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Ice rises or ice rumples act as ice-shelf pinning points that can play an important role in regulating the ice discharge of marine outlet glaciers. As an example, the observed recent gradual ungrounding of the ice shelf of West Antarctica's Thwaites Glacier from its last pinning points likely diminished the buttressing effect of the ice shelf and thus contributed to the destabilization of the outlet. Here we use an idealized experimental setting to simulate the response of a marine outlet glacier resting on a landward down-sloping (retrograde) bed to a stepwise ungrounding of its ice shelf from a topographic high and a subsequent re-grounding. We show that the glacier retreat down the retrograde bed, induced by the loss in pinning-point buttressing, can be unstable and irreversible given a relatively deep subglacial bed depression. In this case, glacier retreat and re-advance show a hysteretic behavior, and if the bed depression is sufficiently deep, the glacier does not recover but remains locked in its retreated state. Conversely, reversibility requires a sufficiently shallow bed depression. Based on a simple flux balance analysis, we argue that the combination of a deep bed depression and limited ice-shelf buttressing hampers grounding-line re-advance due to the dominant and highly non-linear influence of the bed depth on the ice discharge across the grounding line. We conclude that outlets that rest on a deep bed depression and are weakly buttressed, such as Thwaites Glacier, are more susceptible to abrupt and irreversible retreat than more strongly buttressed glaciers on more moderate retrograde slopes, such as Pine Island Glacier. Our findings further suggest that the (ir)reversibility of large-scale grounding-line retreat may be strongly affected by calving-front migration and associated changes in ice-shelf buttressing.

The timescales of the flow and retreat of Greenland's and Antarctica's outlet glaciers and their potential instabilities are arguably the largest uncertainty in future sea-level projections. Here we derive a scaling relation that allows the comparison of the timescales of observed complex ice flow fields with geometric similarity. The scaling relation is derived under the assumption of fast, laterally confined, geometrically similar outlet-glacier flow over a slippery bed, i.e., with negligible basal friction. According to the relation, the time scaling of the outlet flow is determined by the product of the inverse of (1) the fourth power of the width-to-length ratio of its confinement, (2) the third power of the confinement depth and (3) the temperature-dependent ice softness. For the outflow at the grounding line of streams with negligible basal friction, this means that the volume flux is proportional to the ice softness and the bed depth, but goes with the fourth power of the gradient of the bed and with the fifth power of the width of the stream. We show that the theoretically derived scaling relation is supported by the observed velocity scaling of outlet glaciers across Greenland as well as by idealized numerical simulations of marine ice-sheet instabilities (MISIs) as found in Antarctica. Assuming that changes in the ice-flow velocity due to ice-dynamic imbalance are proportional to the equilibrium velocity, we combine the scaling relation with a statistical analysis of the topography of 13 MISI-prone Antarctic outlets. Under these assumptions, the timescales in response to a potential destabilization are fastest for Thwaites Glacier in West Antarctica and Mellor, Ninnis and Cook Glaciers in East Antarctica; between 16 and 67 times faster than for Pine Island Glacier. While the applicability of our results is limited by several strong assumptions, the utilization and potential further development of the presented scaling approach may help to constrain timescale estimates of outlet-glacier flow, augmenting the commonly exploited and comparatively computationally expensive approach of numerical modeling.

Owing to global warming and particularly high regional ocean warming, both Thwaites and Pine Island Glaciers in the Amundsen region of the Antarctic Ice Sheet could lose their buttressing ice shelves over time. We analyse the possible consequences using the parallel ice sheet model (PISM), applying a simple cliff-calving parameterization and an ice mélange-buttressing model. We find that the instantaneous loss of ice-shelf buttressing, due to enforced ice-shelf melting, initiates grounding-line retreat and triggers marine ice sheet instability (MISI). As a consequence, the grounding line progresses into the interior of the West Antarctic Ice Sheet and leads to a sea level contribution of 0.6 m within 100 a. By subjecting the exposed ice cliffs to cliff calving using our simplified parameterization, we also analyse marine ice cliff instability (MICI). In our simulations it can double or even triple the sea level contribution depending on the only loosely constrained parameter that determines the maximum cliff-calving rate. The speed of MICI depends on this upper bound of the calving rate, which is given by the ice mélange buttressing the glacier. However, stabilization of MICI may occur for geometric reasons. Because the embayment geometry changes as MICI advances into the interior of the ice sheet, the upper bound on calving rates is reduced and the progress of MICI is slowed down. Although we cannot claim that our simulations bear relevant quantitative estimates of the effect of ice-mélange buttressing on MICI, the mechanism has the potential to stop the instability. Further research is needed to evaluate its role for the past and future evolution of the Antarctic Ice Sheet.

Basal ice-shelf melting is the key driver of Antarctica's increasing sea-level contribution. In diminishing the buttressing force of the ice shelves that fringe the ice sheet, the melting increases the ice discharge into the ocean. Here we contrast the influence of basal melting in two different ice-shelf regions on the time-dependent response of an isothermal, inherently buttressed ice-sheet-shelf system. In the idealized numerical simulations, the basal-melt perturbations are applied close to the grounding line in the ice-shelf's (1) ice-stream region, where the ice shelf is fed by the fastest ice masses that stream through the upstream bed trough and (2) shear margins, where the ice flow is slower. The results show that melting below one or both of the shear margins can cause a decadal to centennial increase in ice discharge that is more than twice as large compared to a similar perturbation in the ice-stream region. We attribute this to the fact that melt-induced ice-shelf thinning in the central grounding-line region is attenuated very effectively by the fast flow of the central ice stream. In contrast, the much slower ice dynamics in the lateral shear margins of the ice shelf facilitate sustained ice-shelf thinning and thereby foster buttressing reduction. Regardless of the melt location, a higher melt concentration toward the grounding line generally goes along with a stronger response. Our results highlight the vulnerability of outlet glaciers to basal melting in stagnant, buttressing-relevant ice-shelf regions, a mechanism that may gain importance under future global warming.

Fusarium oxysporum f. sp. fragariae (Fof) race 1 is avirulent on cultivars with the dominant resistance gene FW1, while Fof race 2 is virulent on FW1-resistant cultivars. We hypothesized there was a gene-for-gene interaction between a gene at the FW1 locus and an avirulence gene (AvrFW1) in Fof race 1. To identify a candidate AvrFW1, we compared genomes of 24 Fof race 1 and three Fof race 2 isolates. We found one candidate gene that was present in race 1, was absent in race 2, was highly expressed in planta, and was homologous to a known effector, secreted in xylem 6 (SIX6). We knocked out SIX6 in two Fof race 1 isolates by homologous recombination. All SIX6 knockout transformants (ΔSIX6) gained virulence on FW1/fw1 cultivars, whereas ectopic transformants and the wildtype isolates remained avirulent. ΔSIX6 isolates were quantitatively less virulent on FW1/fw1 cultivars Fronteras and San Andreas than fw1/fw1 cultivars. Seedlings from an FW1/fw1 × fw1/fw1 population were genotyped for FW1 and tested for susceptibility to a SIX6 knockout isolate. Results suggested that additional minor-effect quantitative resistance genes could be present at the FW1 locus. This work demonstrates that SIX6 acts as an avirulence factor interacting with a resistance gene at the FW1 locus. The identification of AvrFW1 enables surveillance for Fof race 2 and provides insight into the mechanisms of FW1-mediated resistance. [Graphic: see text] Copyright © 2024 The Author(s). This is an open access article distributed under the CC BY-NC-ND 4.0 International license.

Abstract The annual production of strawberry has increased by one million tonnes in the US and 8.4 million tonnes worldwide since 1960. Here we show that the US expansion was driven by genetic gains from Green Revolution breeding and production advances that increased yields by 2,755%. Using a California population with a century-long breeding history and phenotypes of hybrids observed in coastal California environments, we estimate that breeding has increased fruit yields by 2,974-6,636%, counts by 1,454-3,940%, weights by 228-504%, and firmness by 239-769%. Using genomic prediction approaches, we pinpoint the origin of the Green Revolution to the early 1950s and uncover significant increases in additive genetic variation caused by transgressive segregation and phenotypic diversification. Lastly, we show that the most consequential Green Revolution breeding breakthrough was the introduction of photoperiod-insensitive, PERPETUAL FLOWERING hybrids in the 1970s that doubled yields and drove the dramatic expansion of strawberry production in California.

Abstract Verticillium wilt (VW), a devastating vascular wilt disease of strawberry (Fragaria × ananassa), has caused economic losses for nearly a century. This disease is caused by the soil‐borne pathogen Verticillium dahliae, which occurs nearly worldwide and causes disease in numerous agriculturally important plants. The development of VW‐resistant cultivars is critically important for the sustainability of strawberry production. We previously showed that a preponderance of the genetic resources (asexually propagated hybrid individuals) preserved in public germplasm collections were moderately to highly susceptible and that genetic gains for increased resistance to VW have been negligible over the last 60 years. To more fully understand the challenges associated with breeding for increased quantitative resistance to this pathogen, we developed and phenotyped a training population of hybrids (n=564) among elite parents with a wide range of resistance phenotypes. When these data were combined with training data from a population of elite and exotic hybrids (n=386), genomic prediction accuracies of 0.47–0.48 were achieved and were predicted to explain 70%–75% of the additive genetic variance for resistance. We concluded that breeding values for resistance to VW can be predicted with sufficient accuracy for effective genomic selection with routine updating of training populations.

Abstract Genomic prediction in breeding populations containing hundreds to thousands of parents and seedlings is prohibitively expensive with current high‐density genetic marker platforms designed for strawberry. We developed mid‐density panels of molecular inversion probes (MIPs) to be deployed with the “DArTag” marker platform to provide a low‐cost, high‐throughput genotyping solution for strawberry genomic prediction. In total, 7742 target single nucleotide polymorphism (SNP) regions were used to generate MIP assays that were tested with a screening panel of 376 octoploid Fragaria accessions. We evaluated the performance of DArTag assays based on genotype segregation, amplicon coverage, and their ability to produce subgenome‐specific amplicon alignments to the FaRR1 assembly and subsequent alignment‐based variant calls with strong concordance to DArT's alignment‐free, count‐based genotype reports. We used a combination of marker performance metrics and physical distribution in the FaRR1 assembly to select 3K and 5K production panels for genotyping of large strawberry populations. We show that the 3K and 5K DArTag panels are able to target and amplify homologous alleles within subgenomic sequences with low‐amplification bias between reference and alternate alleles, supporting accurate genotype calling while producing marker genotypes that can be treated as functionally diploid for quantitative genetic analysis. The 3K and 5K target SNPs show high levels of polymorphism in diverse F. × ananassa germplasm and UC Davis cultivars, with mean pairwise diversity (π) estimates of 0.40 and 0.32 and mean heterozygous genotype frequencies of 0.35 and 0.33, respectively.

Crop production is becoming an increasing challenge as the global population grows and the climate changes. Modern cultivated crop species are selected for productivity under optimal growth environments and have often lost genetic variants that could allow them to adapt to diverse, and now rapidly changing, environments. These genetic variants are often present in their closest wild relatives, but so are less desirable traits. How to preserve and effectively utilize the rich genetic resources that crop wild relatives offer while avoiding detrimental variants and maladaptive genetic contributions is a central challenge for ongoing crop improvement. This Essay explores this challenge and potential paths that could lead to a solution.

Abstract The development of strawberry (Fragaria × ananassa Duchesne ex Rozier) cultivars resistant to Phytophthora crown rot (PhCR), a devastating disease caused by the soil‐borne pathogen Phytophthora cactorum (Lebert & Cohn) J. Schröt., has been challenging partly because the resistance phenotypes are quantitative and only moderately heritable. To develop deeper insights into the genetics of resistance and build the foundation for applying genomic selection, a genetically diverse training population was screened for resistance to California isolates of the pathogen. Here we show that genetic gains in breeding for resistance to PhCR have been negligible (3% of the cultivars tested were highly resistant and none surpassed early 20th century cultivars). Narrow‐sense genomic heritability for PhCR resistance ranged from 0.41 to 0.75 among training population individuals. Using multivariate genome‐wide association studies (GWAS), we identified a large‐effect locus (predicted to be RPc2) that explained 43.6–51.6% of the genetic variance, was necessary but not sufficient for resistance, and was associated with calcium channel and other candidate genes with known plant defense functions. The addition of underutilized gene bank resources to our training population doubled additive genetic variance, increased the accuracy of genomic selection, and enabled the discovery of individuals carrying favorable alleles that are either rare or not present in modern cultivars. The incorporation of an RPc2‐associated single‐nucleotide polymorphism (SNP) as a fixed effect increased genomic prediction accuracy from 0.40 to 0.55. Finally, we show that parent selection using genomic‐estimated breeding values, genetic variances, and cross usefulness holds promise for enhancing resistance to PhCR in strawberry.

Many oil and gas developments will soon be decommissioned and, knowledge on the accumulation of mercury (Hg), throughout offshore infrastructure is limited. Any release of Hg could have a detrimental impact on marine ecosystems. To bridge this knowledge gap, a fractionation approach was taken on steel samples exposed to Hg 0 and H 2 S, separating Hg compounds removed from the surface into polar, non-polar and insoluble fractions. Hg 0 reacted on corroded surfaces to form several compounds, over 50 % of which were removed by seawater. This suggests that pipelines on the seabed could release a dramatic amount of Hg into the sea if they are left in place. Furthermore, a Cu-Hg amalgam, was identified to be a dominant species, by a combination of XFM, XANES and LA-ICP-TOFMS. Seawater-soluble and amalgam-bound Hg were present regardless of co-exposure to H 2 S. When H 2 S was present Hg nanoparticles accounted for up to 1 % of the total Hg on the steel. This investigation has shown that the Hg speciation on the surfaces of pipelines is complex and future decommissioning strategies should consider a range of Hg species beyond only Hg 0 and metacinnabar (β-HgS), all of which could interact with biota and impact Hg biomagnification through the marine the food web., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Background: If identifying target species is challenging regarding chemical speciation, non-target species present even more significant difficulties. Thus, to improve the performance of the methods, multimodal online coupling involving atomic and molecular mass spectrometry (LC-ICP-MS-ESI-HRMS) is an advance in this direction. Then, this kind of coupling is highlighted in this Tutorial Review, as well as some references emphasizing its potentialities and possible limitations. Some crucial definitions of speciomics, chemical speciation, and others are also included., Results: The main parameters that influence the coupling of an inductively coupled plasma mass spectrometer with a high-resolution mass spectrometer through a chromatographic system are critically commented on, and a diversity of results is demonstrated by using a turtle liver (Caretta caretta) as a model sample. The parameters were discussed in detail in a step-by-step manner: ICP-MS/MS acquisition modes and instrumental parameters, HRMS acquisition modes and instrumental parameters, and data processing strategies (Full MS - Top N, All Ion Fragmentation - AIF, Parallel Reaction Monitoring - PRM). Additionally, this Tutorial Review also demonstrates a diversity of results through target and non-target analysis., Significance: Constituting a guide for those who are interested in a non-targeted analysis of molecular non-volatile/semi-volatile compounds, this Tutorial Review presents trans and multidisciplinary proposals for those communities involving chemistry, biochemistry, medicine, biology, environmental, pharmaceutical, food safety, and omics, among others, where metal (also metalloids or semi-metals and non-metals or heteroatoms) and molecular species are necessary for a good understanding of the studied system. This kind of coupling also allows the discovery of novel biological active elemental species in diverse matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In photocatalysis, photogenerated charge separation is pivotal and can be achieved through various mechanisms. Building heterojunctions is a promising method to enhance charge separation, where effective contact and charge exchange between heterojunction components remains challenging. Mostly used synthesis processes for making heterostructures require high temperatures, difficult processes, or expensive materials. Herein, a heterojunction of potassium intercalated graphitic carbon nitride (K-CN) and nanoflakes of iron phosphor trisulfide (FPS) is designed via a simple mechanical grinding process to boost the hydrogen evolution by a factor of more than 25 compared to pure K-CN. This significant improvement is rarely reached by other combinations of two semiconductors without cocatalysts, such as platinum. It can be attributed to the band alignment and band bending of an S-scheme that is validated via optical and X-ray photoelectron spectroscopy. As a consequence, strong quenching of the photoluminescence and significant H 2 evolution occur for this unique heterojunction. Furthermore, the excellent durability of the designed photocatalytic heterostructure is confirmed by monitoring the catalysts' H 2 -evolution rate and crystal structure after 72 h under light illumination. This study opens up promising and simple pathways for constructing efficient S-scheme heterojunctions for photocatalytic water-splitting.

Quantum dots (QDs) are semiconductor nanocrystals whose optical properties can be tuned by altering their size. By combining QDs with dyes we can make hybrid QD-dye systems exhibiting energy transfer (ET) between QDs and dyes, which is important in sensing and lighting applications. In conventional QDs that need a shell to passivate surface defects, ET usually proceeds through Förster resonance energy transfer (FRET) that requires significant spectral overlap between QD emission and dye absorbance, as well as large oscillator strengths of those transitions. This considerably limits the choice of dyes. In contrast, perovskite QDs do not require passivating shells for bright emission, which makes ET mechanisms beyond FRET accessible. This work explores the design of a CsPbBr 3 QD-dye system to achieve efficient ET from CsPbBr 3 QDs to dyes with dimethyl iminium binding groups where the close binding of dyes to CsPbBr 3 surface facilitates spatial wavefunction overlap. Using steady-state and time-resolved photoluminescence experiments, we demonstrate that efficient ET from CsPbBr 3 to dyes with minimal spectral overlap proceeds via the Dexter exchange-type mechanism, which overcomes the conventional restriction of spectral overlap that severely limits the tunability of these systems. This approach opens new avenues for QD-molecule hybrids for a wide range of applications, such as lighting., (© 2024 Wiley-VCH GmbH.)

Arsenic-containing hydrocarbons (AsHC), a subclass of arsenolipids (AsL), have been proven to exert neuro- and cytotoxic effects in in-vitro and in-vivo studies and were shown to pass through biological barriers like the blood-brain barrier. However, there has been no connection as to the environmental relevance of these findings, meaning there is no study based on samples from free living animals that are exposed to these compounds. Here, we report the identification of two AsHC as well as 3 arsenosugar phospholipids (AsPL) in the brains of a pod of stranded long-finned pilot whales (Globicephala melas) as well as the absence of arsenobetaine (AsB) which is often found to be a dominant As species in fish. We show data which suggests that there is an age-dependent accumulation of AsL in the brains of the animals. The results show that, in contrast to other organs, total arsenic as well as arsenolipids accumulate in an asymptotic pattern in the brains of the animals. Total As concentrations were found to range from 87 to 260 μg As/kg wet weight and between 0.6 and 27.6 μg As/kg was present in the form of AsPL958 in the brains of stranded pilot whales which was the most dominant lipophilic species present. The asymptotic relationship between total As, as well as AsPL, concentration in the brain and whale age may suggest that the accumulation of these species takes place prior to the full development of the blood-brain barrier in young whales. Finally, comparison between the organs of local squid, a common source of food for pilot whales, highlighted a comparable AsL profile which indicates a likely bioaccumulation pathway through the food chain., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Background: Including seaweed in cattle feed has gained increased interest, but it is important to take into account that the concentration of toxic metals, especially arsenic, is high in seaweed. This study investigated the arsenic species in milk from seaweed-fed cows., Results: Total arsenic in milk of control diets (9.3 ± 1.0 μg As kg -1 , n = 4, dry mass) was significantly higher than seaweed-based diet (high-seaweed diet: 7.8 ± 0.4 μg As kg -1 , P < 0.05, n = 4, dry mass; low-seaweed diet: 6.2 ± 1.0 μg As kg -1 , P < 0.01, n = 4, dry mass). Arsenic speciation showed that the main species present were arsenobetaine (AB) and arsenate (As(V)) (37% and 24% of the total arsenic, respectively). Trace amounts of dimethylarsinic acid (DMA) and arsenocholine (AC) have also been detected in milk. Apart from arsenate being significantly lower (P < 0.001) in milk from seaweed-fed cows than in milk from the control group, other arsenic species showed no significant differences between groups., Conclusion: The lower total arsenic and arsenate in seaweed diet groups indicates a possible competition of uptake between arsenate and phosphate, and the presence of AC indicates that a reduction of AB occurred in the digestive tract. Feeding a seaweed blend (91% Ascophyllum nodosum and 9% Laminaria digitata) does not raise As-related safety concerns for milk. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry., (© 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.)

The unique properties of per- and polyfluoroalkyl substances (PFAS) have led to their extensive use in consumer products, including ski wax. Based on the risks associated with PFAS, and to align with PFAS regulations, the international ski federation (FIS) implemented a ban on products containing "C 8 fluorocarbons/perfluorooctanoate (PFOA)" at all FIS events from the 2021/2022 season, leading manufactures to shift their formulations towards short-chain PFAS chemistries. To date, most studies characterising PFAS in ski waxes have measured a suite of individual substances using targeted analytical approaches. However, the fraction of total fluorine (TF) in the wax accounted for by these substances remains unclear. In this study, we sought to address this question by applying a multi-platform, fluorine mass balance approach to a total of 10 commercially available ski wax products. Analysis of TF by combustion ion chromatography (CIC) revealed concentrations of 1040-51700 μg F g -1 for the different fluorinated waxes. In comparison, extractable organic fluorine (EOF) determined in methanol extracts by CIC (and later confirmed by inductively-coupled plasma-mass spectrometry and 19 F- nuclear magnetic resonance spectroscopy) ranged from 92 to 3160 μg g -1 , accounting for only 3-8.8 % of total fluorine (TF). Further characterisation of extracts by cyclic ion mobility-mass spectrometry (IMS) revealed 15 individual PFAS with perfluoroalkyl carboxylic acid concentrations up to 33 μg F g -1 , and 3 products exceeding the regulatory limit for PFOA (0.025 μg g -1 ) by a factor of up to 100. The sum of all PFAS accounted for only 0.01-1.0 % of EOF, implying a high percentage of unidentified PFAS, thus, pyrolysis gas chromatography-mass spectrometry was used to provide evidence of the nature of the non-extractable fluorine present in the ski wax products., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Due to the increasing number of chemicals released into the environment, nontarget screening (NTS) analysis is a necessary tool for providing comprehensive chemical analysis of environmental pollutants. However, NTS workflows encounter challenges in detecting both known and unknown pollutants with common chromatography high-resolution mass spectrometry (HRMS) methods. Identification of unknowns is hindered by limited elemental composition information, and quantification without identical reference standards is prone to errors. To address these issues, we propose the use of inductively coupled plasma mass spectrometry (ICP-MS) as an element-specific detector. ICP-MS can enhance the confidence of compound identification and improve quantification in NTS due to its element-specific response and unambiguous chemical composition information. Additionally, mass balance calculations for individual elements (F, Br, Cl, etc.) enable assessment of total recovery of those elements and evaluation of NTS workflows. Despite its benefits, implementing ICP-MS in NTS analysis and environmental regulation requires overcoming certain shortcomings and challenges, which are discussed herein.

Food contact materials (FCMs) from three countries were analysed for all extractable organofluorines (EOFs) from the materials and subsequently by target and non-target analysis for per- and polyfluoroalkyl substances (PFAS). The EOF varied by two orders of magnitude for FCM from UK and Saudi Arabia ranging between 2.14 and 483 ng cm -2 (0.2-48 ng g -1 ) showing that one quarter of all samples were above the Danish regulation for PFAS in FCM. Target PFAS showed high variability in composition and accounted for less than 1% of the EOF. Non-target PFAS screening using HPLC-ICP-MS and coupled simultaneously to HRMS showed the occurrence of organofluorines which were identified by neither LC-MS/MS nor LC-HRMS. This illustrates that the current target PFAS approaches fail to identify EOFs from FCM, which would be a problem with the new EU proposal to ban all PFAS.

In this study, arsenic (As) speciation was investigated in the freshwater alga Chlamydomonas reinhardtii treated with 20 μg/L arsenate using fractionation as well as ICP-MS/ESI-MS analyses and was compared with the known As metabolite profile of wild-grown Saccharina latissima. While the total As accumulation in C. reinhardtii was about 85% lower than in S. latissima, the relative percentage of arsenolipids was significantly higher in C. reinhardtii (57.0% vs. 5.01%). As-containing hydrocarbons and phospholipids dominated the hydrophobic As profile in S. latissima, but no As-containing hydrocarbons were detectable in C. reinhardtii. Instead for the first time, an arsenoriboside-containing phytol (AsSugPhytol) was found to dominate the hydrophobic arsenicals of C. reinhardtii. Interestingly, this compound and its relatives had so far been only found in green marine microalgae, open sea plankton (mixed assemblage), and sediments but not in brown or red macroalgae. This compound family might therefore relate to differences in the arsenic metabolism between the algae phyla., (© 2024. The Author(s).)

Rice is a staple food and known to accumulate inorganic arsenic (iAs), which is a class 1 carcinogen to humans. Arsenic field-deployable method kits, designed for water testing, are able to screen iAs in rice, to assure food safety and quick decision-making without the need for laboratory analysis. For the arsenic extraction within the field method, nitric acid is used. To make the field method on-site safer, cost-effective and easier to handle, the method was adapted using a Cola in the extraction process. The adapted field-deployable method was tested by screening a total of 30 rice and rice products from the Austrian market. To verify the results obtained by the Cola extraction field-deployable method, the obtained iAs concentration was compared to HPLC-ICP-MS results. The Cola extraction field method obtained an LOD of 39 µg iAs kg -1 rice, and with an average reproducibility of 14% RSD, the method was capable of recording no false-negative but 7% false-positive values at the 2023 updated European Commission (EC) limits for rice. All, but one, screened rice samples were within the EU limits for iAs in rice and rice products., (© 2023. The Author(s).)

Per- and polyfluoroalkyl substances (PFAS) analysis has become crucial due to their presence in the environment, their persistence and potential health risks. These compounds are commonly used in food contact materials (FCM) as a coating to provide water and grease-repellent properties. One of the pathways for PFAS to enter the human body is either through direct consumption of contaminated food or indirectly through migration from FCM into food. The purpose of this study was to investigate where the initial contamination of paper FCM occurs. We analysed paper material consisting of fresh fibre and secondary materials, intended to produce food packaging for the presence of PFAS. The samples were extracted and analysed for 23 different PFAS substances using the targeted approach with LC tandem mass spectrometry (LC-MS/MS). This analytical technique detects specific, easily ionisable PFAS with high sensitivity. However, one drawback of this approach is that it allows the identification of less than 1% of the PFAS known today. For this reason, we used combustion ion chromatography (CIC) to determine the content of extractable organic fluorine compounds (EOF) and compare it to the total fluorine content. The targeted analysis using LC-MS/MS measured an average sum concentration of PFAS of 0.17 ng g -1 sample. Our research shows that the primary PFAS contamination happens during the recycling process since all of the samples in which the targeted PFAS were measured belonged to the secondary material. The most frequently detected analytes were PFOA and PFOS, detected in 90% and 62% of the samples, respectively, followed by PFBS (in 29% of the samples). CIC showed that measured PFAS via LC-MS/MS amount to an average of 2.7 × 10 -4 % of total fluorine content, whereas the EOF was under the LOD in all of the measured samples. This result highlights the complexity of the accurate determination of PFAS compounds, displaying what kind of information the chosen methods provide.

Wild boars have been reported as bioindicators for per- and polyfluoroalkyl substances (PFAS) in a variety of studies. However, data about PFAS levels in wild boars from sites with limited industrial and general human activity is scarce. In this study, wild boar (Sus scrofa) organs from the Bohemian Forest National Park (Czech Republic) were used as bioindicators for PFAS pollution. In this work, 29 livers and 24 kidneys from 30 wild boars (0.5-5 years) were investigated using a fluorine mass balance approach. For this, the samples were measured using high performance liquid chromatography with electrospray ionisation tandem mass spectrometry (HPLC-ESI-MS/MS), targeting 30 PFAS, including legacy and replacement PFAS, direct total oxidisable precursor assay (dTOPA) and combustion ion chromatography (CIC). Perfluorocarboxylic acids (PFCAs) from C 7 to C 14 and perfluorooctanesulfonic acid (PFOS) were detected in >50 % of samples. In the livers, PFCAs dominated the profile with median concentrations of 230 μg/kg for perfluorononanoic acid (PFNA) and 75 μg/kg perfluorooctanoic acid (PFOA). PFOA and PFNA concentrations in the livers were one order of magnitude higher than in livers from wild boars caught in rural NE Germany considered as background concentration. PFOS in liver contributed only 30 % to the Σc(PFAS Target ) with a median concentration of 170 μg/kg. Kidneys and livers contain an average of 2460 μg F/kg and 6800 μg F/kg extractable organic fluorine (EOF) respectively. Σc(PFAS Target ) add up to a maximum of 10 % of the extractable organic fluorine. After oxidisation of the samples, PFOA, PFNA and Σc(PFAS dTOPA ) increased in livers, but could not explain the EOF. The elevated concentration of PFOA and PFNA may indicate differences in biomagnification for different habitats or an unidentified PFAS source in proximity to the national park., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

Manganese doping has been demonstrated as a versatile tool to tune the emission of CsPbCl 3 nanocrystals (NCs). Although this has been demonstrated in nanocubes and nanoplatelets, strategies for doping Mn 2+ in size-tunable, excitonic CsPbCl 3 quantum dots (QDs) remain absent. In this work, we demonstrate the synthesis of size-tunable spheroidal CsPbCl 3 :Mn 2+ QDs, which can be obtained by a water-hexane interfacial combined anion and cation exchange strategy starting from CsPbBr 3 QDs. Interestingly, the QDs exhibit a fast 0.2 ms Mn 2+ photoluminescence (PL) lifetime and an energy transfer (ET) time of approximately 100 ps from the excitonic state of the QD to the atomic state of the Mn 2+ ion. The size dependence observation of the manganese PL efficiency and the slow ET rate suggest that Mn 2+ mainly gets incorporated at the QD's surface, highlighting the importance of strategies chosen for the incorporation of Mn 2+ into perovskite QDs.

Trace element concentrations in toenail clippings have increasingly been used to measure trace element exposure in epidemeological research. Conventional methods such as inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography ICP-MS (HPLC-ICP-MS) are commonly used to measure trace elements and their speciation in toenails. However, the impact of the removal of external contamination on trace element quantification has not been thoroughly studied. In this work, the microdistribution of trace elements (As, Ca, Co, Cu, Fe, K, Mn, Ni, Rb, S, Sr, Ti, and Zn) in dirty and washed toenails and the speciation of As in situ in toenails were investigated using synchrotron X-ray fluorescence microscopy (XFM) and laterally resolved X-ray absorption near edge spectroscopy (XANES). XFM showed different distribution patterns for each trace element, consistent with their binding properties and nail structure. External (terrestrial) contamination was identified and distinguished from the endogenous accumulation of trace elements in toenails─contaminated areas were characterized by the co-occurrence of Co, Fe, and Mn with elements such as Ti and Rb (i.e., indicators of terrestrial contamination). The XANES spectra showed the presence of one As species in washed toenails, corresponding to As bound to sulfhydryl groups. In dirty specimens, a mixed speciation was found in localized areas, containing As III -S species and As V species. Arsenic V is thought to be associated with surface contamination and exogenous As. These findings provide new insights into the speciation of arsenic in toenails, the microdistribution of trace elements, and the effectiveness of a cleaning protocol in removing external contamination.

Optically excited electronic excitations are coupled to the soft and polar halide perovskite lattice, generating coherent phonons after subpicosecond interband laser-excitation. In Ag-based halide double perovskites, Ag-vacancies can bind free excitons, resulting in a pronounced bound exciton resonance. Here, we report the detection of three modulation frequencies corresponding to coherent phonons in Ag-based double perovskite nanocrystals at distinct spectral positions at the bound exciton resonance. Two of them are found in oscillatory spectral shifts of the bound exciton resonance and are identified as Cs- and Br-related bulk phonons. Surprisingly, a third frequency is observed as an intensity modulation. We argue that this amplitude oscillation is a consequence of an optically generated vibronic wave packet localized at a Ag-vacancy. Consequently, the localized coherent phonon modulates the giant oscillator strength of the bound exciton. This optically induced and spatially localized lattice shaking could potentially be useful for initiating photochemical reactions with atomic precision.

GenX (hexafluoropropylene oxide dimer acid) belongs to the group of per- and poly-fluoroalkyl substance (PFAS) compounds introduced to replace perfluorooctanoic acid (PFOA), which has been phased out in industrial and consumer product formulations. While GenX has been investigated in lab animals, there is limited information available regarding its uptake and translocation in wheat and rice. This study reports on a greenhouse experiment in which wheat and rice grown under flooded and non-flooded conditions were exposed to two GenX concentrations in the soil (0.4 mg kg -1 and 2 mg kg -1 ). GenX was analysed in the soil, porewater and shoots using targeted liquid chromatography-tandem mass spectroscopy (LC-MS/MS) analysis. Extractable organic fluorine (EOF) was determined using high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-GFMAS) instrument. Results showed that different species took up different amounts of GenX. The GenX concentration in rice shoots was found to be 2.34 (± 0.45) and 4.11 (± 0.87) μg g -1 under flooded and non-flooded conditions, respectively, at a low exposure level. At high exposure, the GenX concentrations in flooded and non-flooded rice shoots increased threefold to 10.4 (± 0.41) and 13.4 (± 0.72) μg g -1 , respectively. Wheat shoots showed similar concentrations and increases between low- and high-level exposure. The translocation factor was significantly higher (P = 0.013) in non-flooded rice compared to flooded rice. The GenX bioaccumulation behaviours under the same culture conditions (e.g. temperature, humidity, light, same GenX concentration in the soil) were significantly different in non-flooded and flooded rice (P < 0.001). Non-flooded rice plants displayed a higher level of GenX bioaccumulation than flooded ones. Following exposure to GenX, flooded rice plants showed a reduction in biomass (25%) compared to the control plants (P < 0.014). Our findings indicate that GenX is a bioaccumulative compound, the presence of which likely inhibits the growth of plants., (© 2023. The Author(s).)

Per and polyfluoroalkylated substances (PFAS) are common additives in ski waxes for their water repellent characteristic. Abrasion of ski wax leaves PFAS on the snow surface, however, little is known about the distribution and concentration of PFAS in snow and soil due to skiing. In this study we analysed different ski waxes, snowmelts and soil from family skiing areas from Alpine locations using targeted high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) to understand more about PFAS distribution in the environment. In general, we found a very diverse PFAS pattern in the analysed media. PFAS level was higher in skiing areas compared to the non-skiing ones that were used as control. ∑target PFAS ranged between <1.7 ng L -1 and 143 ng L -1 in snowmelt, <0.62 ng g -1 and 5.35 ng g -1 in soil and <1.89 and 874 ± 240 ng g -1 in ski wax samples. Snowmelt was dominated by short-chained PFAS, while soil and wax contained both short and long-chained PFAS. Extractable organic fluorine (EOF) was several orders of magnitude higher for waxes (0.5-2 mg g -1 ) than for soils (up to 0.3 μg g -1 ), while total fluorine (TF) content of the waxes was even higher, up to 31 210 ± 420 μg g -1 . We also showed that the ∑ target PFAS accounts for up to 1.5% in EOF content, showing that targeted LC-MS/MS gives a limited measure of the pollution originated from ski waxes and non-targeted analysis and EOF is necessary for a better overview on PFAS distribution.

Wastewater treatment plants are a major source of per and polyfluoroalkyl substances (PFAS) in the environment; moreover, long chain PFAS are known to accumulate in sewage sludge. Although publications on PFAS in wastewater are available from around the globe, little information is available from Central Europe. In this study influent, effluent, and sludge from two wastewater treatment plants from Austria were analysed for target PFAS compounds with HPLC MS/MS and extractable organic fluorine (EOF) content with combustion ion chromatography (CIC). The sum of 31 target PFAS increased from 22 to 47 ng L -1 in influent to 140 - 213 ng L -1 in effluent and around 10 ng g -1 in sludge, while EOF were found to be consistent (2.3 - 3.5 µg F L -1 ) in influent/effluent and 280 ng F g -1 in sludge. Mass balance analysis showed an increase in the identified PFAS compounds in the effluent compared to the influent (from 0.9% - 1.3% to 3.6% - 6.1%), suggesting biotransformation of non-targeted PFAS precursor compounds. In conclusion, wastewater treatment plants transform some PFAS, and wastewater effluent is a source of PFAS contamination in surface water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The rate of decommissioning of global oil and gas production facilities will accelerate over coming decades, as mature developments reach the end of use, and consumers transition towards renewable energy. Decommissioning strategies should include thorough environmental risk assessments which consider contaminants which are known to be present in oil and gas systems. Mercury (Hg) is a global pollutant that occurs naturally in oil and gas reservoirs. However, knowledge of Hg contamination in transmission pipelines and process equipment is limited. We investigated the potential for accumulation of Hg 0 within production facilities, particularly those transporting gases, by considering the deposition of Hg onto steel surfaces from the gas phase. Following incubation experiments in a Hg saturated atmosphere; fresh API 5L-X65 and L80-13Cr steels were found to adsorb 1.4 × 10 -5 ± 0.04 × 10 -5 and 1.1 × 10 -5 ± 0.04 × 10 -5 g m -2 , respectively, while corroded samples of the same steels adsorbed 0.12 ± 0.01 and 0.83 ± 0.02 g m -2 ; an increase in adsorbed mercury by four orders of magnitude. The association between surface corrosion and Hg was demonstrated by laser ablation ICPMS. The levels of Hg measured on the corroded steel surfaces indicates a potential environmental risk; therefore, mercury speciation (including the presence of ß-HgS, not considered in this study), concentrations and cleaning methods should be considered when developing oil and gas decommissioning strategies., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Lhiam Paton reports financial support was provided by TechnipFMC Aberdeen., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Background: Cultivated lands in the vicinity of industry are vulnerable due to trace element releases from industrial activities. One such situation concerns the surrounding of the largest cement-manufacturing plant in sub-Saharan Africa, located in Obajana, Nigeria., Objective: This study aimed at examining the trace element concentrations in the soil as they contaminate corn crops in the vicinity of a cement manufacturing plant. A case study of the cement-manufacturing plant located in Obajana, Nigeria is presented., Methods: We used inductively coupled plasma-mass spectrometer to analyse for total arsenic (As), cadmium (Cd), chromium(Cr), copper (Cu), lead (Pb), and nickel (Ni) concentrations and microwave-induced plasma-atomic emission spectrometer to measure total iron (Fe) and zinc (Zn) contents in 89 samples of corn and surface soil (0-15 cm) from five farmlands including reference farmland and evaluated health hazard of human exposure to the trace elements via the consumption of corn cultivated in the area., Results: The results showed the average Cr concentrations in µg/g dry weight (±standard error of the mean) in corn ranged from 2.08 ± 0.17 to 3.56 ± 0.65 in all the farmlands including control, while the mean Pb levels in µg/g dry weight (± standard error of the mean) in corn extended from 0.23 ± 0.03 to 0.38 ± 0.02 in the farmlands downwind of the cement plant. The Cr values were several factors higher than the stable concentration range of 0.01 to 0.41 µg/g reported in cereal grains, while the Pb values exceeded the limit of 0.2 µg/g set by the Food and Agriculture Organization of the United Nations/World Health Organization in grains. Lead is a trace element of environmental concern and its average levels in the farmlands downwind of the plant were found to be several orders of magnitude higher than the values in µg/g dry weight (± standard error of the mean) (0.01 ± 0.00 to 0.02 ± 0.00) observed in the farmlands upwind of the plant and were statistically significant (p < 0.0001)., Impact Statement: Our findings provide the first health hazard assessment from the consumption of corn cultivated in the vicinity of the largest cement-manufacturing plant in Nigeria as far as we know., (© 2023. The Author(s).)

Background: Following a well-balanced diet ensures that a person gets all the essential elements for health sustenance. However, in the United Kingdom an increasing proportion of people are transiting to become vegans who exclude animal-based products in their diets. Consequently, people may have a deficit of essential elements such as iodine which is not present in most plant-based meals, additionally iodide fortified table salt is not commonly used in the UK. Without iodine people consuming a vegan diet risk developing iodine deficiency and diseases like goiter., Methods: The objective of this study is to determine the difference in iodine content and iodine speciation between plant-based and dairy products. More than 100 market samples of plant-based and dairy milk products were collected in Scotland, UK., Results: Iodine concentrations in dairy milk is ten times higher compared to plant-based milks. Similar differences were also apparent for butter, yogurt and cheese. A total of 20% of plant-based milk products were fortified with iodine, however these products had lower iodine concentrations compare to the equivalent dairy products. In this study we calculated that people with average diet have an iodine intake of 226 + /- 103 μg day -1 from dairy products which satisfies the WHO recommended intake of adults and 90% of the recommend intake for pregnant and breast-feeding women. A diet from substituted dairy products gives only 21.8 µg day -1 for the respective WHO guideline intake values, which accounts only 15% of the iodine intake for adults and 9% for pregnant and lactating women. Iodine fortified diet could increase the iodine intake to 55% or 33% of the WHO recommended daily intake respectively., Conclusion: Plant-based dairy consumers are encouraged to use iodine fortified dairy products or use of iodized salt in the UK for home cooking, otherwise there are at risk to get iodine deficient., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests Ali Alzahrani reports financial support was provided by Saudi Arabian Cultural Bureau. Declaration of interest All authors have no conflict of interest. Declaration of generative AI and AI assisted technologies in the writing process. No AI was used in the writing process and in the final manuscript. One artistic image was generated using AI technology as part of the graphical abstract., (Copyright © 2023 The Authors. Published by Elsevier GmbH.. All rights reserved.)

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps-to-ns timescales, is much faster than proton delivery (∼μs), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady-state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four-level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

This review aimed to investigate the reported concentrations of arsenic (As), cadmium (Cd), and lead (Pb) in rice cultivated in Africa and African rice paddies compared to other regions. It also aimed to explore the factors influencing these concentrations and evaluate the associated health risks of elevated As, Cd, and Pb exposure. Relevant data were obtained from electronic databases such as PubMed, Scopus, and Google Scholar using specific keywords related to arsenic, cadmium, lead, rice, Africa, paddy, and grain. While the number of studies reporting the concentrations of As, Cd, and Pb in rice and rice paddies in Africa is relatively low compared to other regions, this review revealed that most of the African rice and paddy soils have low concentrations of these metals. However, some studies have reported elevated concentrations of As, Cd, and Pb in paddy fields, which is concerning due to the increased use of agrochemicals containing heavy metals in rice production. Nonetheless, agronomical interventions such as implementing alternate wetting and drying water management, cultivating cultivars with low accumulation of As, Cd, and Pb, amending rice fields with sorbents, and screening irrigation water can limit the bioaccumulation of these carcinogens in paddy fields using phytoremediation techniques. Therefore, we strongly urge African governments and organizations operating in Africa to enhance the capacity of rice farmers and extension officers in adopting approaches and practices that reduce the accumulation of these carcinogenic metals in rice. This is essential to achieve the sustainable development goal of providing safe food for all., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (© 2023 The Authors.)