EOF and target PFAS analysis in surface waters affected by sewage treatment effluents in Berlin, Germany.

Per- and polyfluoroalkyl substances (PFAS) are emerging organic pollutants and can occur in surface and groundwater. To identify the degree of pollution in surface water with PFAS, often targeted HPLC-ESI-MS/MS has been employed in which commonly 30-40 compounds are analyzed. However, other PFAS and organofluorines remain undetected.

Mercury speciation in Scottish raptors reveals high proportions of inorganic mercury in Scottish golden eagles (Aquila chrysaetos): Potential occurrence of mercury selenide nanoparticles.

Knowledge of the uptake and fate of mercury (Hg) compounds in biota is important in understanding the global cycling of Hg and its transfer pathways through food chains. In this study, we analysed total mercury (T-Hg) and methylmercury (MeHg) concentrations in 117 livers of Scottish birds of prey that were found across Scotland and submitted for post-mortem examination through the Raptor Health Scotland project between 2009 and 2019. Statistical comparisons focussed on six species (barn owl, Tyto alba; Eurasian common buzzard, Buteo buteo; golden eagle, Aquila chrysaetos; hen harrier, Circus cyaneus; Eurasian sparrowhawk, Accipiter nisus; and tawny owl, Strix aluco) and showed that golden eagles had a statistically lower fraction of MeHg compared to other raptor species.

Wild shrimp have an order of magnitude higher arsenic concentrations than farmed shrimp from Brazil illustrating the need for a regulation based on inorganic arsenic.

Background: Shrimp is a worldwide food commodity, it is a source of several nutrients and vitamins; however, this food is one of the major sources of arsenic for humans. Legislation around the world set limits for the concentration of this element in crustaceans but is mainly concerned with total analysis. Although, arsenic species have different toxicities and total analysis could be ineffective for making decisions about food security.

Development of Mercury Analysis by NanoSIMS for the Localization of Mercury-Selenium Particles in Whale Liver.

Nanoscale secondary ion mass spectrometry (NanoSIMS) is a dynamic SIMS technique, which offers high spatial resolution allowing the mapping of chemical elements at the nanometer scale combined with high sensitivity. However, SIMS for mercury analysis is a challenging issue due to the low secondary ion yield and has never been done on NanoSIMS. The introduction of an rf plasma oxygen primary ion source on NanoSIMS enabled higher lateral resolution and higher sensitivity for electropositive elements such as most metals.

Higher zero valent iron soil amendments dosages markedly inhibit accumulation of As in Faya and Kilombero cultivars compared to Cd.

Impact of zero valent iron (Fe°) amendment on grain-yield (GY) and grain-As and Cd accumulation in rice (Oryza sativa L.) cultivars Kilombero and Faya were investigated. Rice plants were amended with Fe° dosages of 0, 3.

The use of microwave-induced plasma optical emission spectrometry for fluorine determination and its application to tea infusions.

This study presents a novel method for fluorine quantification determination by microwave-induced plasma optical emission spectrometry (MIP-OES). Due to the low temperature of this plasma, atomic emission of fluorine could not be measured, instead CaF molecular emissions were measured by using a calcium solution mixed in the spray chamber with the sample using a T-piece. Several wavelengths were studied to find the best signal to noise ratio for fluorine determination and 530.

The use of high resolution graphite furnace molecular absorption spectrometry (HR -MAS) for total fluorine determination in extractable organofluorines (EOF).

The determination of total fluorine content using high-resolution graphite furnace continuum source molecular absorption spectrometry (HR- MAS) has been employed in a variety of samples for over 10 years. However, most of the samples analysed by HR- MAS are rich in fluoride, with negligible levels of organic fluorinated species. With an increase in concern surrounding per- and polyfluoroalkyl substances (PFASs), new methods to measure total fluorine of organofluorine using different techniques have been developed.

Simultaneous stimulation of arsenic methylation and inhibition of cadmium bioaccumulation in rice grain using zero valent iron and alternate wetting and drying water management.

Studies aiming to limit bioaccumulation of arsenic (As) and cadmium (Cd) in rice grain has attracted global attention. In this study, simultaneous impact of zero valent iron (Fe⁰) and various water management regimes (continuous flooding (CF), alternate wetting and drying (AWD) and low water (LW)) on rice grain yield (GYM) and bioaccumulation of As and Cd in unpolished rice grain (URG) were investigated. Compared to respective control treatments, Fe⁰ significantly reduced GYM under LW by 32% (p < 0.

High-precision isotopic analysis sheds new light on mercury metabolism in long-finned pilot whales (Globicephala melas).

Whales accumulate mercury (Hg), but do not seem to show immediate evidence of toxic effects. Analysis of different tissues (liver, kidney, muscle) and biofluids (blood, milk) from a pod of stranded long-finned pilot whales (Globicephala melas) showed accumulation of Hg as a function of age, with a significant decrease in the MeHg fraction. Isotopic analysis revealed remarkable differences between juvenile and adult whales.

Novel non-targeted analysis of perfluorinated compounds using fluorine-specific detection regardless of their ionisability (HPLC-ICPMS/MS-ESI-MS).

Although perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have been phased out, there is a plethora of per- or polyfluoroalkyl substances (PFAS) generated and only a small number of these compounds are currently being monitored in environmental and biological sample using molecular mass spectrometry (MS). Total fluorine determination has revealed that a substantial amount of fluorinated organic compounds has not been identified. Due to the small mass deficiency of fluorine, it is not an easy task to screen successfully all fluorinated compounds including those which are not easy ionisable, hence a novel fluorine-specific detector is needed.

AF4-UV-MALS-ICP-MS/MS, spICP-MS, and STEM-EDX for the Characterization of Metal-Containing Nanoparticles in Gas Condensates from Petroleum Hydrocarbon Samples.

The coupling of flow field flow fractionation (FlFFF) with ICP-MS/MS for the fractionation and analysis of natural nanoparticles (NPs) in environmental samples is becoming more popular. However, the applicability of this technique to nonaqueous samples, such as gas condensates from petroleum hydrocarbon samples, has not been reported yet. In this study, an asymmetric flow-field flow fractionation (AF4) system coupled with UV and MALS detectors has been optimized to perform the fractionation of natural NPs present in a gas condensate sample, using THF as the carrier liquid.

Metallomics Study in Plants Exposed to Arsenic, Mercury, Selenium and Sulphur.

This chapter is focussing on the interaction of arsenic, mercury and selenium with plans. Aspects of biotransformations are discussed, before the analytical methodologies are listed and critically appraised in the second part. A holistic view is given, starting from the soil environment and continuing to the plant roots and the translocations into the upper part of the plants.

Comparison of on-site field measured inorganic arsenic in rice with laboratory measurements using a field deployable method: Method validation.

A commercial arsenic field kit designed to measure inorganic arsenic (iAs) in water was modified into a field deployable method (FDM) to measure iAs in rice. While the method has been validated to give precise and accurate results in the laboratory, its on-site field performance has not been evaluated. This study was designed to test the method on-site in Malawi in order to evaluate its accuracy and precision in determination of iAs on-site by comparing with a validated reference method and giving original data on inorganic arsenic in Malawian rice and rice-based products.

Reactive gaseous mercury is generated from chloralkali factories resulting in extreme concentrations of mercury in hair of workers.

Occupational exposure of chloralkali workers to highly concentrated mercury (Hg) vapour has been linked to an increased risk of renal dysfunction and behavioural changes. It is generally believed that these workers are exposed to elemental Hg, which is used in abundance during the production process however, the lack in analytical techniques that would allow for identification of gaseous Hg species poses a challenge, which needs to be addressed in order to reach a consensus. Here, we present the results from simulated exposure studies, which provide sound evidence of higher adsorption rate of HgCl than Hg and its irreversible bonding on the surface of hair.

Importance of ICPMS for speciation analysis is changing: future trends for targeted and non-targeted element speciation analysis.

This article is aimed at researchers interested in organic molecules which contain a heteroatom but who have never considered using inductively coupled plasma mass spectrometry (ICPMS) or who have used ICPMS for years and developed numerous methods for analysis of target elemental species. We try to illustrate (1) that ICPMS has been very useful for speciation analysis of metal(loid) target species and that there is now a trend to replace the costly detector with cheaper detection systems for routine target analysis, and (2) that ICPMS has been used and will be used even more in the future for non-targeted analysis of elements which are not normally associated with ICPMS analysis, such as non-metals such as sulfur, phosphorus, chlorine and fluorine. Graphical Abstract Starting with HPLC-ICPMS for non-targeted analysis of heteroatom containing molecules, once target molecule is identified alternative detectors can be used for routine measurements.

A field deployable method for a rapid screening analysis of inorganic arsenic in seaweed.

Inorganic arsenic (iAs) in 13 store-bought edible seaweed samples and 34 dried kelp () samples was determined by a newly developed, field-deployable method (FDM) with the aid of a field test kit for arsenic in water. Results from the FDM were compared to results from speciation analysis achieved by using high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The FDM consisted of a simple extraction method using diluted HNO to quantitatively extract iAs without decomposing the organoarsenicals to iAs followed by the selective volatilisation of iAs as arsine (AsH) and subsequent chemo-trapping on a filter paper soaked in mercury bromide (HgBr) solution.

Cobalamin Concentrations in Fetal Liver Show Gender Differences: A Result from Using a High-Pressure Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry as an Ultratrace Cobalt Speciation Method.

Maternal diet and lifestyle choices may affect placental transfer of cobalamin (Cbl) to the fetus. Fetal liver concentration of Cbl reflects nutritional status with regards to vitamin B12, but at these low concentration current Cbl measurement methods lack robustness. An analytical method based on enzymatic extraction with subsequent reversed-phase-high-pressure liquid chromatography (RP-HPLC) separation and parallel ICPMS and electrospray ionization (ESI)-Orbitrap-MS to determine specifically Cbl species in liver samples of only 10-50 mg was developed using 14 pig livers.

The importance of glutathione and phytochelatins on the selenite and arsenate detoxification in Arabidopsis thaliana.

We investigated the role of glutathione (GSH) and phytochelatins (PCs) on the detoxification of selenite using Arabidopsis thaliana. The wild-type (WT) of Arabidopsis thaliana and its mutants (glutathione deficient Cad 2-1 and phytochelatins deficient Cad 1-3) were separately exposed to varying concentrations of selenite and arsenate and jointly to both toxicants to determine their sensitivities. The results of the study revealed that, the mutants were about 20-fold more sensitive to arsenate than the WT, an indication that the GSH and PCs affect arsenate detoxification.

In vivo formation of natural HgSe nanoparticles in the liver and brain of pilot whales.

To understand the biochemistry of methylmercury (MeHg) that leads to the formation of mercury-selenium (Hg-Se) clusters is a long outstanding challenge that promises to deepen our knowledge of MeHg detoxification and the role Se plays in this process. Here, we show that mercury selenide (HgSe) nanoparticles in the liver and brain of long-finned pilot whales are attached to Se-rich structures and possibly act as a nucleation point for the formation of large Se-Hg clusters, which can grow with age to over 5 μm in size. The detoxification mechanism is fully developed from the early age of the animals, with particulate Hg found already in juvenile tissues.

Methylmercury varies more than one order of magnitude in commercial European rice.

Rice is known to accumulate methylmercury (MeHg) in the rice grains. MeHg as a neurotoxin impacts on the human central nervous systems and especially on the developing brain. In this exploratory study, 87 commercial rice products sold in Europe, including nine baby-rice products, were analyzed for total Hg and MeHg content.

Possible link between Hg and Cd accumulation in the brain of long-finned pilot whales (Globicephala melas).

The bioaccumulation of metals was investigated by analysis of liver, kidney, muscle and brain tissue of a pod of 21 long-finned pilot whales (Globicephala melas) of all ages stranded in Scotland, UK. The results are the first to report cadmium (Cd) passage through the blood-brain barrier of pilot whales and provide a comprehensive study of the long-term (up to 35 years) mammalian exposure to the environmental pollutants. Additionally, linear accumulation of mercury (Hg) was observed in all studied tissues, whereas for Cd this was only observed in the liver.

Detection of Inorganic Arsenic in Rice Using a Field Test Kit: A Screening Method.

Rice is a staple food eaten by more than 50% of the world's population and is a daily dietary constituent in most South East Asian countries where 70% of the rice export comes from and where there is a high level of arsenic contamination in groundwater used for irrigation. Research shows that rice can take up and store inorganic arsenic during cultivation, and rice is considered to be one of the major routes of exposure to inorganic arsenic, a class I carcinogen for humans. Here, we report the use of a screening method based on the Gutzeit methodology to detect inorganic arsenic (iAs) in rice within 1 h.

Biosynthesis of the Fluorinated Natural Product Nucleocidin in Streptomyces calvus Is Dependent on the bldA-Specified Leu-tRNA(UUA) Molecule.

Nucleocidin is one of the very few natural products known to contain fluorine. Mysteriously, the nucleocidin producer Streptomyces calvus ATCC 13382 has not been observed to synthesize the compound since its discovery in 1956. Here, we report that complementation of S.

Selenopeptides and elemental selenium in Thunbergia alata after exposure to selenite: quantification method for elemental selenium.

Three month old Thunbergia alata were exposed for 13 days to 10 μM selenite to determine the biotransformation of selenite in their roots. Selenium in formic acid extracts (80 ± 3%) was present as selenopeptides with Se-S bonds and selenium-PC complexes (selenocysteinyl-2-3-dihydroxypropionyl-glutathione, seleno-phytochelatin2, seleno-di-glutathione). An analytical method using HPLC-ICPMS to detect and quantify elemental selenium in roots of T.

Direct online HPLC-CV-AFS method for traces of methylmercury without derivatisation: a matrix-independent method for urine, sediment and biological tissue samples.

Mercury (Hg) is a global pollutant which occurs in different species, with methylmercury (MeHg) being the critical compound due to its neurotoxicity and bioaccumulation through the food chain. Methods for trace speciation of MeHg are therefore needed for a vast range of sample matrices, such as biological tissues, fluids, soils or sediments. We have previously developed an ultra-trace speciation method for methylmercury in water, based on a preconcentration HPLC cold vapour atomic fluorescence spectrometry (HPLC-CV-AFS) method.