Scallop shells as biosorbents for water remediation from heavy metals: Contributions and mechanism of shell components in the adsorption of cadmium from aqueous matrix.

To ascertain their potential for heavy metal pollution remedy, we studied the adsorption mechanism of cadmium onto scallop shells and the interactions between the heavy metal and the shell matrix. Intact shells were used to investigate the uptake and diffusion of the metal contaminant onto the shell carbonatic layers, as well as to evaluate the distribution of major and trace elements in the matrix. LA-ICPMS measurements demonstrate that Cd is adsorbed on a very thin layer on the inner and outer surfaces of the shell. Structural and thermal analyses showed the presence of 9 wt.-% of a CdCO3 phase indicating that the adsorption is mainly a superficial process which involves different processes, including ion exchange of Ca by Cd. In addition, organic components of the shell could contribute to adsorption as highlighted by different metal uptake observed for shells with different colours. In particular, darker shells appeared to adsorb more contaminant than the white ones. The contribution of the organic shell components on the adsorption of heavy metals was also highlighted by the element bulk content which showed higher concentrations of different metals in the darker specimen. Raman spectroscopy allowed to identify the pigments as carotenoids, confirmed by XRD measurements which highlighted the presence of astaxanthin phases. The results presented here provide new insights into the Cd adsorption mechanism highlighting the important contribution given by the organic components present in the biogenic carbonate matrix. Furthermore, the high efficiency of Cd removal from water by scallop shells, supported by adsorption kinetic and isotherm studies, has been demonstrated.

Questions for Classroom Response Systems and Teaching Instrumental Element Analysis.

Asking students questions is a central, although understudied and underappreciated, ingredient of teaching. Formative questioning provides many opportunities for teachers and students, e.g. to practice skills and receive feedback. Among other approaches, classroom response systems (CRSs), which run on the mobile electronic devices of students, facilitate such active engagement of students in the lecture hall. This paper presents an overview on questions for teaching with a focus on questions for CRSs and provides considerations and brief guidelines for the development of multiple-choice questions. Examples from a mid-sized analytical chemistry lecture illustrate additional challenges and different probes for potential misconceptions. Moreover, limitations of valid interpretation of students' responses are emphasized. This leads to a discussion of the value of incorporating prompts for justifications into questions.

Cadmium accumulation and allocation in different cacao cultivars.

Cadmium (Cd) is a biologically non-essential heavy metal that can cause toxic effects in plants, animals and humans already at low concentrations compared to other metals. After Cd concentrations in cacao beans of various provenances, particularly from Latin America, were found to exceed the new regulations enforced by the European Union in 2019, there is an urgent need to find measures to lower Cd accumulation in cacao beans to acceptable values. In this research, the long-term cacao cultivar trial CEDEC-JAS in northern Honduras was used to investigate differences between 11 cultivars in Cd uptake and translocation. Sampling of various plant parts, including rootstocks, scions, leaves and beans, from three replicate trees per cultivar and the soil around each tree was conducted at this site. Results indicate that concentrations of available soil Cd were more closely correlated with Cd concentrations of the rootstocks (R2 = 0.56), scions (R2 = 0.59) and leaves (R2 = 0.46) than with bean Cd concentrations (R2 = 0.26). In addition, Cd concentrations of rootstocks, scions and leaves showed close relationships to available soil Cd concentrations, with no significant differences between the cultivars. In contrast, bean Cd concentrations showed only weak correlations to available soil Cd and Cd concentrations in the vegetative plant parts, but significant variation among cultivars. Three cultivars, which were analysed in more detail, showed significant differences in Cd concentrations of mature beans, but not of immature beans. These results suggest that cultivar-related differences in bean Cd concentrations primarily result from differences in Cd loading during bean maturation, possibly due to cultivar-specific differences in the xylem-to-phloem transfer of Cd. The results show that selection of cultivars with low Cd transfer from vegetative parts into the beans has high potential to keep Cd accumulation in cacao beans at levels that are safe for consumption.

High-speed, high-resolution, multielemental laser ablation-inductively coupled plasma-time-of-flight mass spectrometry imaging: part I. Instrumentation and two-dimensional imaging of geological samples.

Low-dispersion laser ablation (LA) has been combined with inductively coupled plasma-time-of-flight mass spectrometry (ICP-TOFMS) to provide full-spectrum elemental imaging at high lateral resolution and fast image-acquisition speeds. The low-dispersion LA cell reported here is capable of delivering 99% of the total LA signal within 9 ms, and the prototype TOFMS instrument enables simultaneous and representative determination of all elemental ions from these fast-transient ablation events. This fast ablated-aerosol transport eliminates the effects of pulse-to-pulse mixing at laser-pulse repetition rates up to 100 Hz. Additionally, by boosting the instantaneous concentration of LA aerosol into the ICP with the use of a low-dispersion ablation cell, signal-to-noise (S/N) ratios, and thus limits of detection (LODs), are improved for all measured isotopes; the lowest LODs are in the single digit parts per million for single-shot LA signal from a 10-µm diameter laser spot. Significantly, high-sensitivity, multielemental and single-shot-resolved detection enables the use of small LA spot sizes to improve lateral resolution and the development of single-shot quantitative imaging, while also maintaining fast image-acquisition speeds. Here, we demonstrate simultaneous elemental imaging of major and minor constituents in an Opalinus clay-rock sample at a 1.5 µm laser-spot diameter and quantitative imaging of a multidomain Pallasite meteorite at a 10 µm LA-spot size.

High-speed, high-resolution, multielemental LA-ICP-TOFMS imaging: part II. critical evaluation of quantitative three-dimensional imaging of major, minor, and trace elements in geological samples.

Here we describe the capabilities of laser-ablation coupled to inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOFMS) for high-speed, high-resolution, quantitative three-dimensional (3D) multielemental imaging. The basic operating principles of this instrumental setup and a verification of 3D quantitative elemental imaging are provided. To demonstrate the potential of 3D LA-ICP-TOFMS imaging, high-resolution multielement images of a cesium-infiltrated Opalinus clay rock were recorded using LA with a laser-spot diameter of 5 µm coupled to ICP-TOFMS. Quantification of elements ablated from each individual laser pulse was carried out by 100% mass normalization, and the 3D elemental concentration images generated match well with the expected distribution of elements. After laser-ablation imaging, the sample surface morphology was investigated using confocal microscopy, which showed substantial surface roughness and evidence of matrix-dependent ablation yields. Depth assignment based on ablation yields from heterogeneous materials, such as Opalinus clay rock, will remain a challenge for 3D LA-ICPMS imaging. Nevertheless, this study demonstrates quantitative 3D multielemental imaging of geological samples at a considerably higher image-acquisition speed than previously reported, while also offering high spatial resolution and simultaneous multielemental detection.

Quantification of intact covalently metal labeled proteins using ESI-MS/MS.

Mass spectrometric methods matured from the successful qualitative characterization of proteins in complex mixtures into methods for quantitative proteomics often based on chemical tags with stable isotope labeling. In the study presented here, we extended the application of lanthanide-ion-based tags from the quantification using inductively coupled plasma-MS into the quantification of labeled intact proteins using electrospray ionization (ESI)-MS and ESI-MS/MS. We applied the metal chelate tag MeCAT-iodoacetamide (IA) (1,4,7,10-tetraazacyclododecane N,N',N″,N″ '-tetra acetic acid with a IA reactive site). Labeled proteins were separated using C3-reversed phase-high-performance liquid chromatography interfaced to ESI-MS. We could prove that even large proteins were completely labeled at all available cysteine residues using MeCAT-IA with only a small excess of reagent. Fragmentation of labeled proteins either using infrared multiphoton dissociation in Fourier transform ion cyclotron resonance-MS or higher-energy collision dissociation with an Orbitrap gave characteristic fragments. We used these fragments to quantify several intact proteins avoiding digestion. To demonstrate the applicability, human serum albumin was quantified in blood serum. The high-performance liquid chromatography/ESI-MS/MS quantification data were validated using inductively coupled plasma-MS. Because the metal within the tag may be any of the lanthanides, multiplexing capabilities are inherent.

MeCAT--comparing relative quantification of alpha lactalbumin using both molecular and elemental mass spectrometry.

Chemical tagging with stable isotopes is one of the best established methods for the quantification of proteins using mass spectrometry, especially in non-proliferating cells and tissue. The absolute quantification of proteins is still a challenge. Metal-coded affinity tagging (MeCAT), used to label proteins and peptides with lanthanide ions, allows both, relative and absolute, quantitative determination. MeCAT loaded with lanthanide ions allows the use of inductively coupled plasma mass spectrometry (ICP-MS) enabling very accurate and sensitive quantification of peptides and proteins based on the metal ion signal. Furthermore, multiplex assays are possible that are not limited to 4- or 8-plex analyses when using different lanthanides. Naturally, different lanthanides also lead to different molecular masses for the same labelled peptides which can be distinguished easily. This enables the relative quantification in electrospray MS based on the relative signal intensities of the differentially labelled peptides. We have studied MeCAT labelled peptides, using LC/ESI-MS and LC/ESI-MS/MS with infrared multiphoton dissociation (IRMPD) to show that both the molecular masses and the specific fragments resulting from the MS/MS experiments can be used for relative quantification. The results are compared with high performance liquid chromatography (HPLC)/ICP-MS and direct ICP-MS analysis as standard methods. We show that the ESI and IRMPD based methods deliver quantitative results comparable to ICP-MS.

MeCAT--new iodoacetamide reagents for metal labeling of proteins and peptides.

Besides protein identification via mass spectrometric methods, protein and peptide quantification has become more and more important in order to tackle biological questions. Methods like differential gel electrophoresis or enzyme-linked immunosorbent assays have been used to assess protein concentrations, while stable isotope labeling methods are also well established in quantitative proteomics. Recently, we developed metal-coded affinity tagging (MeCAT) as an alternative for accurate and sensitive quantification of peptides and proteins. In addition to absolute quantification via inductively coupled plasma mass spectrometry, MeCAT also enables sequence analysis via electrospray ionization tandem mass spectrometry. In the current study, we developed a new labeling approach utilizing an iodoacetamide MeCAT reagent (MeCAT-IA). The MeCAT-IA approach shows distinct advantages over the previously used MeCAT with maleinimide reactivity such as higher labeling efficiency and the lack of diastereomer formation during labeling. Here, we present a careful characterization of this new method focusing on the labeling process, which yields complete tagging with an excess of reagent of 1.6 to 1, less complex chromatographic behavior, and fragmentation characteristics of the tagged peptides using the iodoacetamide MeCAT reagent.