Non-invasive proxies, such as fur and feathers, are likely to be increasingly used to assess the potential exposure of chemicals, including trace metals and metalloids. However, the amount of external contamination is usually unknown, and there is no standard method for removing external contamination of trace metals in fur or feathers. To date, 40 % of studies published related to the measurement of trace metal levels in fur or the hair of non-human mammals and 24 % of studies in feathers do not state any washing methods or did not wash the samples before analysis. We assessed three washing techniques to remove external contamination of arsenic (As), lead (Pb), and zinc (Zn) from bat fur. We selected the three most frequently used fur washing methods from literature. To test these methods, fur samples from great flying foxes (Pteropus neohibernicus neohibernicus, n=15 individuals) from Papua New Guinea preserved over eight decades (AMNH, USA) were used. Percentages of trace metal removed are 87.19 % (SD= 12.28), 92.99 % (SD= 5.5) and 88.57 % (SD= 9.33) for As, 54.72 % (SD= 31.64), 55.89 % (SD= 37.87), and 53.93 % (SD= 41.28) for Pb, and 74.03 % (SD= 22.96), 22.93 % (SD= 73), and 24.95 % (SD= 49.5) for Zn using M2, M3, and M4, respectively. We also assessed four washing techniques to remove external contamination of arsenic (As), mercury (Hg), and zinc (Zn) from bird feathers. We identified the four most prevalent washing techniques in the literature used for feathers. We used feathers from the great horned owl (Bubo virginianus) and the great blue heron (Ardea herodias) to test these methods. Percentages of trace metal removed are 34.35 % (SD= 44.22), 69.22 % (SD= 36.5), 62.59 % (SD= 48.37), and 80.89 % (SD= 14.54) for As, 66.97 % (SD= 13.26), 29.4 % (SD= 67.06), 49.68 % (SD= 42.33), and 28.88 % (SD= 69) for Hg, and <0 % (SD= 80.1), 0 % (SD= 29.55), 11.23 % (SD= 47.73), and 57.09 % (SD= 21.2) for Zn using M2, M3, M4, and M5, respectively. This study shows the importance of washing fur and feather samples prior to trace metals analyses in ecotoxicology and biomonitoring studies.

Organotin compounds (OTCs) are widely regulated but rank among the most used organometallic compounds in various industrial sectors. They are significantly more toxic than inorganic tin compounds. At workplaces, OTCs can be released as vapors or dust particles and can be absorbed by inhalation or skin contact. Occupational exposure thus represents a great risk for the absorption of OTCs for employees. Methods for OTCs speciation in workplace air monitoring currently do not exist. This study describes the development of a separation method for eleven in Germany regulated OTCs via HPLC-ICP-MS. The method allows a near baseline separation of MMT, MBT, MOT, MPhT, DMT, DBT, DPhT, TMT, TBT, TPhT and TTMT within 22 min on a C18 column and a ternary solvent and flow rate gradient using methanol, acetonitrile, and ultrapure water + 6% (v/v) acetic acid + 0.17% (m/v) α-tropolone. Ten analytes show linearity in the working range of 10 - 100 µg OTCs/L with R² > 0.999. Due to its high volatility the analyte TTMT showed a quadratic relationship between concentration and signal intensity with R² = 0.9998. The determination of the instrumental limits resulted in detection limits between 0.14 and 0.57 µg Sn/L and limits of quantification between 0.49 and 1.97 µg Sn/L. Over the course of this study thermal instability and cross reactivity of OTC in solution became apparent. Formation of two reaction products in mixed OTCs solutions have been observed. These effects will further be examined within development of appropriate sampling and sample preparation for workplace air to provide a suitable method for the determination of OTCs at workplaces according to normative references.

Many medical devices contain metals that interface with the body. Additionally, embedded metal fragments from military wounds are typically not removed, to avoid the risk of morbidity associated with invasive surgery. The long-term health consequences of many of these materials are not thoroughly understood. To this end, we have exposed rats for up to one year to implanted single-element metal pellets of any one of Al, Co, Cu, Fe, Ni, Pb, Ta, or W. Various tissues were harvested and flash frozen for analysis of their metal distribution. We discuss approaches to most thoroughly and reliably evaluate the distribution of metal in these tissues. The path to the most appropriate analytical technique took us through extensive examination of the tissues using scanning electron microscopy with energy dispersive X-ray spectroscopy (XPS), X-ray photoelectron spectroscopy (XPS), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Though any one of these methods is highly relied upon in surface chemistry analysis, LA-ICP-MS alone showed presence of metal in the tissue. This information will help build robust methods to bridge the gap in our understanding of biosolubility and distribution of embedded metal throughout the body.

Metal occupational exposure limits mainly focus on total content of the respective metals of interest. The methods applied for trace metal analysis in occupational health and safety laboratories are usually standardized to pragmatic consensus digestion schemes, ensuring comparability of results. The objective of the present study entailed the evaluation of a recently developed HNO3-only microwave-assisted digestion procedure by comparison with the German consensus hot-block digestion and other national digestion schemes. An inter-laboratory comparison test with participation of nine national occupational health and safety laboratories from Europe and North America was organized. For adequate emulation of what workers are at risk of inhaling four different industrial metal processing workplace dusts (electronic recycling, high-speed steel grinding, cylinder head cleaning, and battery combustion ash) were homogenized and sieved to the particle size < 100 µm diameter at IFA. The participants were asked to process air sample-typical amounts according to the German hot-plate technique, the IFA microwave-assisted digestion scheme as well as their national or in-house conventional digestion method for airborne dust and analyze for Cd, Co, Cr, Co, Fe, Mg, Ni, Pb, and Zn. Recoveries (relative to consensus open-vessel digestion) obtained for the new IFA microwave-assisted digestion were between 88 and 114% and relative reproducibility standard deviations were <10% for most metals of interest. The in-house digestion procedures applied varied widely but (whether microwave, hot block, or open vessel) yielded comparable results for the predominantly elemental alloy type dusts supplied. Results become more diverse for the combustion dust, especially if a combination of microwave-assisted digestion procedures with high temperatures and hydrofluoric acid is applied. ISO 15202-2 is currently being revised; this digestion procedure will be included as a possible variant in annex 2.

Post-curing is essential to improve the mechanical properties of 3D printed parts fabricated by stereolithography (SLA), since right after 3D printing they remain in a \"green state\". It means that the 3D printed parts have reached their final shape, but the polymerization reaction has not been yet completed. Herein, we take advantage of the tacky partially polymerized surface of \"green state\" SLA 3D printed parts to immobilize extraction disks and miniature magnets, which after UV post-curing, become permanently attached to the 3D printed part resulting in a rotating-disk sorptive extraction device (RDSE). The developed \"stick & cure\" procedure is reagent-free and does not require any additional preparation time, specialized skills, or instrumentation. As proof of concept, 3D printed RDSE devices with immobilized chelating disks have been applied to the simultaneous extraction of 14 trace metals prior to ICP-OES determination, featuring LODs between 0.03 and 1.27 μg L-1, and an excellent device-to-device reproducibility (n = 5, RSD = 2.7-8.3%). The developed method was validated using certified wastewater and soil reference samples, and satisfactory spiking recoveries were obtained in the analysis of highly polluted solid waste treatment plant leachates (89-110%). In addition, exploiting the versatility of 3D printing, nine RDSE devices with different shapes were fabricated. Their performance was evaluated and compared for the fast extraction of the highly toxic Cr (VI) as its 1,5-diphenylcarbazide complex in reversed-phase mode, showing different extraction performance on depending on the shape of the 3D printed RDSE device.

A systematic electrochemical impedance spectroscopy (EIS) analysis at different potentials of an in situ-prepared bismuth-film glassy carbon electrode (BiFE) in 0.1 M acetate buffer solution is reported. This electrode is employed in the square-wave anodic stripping voltammetry (SWASV) technique for the determination of trace amounts of the heavy metals Zn, Cd, and Pb. The method was first validated for detection limit, linear range, sensitivity, precision and accuracy to clearly prove the superior action of BiFE compared with the bare glassy carbon electrode (GCE). Next, in order to investigate the characteristics of this sensor, EIS measurements were carried out at slightly more negative potentials than the potentials at which each individual stripping signal is detected, after the deposition step at different deposition potentials. For comparison, EIS measurements were also performed at open circuit potential. The studied trace metal concentration range (5-20 ppb) did not significantly influence the capacitive and resistive behaviour of the BiFE which explains why the performance of this sensor is superior compared with the bare GCE. The higher sensitivity of the SWASV method for BiFE compared with the bare GCE was explained by the lower polarisation resistance values of the former. Moreover, the potential of zero charge was also determined, and an explanation whether the system is under kinetic- and/or diffusion-controlled process is given.

The adsorptive stripping voltammetric detection of nickel and cobalt in water samples at metal film electrodes has been extensively studied. In this work, a novel, environmentally friendly, metal-free electrochemical probe was constructed for the ultra-trace determination of Ni2+ in water samples by Adsorptive Cathodic Stripping Voltammetry (AdCSV). The electrochemical platform is based on the adsorptive accumulation of Ni2+ ions directly onto a glassy carbon electrode (GCE) modified with dimethylglyoxime (DMG) as chelating agent and a Nafion-graphene (NGr) nanocomposite to enhance electrode sensitivity. The nafion-graphene dimethylglyoxime modified glassy carbon electrode (NGr-DMG-GCE) shows superior detection capabilities as a result of the improved surface-area-to-volume ratio and enhanced electron transfer kinetics following the incorporation of single layer graphene, while limiting the toxic effects of the sensor by removal of the more common mercury, bismuth and lead films. Furthermore, for the first time the NGr-DMG-GCE, in the presence of common interfering metal ions of Co2+ and Zn2+ demonstrates good selectivity and preferential binding towards the detection of Ni2+ in water samples. Structural and morphological characterisation of the synthesised single layer graphene sheets was conducted by Raman spectrometry, HRTEM and HRSEM analysis. The instrumental parameters associated with the electrochemical response, including accumulation potential and accumulation time were investigated and optimised in addition to the influence of DMG and graphene concentrations. The NGr-DMG-GCE demonstrated well resolved, reproducible peaks, with RSD (%) below 5% and a detection limit of 1.5 µg L-1 for Ni2+ reduction at an accumulation time of 120 s., the prepared electrochemical sensor exhibited good detection and quantitation towards Ni2+ detection in tap water samples, well below 0.1 mg L-1 set by the WHO and EPA standards. This comparable to the South African drinking water guidelines of 0.15 mg L-1.

Little knowledge is available about water concentrations of rare earth elements (REEs) in the marine environment. The direct measurement of REEs in coastal waters is a challenging task due to their ultra-low concentrations as well as the high salt content in the water samples. To quantify these elements at environmental concentrations (pg L(-1) to low ng L(-1)) in coastal waters, current analytical techniques are generally expensive and time consuming, and require complex chemical preconcentration procedures. Therefore, an integrative passive sampler was tested as a more economic alternative sampling approach for REE analysis. We used a Chemcatcher-Metal passive sampler consisting of a 3M Empore Chelating Disk as the receiving phase, as well as a cellulose acetate membrane as the diffusion-limiting layer. The effect of water turbulence and temperature on the uptake rates of REEs was analyzed during 14-day calibration experiments by a flow-through exposure tank system. The sampling rates were in the range of 0.42 mL h(-1) (13 °C; 0.25 m s(-1)) to 4.01 mL h(-1) (13 °C; 1 m s(-1)). Similar results were obtained for the different REEs under investigation. The water turbulence was the most important influence on uptake. The uptake rates were appropriate to ascertain time-weighted average concentrations of REEs during a field experiment in the Elbe Estuary near Cuxhaven Harbor (exposure time 4 weeks). REE concentrations were determined to be in the range 0.2 to 13.8 ng L(-1), where the highest concentrations were found for neodymium and samarium. In comparison, most of the spot samples measured along the Chemcatcher samples had REE concentrations below the limit of detection, in particular due to necessary dilution to minimize the analytical problems that arise with the high salt content in marine water samples. This study was among the first efforts to measure REE levels in the field using a passive sampling approach. Our results suggest that passive samplers could be an effective tool to monitor ultra-trace concentrations of REEs in coastal waters with high salt content.

The redox sensitive trace metals iron and manganese are two important elements that help shape the biogeochemistry of aquatic systems and thus their measurement is important. Current laboratory methods are expensive, time consuming and cannot provide the spatial and temporal resolution needed to characterize these elements in natural waters. Here we describe the first autonomous analyzer capable of providing vertical profiles as well as routine in-situ determinations of dissolved Fe(II) and Mn in aquatic environments. The spectrophotometric sensor uses microfluidic methods (Lab-on-a-chip technology) and mixes reagents and samples using a novel in-cell diffusion process. Fe(II) and Mn can be measured with a frequency of up to 12 and 6 samples per hour respectively with limits of detection of 27nM for Fe(II), 2.1% precision (n=20), and 28nM for Mn, 2.4% precision (n=19). The device combines relatively low cost, low power usage, low reagent consumption, portability, and tolerance to pressures up to at least 170 bars, with high precision and accuracy. We present data from a successful demonstration of the sensor during a cruise to the Gotland and Landsort Deep Basins of the Baltic Sea.

Effective specific activity of (64)Cu (amount of radioactivity per µmol metal) is important in order to determine purity of a particular (64)Cu lot and to assist in optimization of the purification process. Metal impurities can affect effective specific activity and therefore it is important to have a simple method that can measure trace amounts of metals. This work shows that ion chromatography (IC) yields similar results to ICP mass spectrometry for copper, nickel and iron contaminants in (64)Cu production solutions.