Imaging the elemental distribution within human malignant melanomas using Laser-Induced Breakdown Spectroscopy.

The diagnosis of malignant melanoma, often an inconspicuous but highly aggressive tumor, is most commonly done by histological examination, while additional diagnostic methods on the level of elements and molecules are constantly being developed. Several studies confirmed differences in the chemical composition of healthy and tumor tissue. Our study presents the potential of the LIBS (Laser-Induced-Breakdown Spectroscopy) technique as a diagnostic tool in malignant melanoma (MM) based on the quantitative changes in elemental composition in cancerous tissue. Our patient group included 17 samples of various types of malignant melanoma and one sample of healthy skin tissue as a control. To achieve a clear perception of results, we have selected two biogenic elements (calcium and magnesium), which showed a dissimilar distribution in cancerous tissue from its healthy surroundings. Moreover, we observed indications of different concentrations of these elements in different subtypes of malignant melanoma, a hypothesis that requires confirmation in a more extensive sample set. The information provided by the LIBS Imaging method could potentially be helpful not only in the diagnostics of tumor tissue but also be beneficial in broadening the knowledge about the tumor itself.

Comparison of single and double pulse laser-induced breakdown spectroscopy for the detection of biomolecules tagged with photon-upconversion nanoparticles.

BACKGROUND: Laser-induced breakdown spectroscopy (LIBS) is a well-recognized analytical technique used for elemental analysis. This method is gaining considerable attention also in biological applications thanks to its ability for spatial mapping and elemental imaging. The implementation of LIBS in the biomedical field is based on the detection of metals or other elements that either naturally occur in the samples or are present artificially. The artificial implementation of nanoparticle labels (Tag-LIBS) enables the use of LIBS as a readout technique for immunochemical assays. However, one of the biggest challenges for LIBS to meet immunoassay readout standards is its sensitivity. RESULTS: This paper focuses on the improvement of LIBS sensitivity for the readout of nanoparticle-based immunoassays. First, the LIBS setup was optimized on photon-upconversion nanoparticle (UCNP) droplets deposited on the microtiter plate wells. Two collection optics systems were compared, with single pulse (SP) and collinear double pulse (DP) LIBS arrangements. By deploying the second laser pulse, the sensitivity was improved up to 30 times. The optimized SP and DP setups were then employed for the indirect detection of human serum albumin based on immunoassay with UCNP-based labels. Compared to our previous LIBS study, the detection limit was enhanced by two orders of magnitude, from 10 ng mL-1 to 0.29 ng mL-1. In addition, two other immunochemical methods were used for reference, based on the readout of upconversion luminescence of UCNPs and absorbance measurement with enzyme labels. Finally, the selectivity of the assay was tested and the practical potential of Tag-LIBS was demonstrated by the successful analysis of urine samples. SIGNIFICANCE AND NOVELTY: In this work, we improved the sensitivity of the Tag-LIBS method by combining new labels based on UCNPs with the improved collection optics and collinear DP configuration. In the instrumental setup optimization, the DP LIBS showed better sensitivity and signal-to-noise ratio than SP. The optimizations allowed the LIBS readout to surpass the sensitivity of enzyme immunoassay, approaching the qualities of upconversion luminescence readout, which is nowadays a state-of-the-art readout technique.

Laser-based techniques: Novel tools for the identification and characterization of aged microplastics with developed biofilm.

Microplastics found in the environment are often covered with a biofilm, which makes their analysis difficult. Therefore, the biofilm is usually removed before analysis, which may affect the microplastic particles or lead to their loss during the procedure. In this work, we used laser-based analytical techniques and evaluated their performance in detecting, characterizing, and classifying pristine and aged microplastics with a developed biofilm. Five types of microplastics from different polymers were selected (polyamide, polyethylene, polyethylene terephthalate, polypropylene, and polyvinyl chloride) and aged under controlled conditions in freshwater and wastewater. The development of biofilm and the changes in the properties of the microplastic were evaluated. The pristine and aged microplastics were characterized by standard methods (e.g., optical and scanning electron microscopy, and Raman spectroscopy), and then laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were used. The results show that LIBS could identify different types of plastics regardless of the ageing and major biotic elements of the biofilm layer. LA-ICP-MS showed a high sensitivity to metals, which can be used as markers for various plastics. In addition, LA-ICP-MS can be employed in studies to monitor the adsorption and desorption (leaching) of metals during the ageing of microplastics. The use of these laser-based analytical techniques was found to be beneficial in the study of environmentally relevant microplastics.

Analysis of Laser-Induced Breakdown Spectroscopy Data Acquired from Boundary of Two Matrices.

Laser-induced breakdown spectroscopy (LIBS) data obtained from the elemental imaging of heterogenous samples were processed with various chemometric algorithms. The intention was to cluster obtained characteristic spectra and to provide additional information about the sample surface composition and distribution of individual matrices. However, there is a gray zone on the boundary of two matrices and the consequent clustering of the spectra obtained on this boundary is ambiguous. This paper focuses on the transition between two well-defined matrices in a simplified case for a better transparency in data visualization. Steel and aluminum samples that are represented by characteristic spectra with significantly distinct structures (e.g., different number of spectral lines). Using a carefully designed experiment, several Fe:Al ratios were ablated and analyzed by principal component analysis (PCA), self-organizing maps (SOM), and standard data metrics. This paper shows the strategy for the discrimination of unrecognized spectra and possibilities in their clustering.

Interpreting support vector machines applied in laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy is often combined with a multivariate black box model-such as support vector machines (SVMs)-to obtain desirable quantitative or qualitative results. This approach carries obvious risks when practiced in high-stakes applications. Moreover, the lack of understanding of a black-box model limits the user's ability to fine-tune the model. Thus, here we present four approaches to interpret SVMs through investigating which features the models consider important in the classification task of 19 algal and cyanobacterial species. The four feature importance metrics are compared with popular approaches to feature selection for optimal SVM performance. We report that the distinct feature importance metrics yield complementary and often comparable information. In addition, we identify our SVM model's bias towards features with a large variance, even though these features exhibit a significant overlap between classes. We also show that the linear and radial basis kernel SVMs weight the same features to the same degree.

The Development of Dentin Microstructure Is Controlled by the Type of Adjacent Epithelium.

Considerable amount of research has been focused on dentin mineralization, odontoblast differentiation, and their application in dental tissue engineering. However, very little is known about the differential role of functionally and spatially distinct types of dental epithelium during odontoblast development. Here we show morphological and functional differences in dentin located in the crown and roots of mouse molar and analogous parts of continuously growing incisors. Using a reporter (DSPP-cerulean/DMP1-cherry) mouse strain and mice with ectopic enamel (Spry2+/- ;Spry4-/- ), we show that the different microstructure of dentin is initiated in the very beginning of dentin matrix production and is maintained throughout the whole duration of dentin growth. This phenomenon is regulated by the different inductive role of the adjacent epithelium. Thus, based on the type of interacting epithelium, we introduce more generalized terms for two distinct types of dentins: cementum versus enamel-facing dentin. In the odontoblasts, which produce enamel-facing dentin, we identified uniquely expressed genes (Dkk1, Wisp1, and Sall1) that were either absent or downregulated in odontoblasts, which form cementum-facing dentin. This suggests the potential role of Wnt signalling on the dentin structure patterning. Finally, we show the distribution of calcium and magnesium composition in the two developmentally different types of dentins by utilizing spatial element composition analysis (LIBS). Therefore, variations in dentin inner structure and element composition are the outcome of different developmental history initiated from the very beginning of tooth development. Taken together, our results elucidate the different effects of dental epithelium, during crown and root formation on adjacent odontoblasts and the possible role of Wnt signalling which together results in formation of dentin of different quality. © 2021 The Authors. Journal of Bone and Mineral Research published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research (ASBMR).

Laser-induced breakdown spectroscopy as a readout method for immunocytochemistry with upconversion nanoparticles.

Immunohistochemistry (IHC) and immunocytochemistry (ICC) are widely used to identify cancerous cells within tissues and cell cultures. Even though the optical microscopy evaluation is considered the gold standard, the limited range of useful labels and narrow multiplexing capabilities create an imminent need for alternative readout techniques. Laser-induced breakdown spectroscopy (LIBS) enables large-scale multi-elemental analysis of the surface of biological samples, e.g., thin section or cell pellet. It is, therefore, a potential alternative for IHC and ICC readout of various labels or tags (Tag-LIBS approach). Here, we introduce Tag-LIBS as a method for the specific determination of HER2 biomarker. The cell pellets were labeled with streptavidin-conjugated upconversion nanoparticles (UCNP) through a primary anti-HER2 antibody and a biotinylated secondary antibody. The LIBS scanning enabled detecting the characteristic elemental signature of yttrium as a principal constituent of UCNP, thus indirectly providing a reliable way to differentiate between HER2-positive BT-474 cells and HER2-negative MDA-MB-231 cells. The comparison of results with upconversion optical microscopy and luminescence intensity scanning confirmed that LIBS is a promising alternative for the IHC and ICC readout.

Laser-induced breakdown spectroscopy as a straightforward bioimaging tool for plant biologists; the case study for assessment of photon-upconversion nanoparticles in Brassica oleracea L. plant.

The main purpose of this work is to thoroughly describe the implementation protocol of laser-induced breakdown spectroscopy (LIBS) method in the plant analysis. Numerous feasibility studies and recent progress in instrumentation and trends in chemical analysis make LIBS an established method in plant bioimaging. In this work, we present an easy and straightforward phytotoxicity case study with a focus on LIBS method. We intend to demonstrate in detail how to manipulate with plants after exposures and how to prepare them for analyses. Moreover, we aim to achieve 2D maps of spatial element distribution with a good resolution without any loss of sensitivity. The benefits of rapid, low-cost bioimaging are highlighted. In this study, cabbage (Brassica oleracea L.) was treated with an aqueous dispersion of photon-upconversion nanoparticles (NaYF4 doped with Yb3+ and Tm3+ coated with carboxylated silica shell) in a hydroponic short-term toxicity test. After a 72-hour plant exposure, several macroscopic toxicity end-points were monitored. The translocation of Y, Yb, and Tm across the whole plant was set by employing LIBS with a lateral resolution 100 µm. The LIBS maps of rare-earth elements in B.oleracea plant grown with 50 µg/mL nanoparticle-treated and ion-treated exposures showed the root as the main storage, while the transfer via stem into leaves was minimal. On the contrary, the LIBS maps of plants exposed to the 500 µg/mL nanoparticle-treated and ion-treated uncover slightly different trends, nanoparticles as well as ions were transferred through the stem into leaves. However, the main storage organ was a root as well.

Methodology for the Implementation of Internal Standard to Laser-Induced Breakdown Spectroscopy Analysis of Soft Tissues.

The improving performance of the laser-induced breakdown spectroscopy (LIBS) triggered its utilization in the challenging topic of soft tissue analysis. Alterations of elemental content within soft tissues are commonly assessed and provide further insights in biological research. However, the laser ablation of soft tissues is a complex issue and demands a priori optimization, which is not straightforward in respect to a typical LIBS experiment. Here, we focus on implementing an internal standard into the LIBS elemental analysis of soft tissue samples. We achieve this by extending routine methodology for optimization of soft tissues analysis with a standard spiking method. This step enables a robust optimization procedure of LIBS experimental settings. Considering the implementation of LIBS analysis to the histological routine, we avoid further alterations of the tissue structure. Therefore, we propose a unique methodology of sample preparation, analysis, and subsequent data treatment, which enables the comparison of signal response from heterogenous matrix for different LIBS parameters. Additionally, a brief step-by-step process of optimization to achieve the highest signal-to-noise ratio (SNR) is described. The quality of laser-tissue interaction is investigated on the basis of the zinc signal response, while selected experimental parameters (e.g., defocus, gate delay, laser energy, and ambient atmosphere) are systematically modified.

Spatiotemporal spectroscopic characterization of plasmas induced by non-orthogonal laser ablation.

Ablation geometry significantly affects the plasma parameters and the consequent spectroscopic observations in laser-induced breakdown spectroscopy. Nevertheless, plasmas induced by laser ablation under inclined incidence angles are studied to a significantly lesser extent compared to plasmas induced by standard orthogonal ablation. However, inclined ablation is prominent in stand-off applications, such as the Curiosity Mars rover, where the orthogonality of the ablation laser pulse cannot be always secured. Thus, in this work, we characterize non-orthogonal ablation plasmas by applying plasma imaging, tomography, and spectral measurements. We confirm earlier observations according to which non-orthogonal ablation leads to a laser-induced plasma that consists of two distinct parts: one expanding primarily along the incident laser pulse and one expanding along the normal of the sample surface. Moreover, we confirm that the former emits mainly continuum radiation, while the latter emits mainly sample-specific characteristic radiation. We further investigate and compare the homogeneity of the plasmas and report that inclined ablation affects principally the ionic emissivity of laser-induced plasmas. Overall, our results imply that the decreased fluence resulting from inclined angle ablation and the resulting inhomogeneities of the plasmas must be considered for quantitative LIBS employing non-orthogonal ablation.

Influence of sample surface topography on laser ablation process.

In this work we discuss how sample surface topography can significantly influence the laser ablation (LA) process and, in turn, the analytical response of the LA Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) method. Six different surface topographies were prepared on a certified aluminium alloy sample BAM 311 and SRM NIST 610 to investigate the phenomenon. All the samples were repetitively measured by LA-ICP-MS using a spot by spot analysis. The effect of laser fluence in the range of 1-13 J/cm2 was studied. For majority of measured isotopes, the ICP-MS signal was amplified with roughening of the sample surface. A stronger effect was observed on the Al alloy sample, where the more than sixty-time enhancement was achieved in comparison to the polished surface of the sample. Since the effect of surface topography is different for each analyte, it can be stated that surface properties affect not only the ICP-MS response, but also elemental fractionation in LA. The presented results show that different surface topographies may lead to misleading data interpretation because even when applying ablation preshots, the signal of individual elements changes. The utmost care must be taken when preparing the surface for single shot analysis or chemical mapping. On the other hand, by roughening the sample surface, it is possible to significantly increase the sensitivity of the method for individual analytes and supress a matrix effect.

Tomography of double-pulse laser-induced plasmas in the orthogonal geometry.

The temporal evolution of laser-induced plasmas is studied in the orthogonal double-pulse arrangement. Both the pre-ablation mode (an air spark is induced above the sample surface prior to the ablation pulse) and the re-heating mode (additional energy is delivered into the plasma created by the ablation pulse) is considered. The plasmas are investigated in terms of the temporal evolution of their electron density, temperature, and volume. The plasma volumes are determined using a time-resolved tomography technique based on the Radon transformation. The reconstruction is carried out for both white-light and band-pass filtered emissivities. The white-light reconstruction corresponds to the overall size of the plasmas. On the other hand, the band-pass emissivity reconstruction shows the distribution of the atomic sample species (Cu I). Moreover, through spectrally resolved tomographic reconstruction, the spatial homogeneity of the electron density and temperature of the plasmas is also investigated at various horizontal slices of the plasmas. Our results show that the pre-ablation geometry yields a more temporally stable and spatially uniform plasma, which could be beneficial for calibration-free laser-induced breakdown spectroscopy (LIBS) approaches. On the contrary, the plasma generated in the re-heating geometry exhibits significant variations in electron density and temperature along its vertical axis. Overall, our results shed further light on the mechanisms involved in the LIBS signal enhancement using double-pulse ablation.

Detail investigation of toxicity, bioaccumulation, and translocation of Cd-based quantum dots and Cd salt in white mustard.

In this study, a model crop plant white mustard (Sinapis alba L.) was treated with an aqueous dispersion of silica-coated CdTe quantum dots (CdTe/SiO2 QDs) in a 72-h short-term toxicity test. The toxicity was established via measurements of (i) the root length and (ii) the chlorophyll fluorescence. These results were compared to two other sources of cadmium, free Cd ions (CdCl2) and prime un-shell nanoparticles CdTe QDs. Tested compounds were applied in concentrations representing 20 and 200 µM Cd. The uptake and translocation of Cd were investigated using inductively coupled plasma optical emission spectrometry (ICP-OES) and the spatial Cd distribution was investigated in detail applying laser induced breakdown spectroscopy (LIBS). The LIBS maps with a lateral resolution of 100 µm were constructed for the whole plants, and maps with a lateral resolution of 25 µm (micro-LIBS arrangement) were used to analyse only the most interesting parts of plants with Cd presence (e.g. root tips or a part crossing the root into the above-ground part). Our results show that the bioaccumulation patterns and spatial distribution of Cd in CdTe/SiO2 QDs-treated plants differ from the plants of positive control and CdTe QDs. Fluorescence microscopy photographs revealed that CdTe/SiO2 became adsorbed onto the plant surface in comparison to CdTe QDs. Further, a physico-chemical characterization of QDs before and after the test exposure showed only minor changes in the nanoparticle diameters and no tendencies of QDs for agglomeration or aggregation during the exposure.

Benchmark classification dataset for laser-induced breakdown spectroscopy.

In this work, we present an extensive dataset of laser-induced breakdown spectroscopy (LIBS) spectra for the pre-training and evaluation of LIBS classification models. LIBS is a well-established spectroscopic method for in-situ and industrial applications, where LIBS is primarily applied for clustering and classification tasks. As such, our dataset is aimed at helping with the development and testing of classification and clustering methodologies. Moreover, the dataset could be used to pre-train classification models for applications where the amount of available data is limited. The dataset consists of LIBS spectra of 138 soil samples belonging to 12 distinct classes. The spectra were acquired with a state-of-the-art LIBS system. Lastly, the composition of each sample is also provided, including estimated uncertainties.

Laser-induced breakdown spectroscopy as a novel readout method for nanoparticle-based immunoassays.

Laser-induced breakdown spectroscopy (LIBS) was examined as a novel method for readout of microtiter plate immunoassays involving nanoparticles (NP). The so-called Tag-LIBS technique is a sensitive method for the detection of specific biomarkers. It was applied to the determination of NP labels using nanosecond ablation sampling. The NP labels were examined from the bottom of a standard 96-well microtiter plate. Thanks to the flexibility of LIBS instrumentation, both the plasma emission collection and the focusing optics arrangements can be collinearly arranged. The experiments showed that silver NPs and gold NPs can be readily quantified on the bottom of the microtiter plate. Utilizing this technique, a sandwich immunoassay for human serum albumin using streptavidin-coated AgNP labels was developed. The assay has a 10 ng·mL-1 detection limit which is comparable to the sensitivity of fluorometric readout. The main advantage of this LIBS technique is its wide scope in which it enables a detection of almost any type of NP labels, irrespective to any fluorescence or catalytic properties. Owing to the immediate signal response, the relatively simple instrumentation also enables assay automation. The LIBS capability of multi-elemental analyses makes it a promising and fast alternative to other readout techniques, in particular with respect to multiplexed detection of biomarkers. Graphical abstract Laser-induced breakdown spectroscopy (LIBS) is used as a novel readout method of nanoparticle-based immunoassays in microtiter plates. After formation of sandwich immunocomplex, the analyte concentration is quantified as the signal of Ag nanoparticle labels determined by LIBS.

The effects of photon-upconversion nanoparticles on the growth of radish and duckweed: Bioaccumulation, imaging, and spectroscopic studies.

In this study, radish (Raphanus sativus L.) and common duckweed (Lemna minor L.) were treated with an aqueous dispersion of carboxylated silica-coated photon-upconversion nanoparticles containing rare-earth elements (Y, Yb, and Er). The total concentration of rare earths and their bioaccumulation factors were determined in root, hypocotyl, and leaves of R. sativus after 72 h, and in L. minor fronds after 168 h. In R. sativus, translocation factors were determined as the ratio of rare earths concentration in hypocotyl versus root and in leaves versus hypocotyl. The lengths of the root and hypocotyl in R. sativus, as well as the frond area in L. minor, were monitored as toxicity endpoints. To distinguish rare earth bioaccumulation patterns, two-dimensional maps of elemental distribution in the whole R. sativus plant and L. minor fronds were obtained by laser-induced breakdown spectroscopy with a lateral resolution of 100 µm. Moreover, the bioaccumulation was inspected using a photon-upconversion laser microscanner. The results revealed that the tested nanoparticles became adsorbed onto L. minor fronds and R. sativus roots, as well as transferred from roots through the hypocotyl and into leaves of R. sativus. The bioaccumulation patterns and spatial distribution of rare earths in nanoparticle-treated plants therefore differed from those of the positive control. Overall, carboxylated silica-coated photon-upconversion nanoparticles are stable, can easily translocate from roots to leaves, and are expected to become adsorbed onto the plant surface. They are also significantly toxic to the tested plants at nominal concentrations of 100 and 1000 µg/mL.

Feasibility of Nanoparticle-Enhanced Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

Nanoparticles (NPs) applied to the surface of some solids can increase signals in inductively coupled plasma mass spectrometry (ICPMS). Drops containing 20 and/or 40 nm nanoparticles of Ag and/or Au were deposited on metallic and ceramic/glass samples, and after being dried, both the samples treated with NPs and plain targets were ablated by one pulse per spot. The laser ablation ICPMS (LA-ICPMS) signals were enhanced for metallic samples modified with NPs in comparison to signals produced at the plain, untreated surface. Maps of LA-ICPMS signals recorded for several laser fluences show that the NP-induced signal enhancement exceeds even 2 orders of magnitude for metallic samples. No enhancement was achieved for nonconductive samples. This enhancement is limited to the peripheral annular region of the dried droplet area where NPs are concentrated due to the "coffee stain" effect. Ablation crater profilometric inspection revealed a more uniform material rearrangement over the NP-treated surface compared with the ablated plain target. However, besides a smoother crater bottom, no other evidence of an NP-enhancing effect was noticed, although an increased ablation rate was anticipated. Limits of detection dropped by 1 order of magnitude for the minor elements in the presence of NPs. Observed phenomena depend only on the NP surface concentration but not on the material or size of the NPs. An electron microprobe study of the collected ablation aerosol has shown that aerosol particles consisting of target material are aggregated around the NPs. The hypothesis is that such aggregates exhibit better transport/vaporization efficiency, thus enhancing signals for metallic samples. A detailed study of the suggested mechanism will be continued in ongoing work.

Time-Dependent Growth of Silica Shells on CdTe Quantum Dots.

The purpose of this study is to investigate the time dependent growth of silica shells on CdTe quantum dots to get their optimum thicknesses for practical applications. The core/shell structured silica-coated CdTe quantum dots (CdTe/SiO2 QDs) were synthesized by the Ströber process, which used CdTe QDs co-stabilized by mercaptopropionic acid. The coating procedure used silane primer (3-mercaptopropyltrimethoxysilane) in order to make the quantum dots (QDs) surface vitreophilic. The total size of QDs was dependent on both the time of silica shell growth in the presence of sodium silicate, and on the presence of ethanol during this growth. The size of particles was monitored during the first 72 h using two principally different methods: Dynamic Light Scattering (DLS), and Scanning Electron Microscopy (SEM). The data obtained by both methods were compared and reasons for differences discussed. Without ethanol precipitation, the silica shell thickness grew slowly and increased the nanoparticle total size from approximately 23 nm up to almost 30 nm (DLS data), and up to almost 60 nm (SEM data) in three days. During the same time period but in the presence of ethanol, the size of CdTe/SiO2 QDs increased more significantly: up to 115 nm (DLS data) and up to 83 nm (SEM data). The variances occurring between silica shell thicknesses caused by different methods of silica growth, as well as by different evaluation methods, were discussed.

Short-term assessment of cadmium toxicity and uptake from different types of Cd-based Quantum Dots in the model plant Allium cepa L.

We report on the toxicity and bioaccumulation of three different types of Cd-based quantum dots (QDs), dispersed in aqueous medium, for a model plant Allium cepa L. It is believed that encapsulation of nanoparticles should reduce their toxicity and increase their stability in different environments; in this work we studied how QD encapsulation affects their phytotoxicity. Core, core/shell, and core/shell/shell QDs (CdTe, CdTe/ZnS, and CdTe/CdS/ZnS QDs capped by 2-mercaptopropionic acid) were tested and CdCl2 was used as a positive control. After 24-h and 72-h exposure, total Cd content (MCd) and bioaccumulation factors (BAFs) were determined in all parts of A. cepa plants (roots, bulb, shoot), and the total length of the root system was monitored as a toxicity end-point. Measurements of total Cd content versus free Cd2+ content (with Differential Pulse Voltammetry, DPV) in exposure media showed differences in chemical stability of the three QD types. Correspondingly, selected QDs showed different toxicity for A. cepa and different Cd bioaccumulation patterns. CdTe QDs were the most toxic; their effect was similar to CdCl2 due to the release of free Cd2+, which was confirmed by the DPV measurements. Plants exposed to CdTe QDs also bioaccumulated the most Cd among all QD exposure groups. CdTe/ZnS QDs showed no toxicity and very low bioaccumulation of Cd in A. cepa; the main source of measured Cd in the plants were QDs adsorbed on their roots, which was confirmed by fluorescence microscopy. On the contrary, CdTe/CdS/ZnS QD toxicity and bioaccumulation patterns were similar to those of CdTe QDs and pointed to unstable CdS/ZnS shells.

Comparative investigation of toxicity and bioaccumulation of Cd-based quantum dots and Cd salt in freshwater plant Lemna minor L.

The purpose of this study was to determine the toxicity of two different sources of cadmium, i.e. CdCl2 and Cd-based Quantum Dots (QDs), for freshwater model plant Lemna minor L. Cadmium telluride QDs were capped with two coating ligands: glutathione (GSH) or 3-mercaptopropionic acid (MPA). Growth rate inhibition and final biomass inhibition of L. minor after 168-h exposure were monitored as toxicity endpoints. Dose-response curves for Cd toxicity and EC50168h values were statistically evaluated for all sources of Cd to uncover possible differences among the toxicities of tested compounds. Total Cd content and its bioaccumulation factors (BAFs) in L. minor after the exposure period were also determined to distinguish Cd bioaccumulation patterns with respect to different test compounds. Laser-Induced Breakdown Spectroscopy (LIBS) with lateral resolution of 200µm was employed in order to obtain two-dimensional maps of Cd spatial distribution in L. minor fronds. Our results show that GSH- and MPA-capped Cd-based QDs have similar toxicity for L. minor, but are significantly less toxic than CdCl2. However, both sources of Cd lead to similar patterns of Cd bioaccumulation and distribution in L. minor fronds. Our results are in line with previous reports that the main mediators of Cd toxicity and bioaccumulation in aquatic plants are Cd2+ ions dissolved from Cd-based QDs.