particulate carbon in latex and charcoal

There is a broad range of carbon based engineered particles including polymer latex particles and carbon black. Also in environmental systems particulate carbon such as humic acids and soot or coal (the latter two summarized as black carbon) is of great importance and is involved in nutrient storage and (re)cycling. Therefore, detailed characterisation of the size distribution and elemental composition of such particles is required to understand the material properties and their environmental relevance. Field flow fractionation (FFF) online with inductively coupled plasma mass spectrometry (ICP-MS) is routinely applied for the characterisation of metal containing particles. However, the far majority of FFF studies relies on UV detection for organic carbon while elemental detection of carbon has hardly been used. Our previous work demonstrated the capability of FFF-ICP-MS for the determination of carbon in fine particulate matter, focusing on humic acid in water samples. The current work investigates the feasibility of carbon detection and quantification in larger particles with sizes up to about 750 nm. For this purpose, latex particle size standards of 21 nm, 100 nm, 250 nm and 740 nm were analysed as well as extracts of charcoal spiked soil. Elemental analysis using combustion techniques was employed as reference for the total carbon content of the samples to establish a mass balance. Recoveries for FFF separation of latex particle standards were in the range from 69% to 83% and in the range from 78% to 104% in flow injection mode. Carbon mass balance calculated from FFF fractionation, ultrafiltration and total content for the extracts from soil and charcoal spiked soil achieved 76% to 105%. Variation of the sampling depth was investigated to check if increased dwell time of the particles in the plasma affects the carbon ionisation and quantification. No significant change of carbon recoveries was observed, yet the signal to noise ratio improved 3-fold. This study provides a method for the analyses of carbon containing particles via FFF-ICP-MS, which allows for the first time the simultaneous measurement of carbon and other nutrients and is hence more timesaving than other methods.

Sequential extraction as novel approach to compare 12 medicinal plants from Kenya regarding their potential to release Chromium, Manganese, Copper, and Zinc.

This study is focusing on a novel approach to screen a large number of medicinal plants from Kenya regarding their contents and availability of selected metals potentially relevant for treatment of diabetes patients. For this purpose, total levels of zinc, chromium, manganese, and copper were determined by flame atomic absorption spectrometry and inductively coupled plasma mass spectrometry as well as BCR sequential extraction to fractionate the elemental species in anti-diabetic medicinal plants collected from five natural locations in two sub counties in Nyamira County, Kenya. Solanum mauense had the highest zinc level of 123.0xa0±xa03.1xa0mg/kg while Warburgia ugandensis had the lowest level of 13.9xa0±xa00.4xa0mg/kg. The highest level of copper was in Bidens pilosa (29.0xa0±xa00.6xa0mg/kg) while the lowest was in Aloe vera (3.0xa0±xa00.1xa0mg/kg). Croton macrostachyus had the highest manganese level of 1630xa0±xa040xa0mg/kg while Clerodendrum myricoides had the lowest (80.2xa0±xa01.2xa0mg/kg). The highest level of chromium was in Solanum mauense (3.20xa0±xa00.06xa0mg/kg) while the lowest (0.04xa0±xa00.01xa0mg/kg) were in Clerodendrum myricoides and Warburgia ugandesis among the medicinal plants from Nyamira and Borabu, respectively. The levels of the elements were statistically different from that of other elements while the level of a given element was not statistically different in the medicinal plants from the different sub counties. Sequential extraction was performed to determine the solubility and thus estimate the bioavailability of the four investigated essential and potentially therapeutically relevant metals. The results showed that the easily bioavailable fraction (EBF) of chromium, manganese, zinc, and copper ranged from 6.7 to 13.8%, 4.1 to 10%, 2.4 to 10.2%, and 3.2 to 12.0% while the potentially bioavailable fraction (PBF) ranged from 50.1 to 67.6%, 32.2 to 48.7%, 23.0 to 41.1%, and 34.6 to 53.1%, respectively. Bidens pilosa, Croton macrostachyus, Ultrica dioica, and Solanum mauense medicinal plants used to treat diabetes by 80 % of the herbalists in Nyamira County were found to be rich in chromium, manganese, copper, and zinc. The EBF of zinc, manganese, and chromium constitutes adequate amounts recommended for daily intake not exceeding the ADI and delivered a low percentage of RDA when estimating daily intake during therapy from typically applied doses. The plants did not show any significant differences at pxa0<xa00.05 in terms of concentrations of the elements between the two study areas though the levels of the different elements were statistically significant. Another major observation was that high total levels of the metals in a given plant did not necessarily translate to high bioavailable levels, and hence the need to determine bioavailable form as it is the one accessible to the patient.