Terrestrial Contamination Research Articles

Hydrogen Isotopic Composition of Hydrous Minerals in Asteroid Ryugu

Rock fragments of the Cb-type asteroid Ryugu returned to Earth by the JAXA Hayabusa2 mission share mineralogical, chemical, and isotopic properties with the Ivuna-type (CI) carbonaceous chondrites. Similar to CI chondrites, these fragments underwent extensive aqueous alteration and consist predominantly of hydrous minerals likely formed in the presence of liquid water on the Ryugu parent asteroid. Here we present an in situ analytical survey performed by secondary ion mass spectrometry from which we have estimated the D/H ratio of Ryugu’s hydrous minerals, D/HRyugu, to be [165 ± 19] × 10−6, which corresponds to δDRyugu = +59 ± 121‰ (2σ). The hydrous mineral D/HRyugu’s values for the two sampling sites on Ryugu are similar; they are also similar to the estimated D/H ratio of hydrous minerals in the CI chondrites Orgueil and Alais. This result reinforces a link between Ryugu and CI chondrites and an inference that Ryugu’s samples, which avoided terrestrial contamination, are our best proxy to estimate the composition of water at the origin of hydrous minerals in CI-like material. Based on this data and recent literature studies, the contribution of CI chondrites to the hydrogen of Earth’s surficial reservoirs is evaluated to be ∼3%. We conclude that the water responsible for the alteration of Ryugu’s rocks was derived from water ice precursors inherited from the interstellar medium; the ice partially re-equilibrated its hydrogen with the nebular H2 before being accreted on the Ryugu’s parent asteroid.

Homogeneity and heterogeneity in near-infrared FTIR spectra of Ryugu returned samples

Surface and subsurface materials of C-type near-Earth asteroid 162173 Ryugu were collected and successfully returned to the Earth in the Hayabusa2 mission. Fourier Transform Infrared Spectroscopy (FTIR) has been conducted to characterize these returned samples as one of the initial descriptions in a non-destructive manner under a purified nitrogen condition without terrestrial contamination. We selected the individual grains and aggregate samples that were not severely influenced by the reflection of incident beam at the sapphire dish and analyzed their reflectance spectra using the primary component analysis (PCA). The result indicates that Ryugu returned samples are highly homogeneous with only a little heterogeneity. The average spectrum of the main PCA group is represented by four absorption bands at 2.7, 3.05, 3.4, and 3.95 μm. The spectral feature is consistent with that obtained from bulk FTIR measurements, indicating potential presence of hydroxyl, organics, and carbonates. Rarely observed types of grains with unique spectra are categorized into three groups: significantly high reflectance, carbonates, and hydroxyl compounds with broad OH absorption.Graphical

Insights into the formation and evolution of extraterrestrial amino acids from the asteroid Ryugu

All life on Earth contains amino acids and carbonaceous chondrite meteorites have been suggested as their source at the origin of life on Earth. While many meteoritic amino acids are considered indigenous, deciphering the extent of terrestrial contamination remains an issue. The Ryugu asteroid fragments (JAXA Hayabusa2 mission), represent the most uncontaminated primitive extraterrestrial material available. Here, the concentrations of amino acids from two particles from different touchdown sites (TD1 and TD2) are reported. The concentrations show that N,N-dimethylglycine (DMG) is the most abundant amino acid in the TD1 particle, but below detection limit in the other. The TD1 particle mineral components indicate it experienced more aqueous alteration. Furthermore, the relationships between the amino acids and the geochemistry suggest that DMG formed on the Ryugu progenitor body during aqueous alteration. The findings highlight the importance of aqueous chemistry for defining the ultimate concentrations of amino acids in primitive extraterrestrial samples.

Extraterrestrial amino acids and amines identified in asteroid Ryugu samples returned by the Hayabusa2 mission

The hot water and acid extracts of two different Ryugu samples collected by the Hayabusa2 mission were analyzed for the presence of aliphatic amines and amino acids. The abundances and relative distributions of both classes of molecules were determined, as well as the enantiomeric compositions of the chiral amino acids. The Ryugu samples studied here were recovered from sample chambers A and C, which were composed of surface material, and a combination of surface and possible subsurface material, respectively. A total of thirteen amino acids were detected and quantitated in these samples, with an additional five amino acids that were tentatively identified but not quantitated. The abundances of four aliphatic amines identified in the Ryugu samples were also determined in the current work. Amino acids were observed in the acid hydrolyzed and unhydrolyzed hot water extracts of asteroid Ryugu regolith using liquid chromatography with UV fluorescence detection and high-resolution mass spectrometry. Conversely, aliphatic amines were only analyzed in the unhydrolyzed hot water Ryugu extracts. Two- to six-carbon (C2-C6) amino acids with individual abundances ranging from 0.02 to 15.8 nmol g−1, and one- to three-carbon (C1-C3) aliphatic amines with individual abundances from 0.05 to 34.14 nmol g−1, were found in the hot water extracts. Several non-protein amino acids that are rare in biology, including β-amino-n-butyric acid (β-ABA) and β-aminoisobuytric acid (β-AIB), were racemic or very nearly racemic, thus indicating their likely abiotic origins. Trace amounts of select protein amino acids that were enriched in the l-enantiomer may indicate low levels of terrestrial amino acid contamination in the samples. However, the presence of elevated abundances of free and racemic alanine, a common protein amino acid in terrestrial biology, and elevated abundances of the predominately free and racemic non-protein amino acids, β-ABA and β-AIB, indicate that many of the amino acids detected in the Ryugu water extracts were indigenous to the samples. Although the Ryugu samples have been found to be chemically similar to CI type carbonaceous chondrites, the measured concentrations and relative distributions of amino acids and aliphatic amines in Ryugu samples were notably different from those previously observed for the CI1.1 carbonaceous chondrite, Orgueil. This discrepancy could be the result of differences in the original chemical compositions of the parent bodies and/or alteration conditions, such as space weathering. In addition to α-amino acids that could have been formed by Strecker cyanohydrin synthesis during a low temperature aqueous alteration phase, β-, γ-, and δ-amino acids, including C3 – C5 straight-chain n-ω-amino acids that are not formed by Strecker synthesis, were also observed in the Ryugu extracts. The suite of amino acids measured in the Ryugu samples indicates that multiple amino acid formation mechanisms were active on the Ryugu parent body. The analytical techniques used here are well-suited to search for similar analytes in asteroid Bennu material collected by the NASA OSIRIS-REx mission scheduled for Earth return in September 2023.

Direct Production of Bio-Recalcitrant Carboxyl-Rich Alicyclic Molecules Evidenced in a Bacterium-Induced Steroid Degradation Experiment.

Carboxyl-rich alicyclic molecules (CRAM) are highly unsaturated compounds extensively distributed throughout aquatic environments and sediments. This molecular group is widely referred to as a major proxy of recalcitrant organic materials, but its direct biosynthesis remains unclear. Steroids are a typical anthropogenic contaminant and have been previously suggested to be precursors of CRAM; however, experimental evidence to support this hypothesis is lacking. Here, a steroid-degrading bacterium, Comamonas testosteroni ATCC 11996, was incubated in a liquid medium supplemented with testosterone (a typical steroid) as the sole carbon source for 90 days. Testosterone-induced metabolites (TIM) were extracted for molecular characterization and to examine the bioavailability during an additional 90-day incubation after inoculation with a natural coastal microbial assemblage. The results showed that 1,775 molecular formulas (MFs) were assigned to TIM using ultrahigh-resolution mass spectrometry, with 66.99% categorized as CRAM-like constituents. A large fraction of TIM was respired or transformed during the additional 90-day seawater incubation; nevertheless, 638 MFs of the TIM persisted or increased during incubation. Among the 638 MFs, 394 were commonly assigned in natural deep seawater samples (depths of 500 to 2,000 m) from the South China Sea. Compared to the catabolites of the well-established testosterone degradation pathway, we compiled a list of bio-refractory MFs and potential chemical structures, some of which shared structural homology with CRAM. These results demonstrated direct microbial production of bio-refractory CRAM from steroid hormones and indicated that some of the biogenic CRAM resisted microbial decomposition, potentially contributing to the aquatic refractory dissolved organic matter (DOM) pool. IMPORTANCE CRAM are an operationally defined DOM group comprising a complex mixture of carboxylated and fused alicyclic structures. This DOM group is majorly characterized as refractory DOM in the marine environment. However, the origins of the complex CRAM remain unclear. In this study, we demonstrated that testosterone (a typical steroid) could be transformed into bio-refractory CRAM by a single bacterial strain and observed that some of the CRAM highly resisted microbial degradation. Through molecular comparison and screening, potential chemical structures of steroid-induced CRAM were suggested. This study established the biological connection between steroids and bio-refractory CRAM, and it provides a novel perspective explaining the fate of terrestrial contaminants in aquatic environments.

The COSPAR planetary protection requirements for space missions to Venus

The Committee on Space Research's (COSPAR) Planetary Protection Policy states that all types of missions to Venus are classified as Category II, as the planet has significant research interest relative to the processes of chemical evolution and the origin of life, but there is only a remote chance that terrestrial contamination can proliferate and compromise future investigations. "Remote chance" essentially implies the absence of environments where terrestrial organisms could survive and replicate. Hence, Category II missions only require simplified planetary protection documentation, including a planetary protection plan that outlines the intended or potential impact targets, brief Pre- and Post-launch analyses detailing impact strategies, and a Post-encounter and End-of-Mission Report. These requirements were applied in previous missions and are foreseen for the numerous new international missions planned for the exploration of Venus, which include NASA's VERITAS and DAVINCI missions, and ESA's EnVision mission. There are also several proposed missions including India's Shukrayaan-1, and Russia's Venera-D. These multiple plans for spacecraft coincide with a recent interest within the scientific community regarding the cloud layers of Venus, which have been suggested by some to be habitable environments. The proposed, privately funded, MIT/Rocket Lab Venus Life Finder mission is specifically designed to assess the habitability of the Venusian clouds and to search for signs of life. It includes up to three atmospheric probes, the first one targeting a launch in 2023.The COSPAR Panel on Planetary Protection evaluated scientific data that underpins the planetary protection requirements for Venus and the implications of this on the current policy. The Panel has done a thorough review of the current knowledge of the planet's conditions prevailing in the clouds. Based on the existing literature, we conclude that the environmental conditions within the Venusian clouds are orders of magnitude drier and more acidic than the tolerated survival limits of any known terrestrial extremophile organism. Because of this future orbital, landed or entry probe missions to Venus do not require extra planetary protection measures. This recommendation may be revised in the future if new observations or reanalysis of past data show any significant increment, of orders of magnitude, in the water content and the pH of the cloud layer.

The noble gas and nitrogen relationship between Ryugu and carbonaceous chondrites

Carbonaceous chondrites are considered to have originated from C-type asteroids and represent some of the most primitive material in our solar system. Furthermore, since carbonaceous chondrites can contain significant quantities of volatile elements, they may have played a crucial role in supplying volatiles and organic material to Earth and other inner solar system bodies. However, a major challenge of unravelling the volatile composition of chondritic meteorites is distinguishing between which features were inherited from the parent body, and what may be a secondary feature attributable to terrestrial weathering. In December 2020, the Hayabusa2 mission of the Japan Aerospace Exploration Agency (JAXA) successfully returned surface material from the C-type asteroid (162173) Ryugu to Earth. This material has now been classified as closely resembling CI-type chondrites, which are the most chemically pristine meteorites. The analysis of material from the surface of Ryugu therefore provides a unique opportunity to analyse the volatile composition of material that originated from a CI-type asteroid without the complications arising from terrestrial contamination. Given their highly volatile nature, the noble gas and nitrogen inventories of chondrites are highly sensitive to different alteration processes on the asteroid parent body, and to terrestrial contamination. Here, we investigate the nitrogen and noble gas signature of two pelletized grains collected from the first and second touchdown sites (Okazaki et al., 2022a), to provide an insight into the formation and alteration history of Ryugu. The concentration of trapped noble gas in the Ryugu samples is greater than the average composition of previously measured CI chondrites and are primarily derived from phase Q, although a significant contribution of presolar nanodiamond Xe-HL is noted. The large noble gas concentrations coupled with a significant contribution of presolar nanodiamonds suggests that the Ryugu samples may represent some of the most primitive unprocessed material from the early solar system. In contrast to the noble gases, the abundance of nitrogen and δ15N composition of the two Ryugu pellets are lower than the average CI chondrite value. We attribute the lower nitrogen abundances and δ15N measured in this study to the preferential loss of a 15N-rich phase from our samples during aqueous alteration on the parent planetesimal. The analyses of other grains returned from Ryugu have shown large variations in nitrogen concentrations and δ15N indicating that alteration fluids heterogeneously interacted with material now present on the surface of Ryugu. Finally, the ratio of trapped noble gases to nitrogen is higher than CI chondrites, and is closer to refractory phase Q and nanodiamonds. This indicates that Ryugu experienced aqueous alteration that led to the significant and variable loss of nitrogen, likely from soluble organic matter, without modification of the noble gas budget, which is primarily hosted in insoluble organic matter and presolar diamonds and is therefore more resistant to aqueous alteration.

Testing materials to mitigate terrestrial organic contamination of meteorites: Implications for collection, curation, and handling of astromaterials

AbstractOrganic matter in astromaterials can provide important information for understanding the chemistry of our solar system and the prebiotic conditions of the early Earth. However, once astromaterials reach the Earth's surface, they can be readily contaminated through contact with the Earth's surface as well as during processing and curation. Here, we investigate how typical handling and curation materials interact with meteorite specimens by documenting hydrophobic organic compound contamination in the laboratory environment and on materials that might be used for their collection and storage. We use gas chromatography–mass spectrometry analysis of soluble organic compounds in dichloromethane extracts of these materials to gain insights into what materials and methods are best for the collection and curation of astromaterials. Our results have implications for how extraterrestrial samples—especially those containing significant intrinsic organic matter—are handled and curated to preserve them in their most pristine states. Following recommendations of other researchers in the area of returned sample curation, we advocate for a thorough investigation into the materials used in handling and curation of meteorites to create a contamination baseline to inform soluble organic analyses on astromaterials and enable the discrimination of terrestrial and extraterrestrial compounds.

The amino acid and polycyclic aromatic hydrocarbon compositions of the promptly recovered CM2 Winchcombe carbonaceous chondrite

AbstractThe rapid recovery of the Winchcombe meteorite offers a valuable opportunity to study the soluble organic matter (SOM) profile in pristine carbonaceous astromaterials. Our interests in the biologically relevant molecules, amino acids—monomers of protein, and the most prevalent meteoritic organics—polycyclic aromatic hydrocarbons (PAHs) are addressed by analyzing the solvent extracts of a Winchcombe meteorite stone using gas chromatography mass spectrometry. The Winchcombe sample contains an amino acid abundance of ~1132 parts‐per‐billion that is about 10 times lower than other CM2 meteorites. The detection of terrestrially rare amino acids, including α‐aminoisobutyric acid (AIB); isovaline; β‐alanine; α‐, β‐, and γ‐amino‐n‐butyric acids; and 5‐aminopentanoic acid, and the racemic enantiomeric ratios (D/L = 1) observed for alanine and isovaline indicate that these amino acids are indigenous to the meteorite and not terrestrial contaminants. The presence of predominantly α‐AIB and isovaline is consistent with their formation via the Strecker‐cyanohydrin synthetic pathway. The L‐enantiomeric excesses in isovaline previously observed for aqueously altered meteorites were viewed as an indicator of parent body aqueous processing; thus, the racemic ratio of isovaline observed for Winchcombe, alongside the overall high free:total amino acid ratio, and the low amino acid concentration suggest that the analyzed stone is derived from a lithology that has experienced brief episode(s) of aqueous alteration. Winchcombe also contains 2‐ to 6‐ring alkylated and nonalkylated PAHs. The low total PAHs abundance (6177 ppb) and high nonalkylated:alkylated ratio are distinct from that observed for heavily aqueously altered CMs. The weak petrographic properties of Winchcombe, as well as the discrepancies observed for the Winchcombe SOM content—a low total amino acid abundance comparable to heavily altered CMs, and yet the high free:total amino acid and nonalkylated:alkylated PAH ratios are on par with the less altered CMs—suggest that Winchcombe could represent a class of weak, poorly lithified meteorite not been previously studied.

Terrestrial nanoparticle contaminants and geospatial optics using the Sentinel-3B OLCI satellite in the Tinto River estuary region of the Iberian Peninsula

The Tinto River is known globally for having a reddish color due to the high concentration of dissolved metals in its waters. The general objective of this study is to analyze the dispersion of nanoparticles (NPs) and ultra-fine particles in terrestrial and geospatial suspended sediments (SSs) using Sentinel-3B OLCI (Ocean Land Color Instrument) satellite images; by examining water turbidity levels (TSM_NN), suspended pollution potential (ADG_443_NN) and presence of chlorophyll-a (CHL_NN). The images were collected in the estuary of the Tinto River, in the city of Nerva, Spanish province of Huelva, between 2019 and 2021. The following hazardous elements were identified in nanoparticles and ultra-fine particles by FE-SEM/EDS: As, Cd, Ni, V, Se, Mo, Pb, Sb and Sn. Sentinel-3B OLCI satellite images detected a 2019 TSM_NN of 23.47 g−3, and a 2021 reading of 16.38 g−3.

Oxygen isotope evidence from Ryugu samples for early water delivery to Earth by CI chondrites

The delivery of water to the inner Solar System, including Earth, is still a debated topic. A preferential role for hydrated asteroids in this process is supported by isotopic measurements. Carbonaceous chondrite (CC) meteorites represent our main source of information about these volatile-rich asteroids. However, the destruction of weaker materials during atmospheric entry creates a bias in our CC data. The return of surface materials from the C-type asteroid 162173 Ryugu by the Hayabusa2 spacecraft provides a unique opportunity to study high-porosity, low-density, primitive materials, unrepresented in the meteorite record. We measured the bulk oxygen isotope composition from four Ryugu particles and show that they most closely resemble the rare CI (CC Ivuna-type) chondrites, but with some differences that we attribute to the terrestrial contamination of the CI meteorites. We suggest that CI-related material is widespread among carbonaceous asteroids and a more important source of Earth’s water and other volatiles than its limited presence in our meteoritic collection indicates.

Solid-Phase Microextraction for Organic Contamination Control Throughout Assembly and Operational Phases of Space Missions.

Space missions concerned with life detection contain highly sensitive instruments for the detection of organics. Terrestrial contamination can interfere with signals of indigenous organics in samples and has the potential to cause false-positive biosignature detections, which may lead to incorrect suggestions of the presence of life elsewhere in the solar system. This study assessed the capability of solid-phase microextraction (SPME) as a method for monitoring organic contamination encountered by spacecraft hardware during assembly and operation. SPME-gas chromatography-mass spectrometry (SPME-GC-MS) analysis was performed on potential contaminant source materials, which are commonly used in spacecraft construction. The sensitivity of SPME-GC-MS to organics was assessed in the context of contaminants identified in molecular wipes taken from hardware surfaces on the ExoMars Rosalind Franklin rover. SPME was found to be effective at detecting a wide range of common organic contaminants that include aromatic hydrocarbons, aliphatic hydrocarbons, nitrogen-containing compounds, alcohols, and carbonyls. A notable example of correlation of contaminant with source material was the detection of benzenamine compounds in an epoxy adhesive analyzed by SPME-GC-MS and in the ExoMars rover surface wipe samples. The current form of SPME-GC-MS does not enable quantitative evaluation of contaminants, nor is it suitable for the detection of every group of organic molecules relevant to astrobiological contamination concerns, namely large and/or polar molecules such as amino acids. However, it nonetheless represents an effective new monitoring method for rapid, easy identification of organic contaminants commonly present on spacecraft hardware and could thus be utilized in future space missions as part of their contamination control and mitigation protocols.

Hazardous effects of plastic wastes on land biodiversity: A review

Plastic pollution is ubiquitous throughout the world’s ecosystem. Increase in the world’s plastic production and use, inefficient recycling, indiscriminate disposal, synthetic nature and non-biodegradability of plastics have made it a considerable threat to biodiversity. The impact of plastic wastes on humans and the environment is becoming apparent. However, information on the impacts of plastic wastes on biodiversity is mostly directed towards marine environment with scarce information on land biodiversity although terrestrial environment is the major source of marine contamination. Terrestrial plastic waste contaminants are derived from long term used plastic containers and single-use plastic products, which are introduced by anthropological means, flood water, sewage and wind dispersal. Gradual breakdown of large plastic wastes give rise to microplastics, which increase its abundance in the environment. Plastics threaten wildlife in terms of entanglements, ingestion and chocking, which often results in loss of body parts or mortality. Plastics as vectors of invasive species in marine ecosystem have been widely established. Although not much is known on the importation of invasive species on terrestrial ecosystem by plastic wastes, there is possibility that plastic waste can be a potential vector of terrestrial alien species. Contamination of soil with microplastics alters soil habitats and disturbs the natural biophysical properties of the soil environment that leaves a negative impact on soil biota by reducing their activities and indirectly affecting food production. Accumulation of plastic wastes provides breeding ground for disease vectors, which has contributed to increased prevalence of emerging infectious diseases. This review examines the impact of plastic wastes on terrestrial biodiversity as it affects soil organisms, land animals and breeding of disease vectors.

Rapid characterisation of Mars' mantle reservoirs by in situ laser ablation 87Sr/86Sr analysis of shocked feldspar (maskelynite)

The 87Sr/86Sr isotopic properties of martian meteorites, measured by isolation and purification of Rb and Sr fractions, have long been used to partially characterise Mars' mantle. However, this method is time-consuming, destructive, and subject to incorporation of terrestrial contamination due to precipitation of phases in fractures and/or grain boundaries prior to meteorite collection. In this study, we test the effectiveness of in situ acquisition of 87Sr/86Sr by laser ablation in maskelynite - a typically low Rb/Sr (<0.1) feldspar-composition glass formed during high-P shock metamorphism – as a method of rapid characterisation of Mars' mantle Sr isotope ratios. Element concentration maps and the results of unwashed and gently surface-leached bulk rock analyses indicate that terrestrial Sr has infiltrated the studied meteorites and affected bulk rock trace element budgets. However, maskelynite trace element concentrations are largely unaffected and their martian igneous Rb/Sr is preserved. In situ87Sr/86Sr analyses of maskelynite, checked against a newly developed Sr feldspar reference material (KAN, presented here and available on demand), accurately and precisely distinguish different shergottite mantle reservoirs. The measurements reproduce published data, have uncertainties on the 4th to 5th decimal place, and yield statistically indistinguishable results in analytical sessions separated by long periods of time. The data from 11 enriched shergottites reveal there to be subtle Sr isotope variation within the enriched shergottite mantle reservoir, or that there was crustal assimilation of radiogenic components into the shergottites, or that the shergottite liquids were extracted over a time period during which the mantle reservoir 87Sr/86Sr evolved. The limited published age range of the enriched shergottites, coupled with the absence of a correlation between in situ87Sr/86Sr and REE, Sr or Pb concentration in maskelynite, suggests that the isotope range is best explained by small variations in the enriched mantle reservoir. Given the presence of maskelynite (or plagioclase) in many meteorites, the in situ method will be useful when there are only very small volumes of material available and/or where terrestrial contamination is suspected.

Using Organic Contaminants to Constrain the Terrestrial Journey of the Martian Meteorite Lafayette.

A key part of the search for extraterrestrial life is the detection of organic molecules since these molecules form the basis of all living things on Earth. Instrument suites such as SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) onboard the NASA Perseverance rover and the Mars Organic Molecule Analyzer onboard the future ExoMars Rosalind Franklin rover are designed to detect organic molecules at the martian surface. However, size, mass, and power limitations mean that these instrument suites cannot yet match the instrumental capabilities available in Earth-based laboratories. Until Mars Sample Return, the only martian samples available for study on Earth are martian meteorites. This is a collection of largely basaltic igneous rocks that have been exposed to varying degrees of terrestrial contamination. The low organic molecule abundance within igneous rocks and the expectation of terrestrial contamination make the identification of martian organics within these meteorites highly challenging. The Lafayette martian meteorite exhibits little evidence of terrestrial weathering, potentially making it a good candidate for the detection of martian organics despite uncertainties surrounding its fall history. In this study, we used ultrapure solvents to extract organic matter from triplicate samples of Lafayette and analyzed these extracts via hydrophilic interaction liquid chromatography-mass spectrometry (HILIC-MS). Two hundred twenty-four metabolites (organic molecules) were detected in Lafayette at concentrations more than twice those present in the procedural blanks. In addition, a large number of plant-derived metabolites were putatively identified, the presence of which supports the unconfirmed report that Lafayette fell in a semirural location in Indiana. Remarkably, the putative identification of the mycotoxin deoxynivalenol (or vomitoxin), alongside the report that the collector was possibly a student at Purdue University, can be used to identify the most likely fall year as 1919.

Spatiotemporal heterogeneous effects of microplastics input on soil dissolved organic matter (DOM) under field conditions

Microplastics (MPs) as emerging persistent pollutants are ubiquitous in terrestrial environments. The effects of MPs input on soil dissolved organic matter (DOM) yet remain largely unclear, which limits our ability to predict how soil carbon dynamics will respond to the intensifying terrestrial plastic contamination, especially under the context of climate change. Here, a long-term field experiment with MPs addition treatment in soils spanning cold temperate zone to the tropics in China was conducted to evaluate the effects of MPs on DOM composition and to explore the spatial and temporal distribution patterns and relevant mechanistic controls of DOM responses after MPs input. We report that the DOM composition in soils with MPs addition was significantly changed relative to the ambient, in which tryptophan-like substances were decreased and humic-like substances were increased. Moreover, we find more apparent transformations of DOM composition in soils for longer treatment time, suggesting a long-lasting effect of MPs on DOM. The overall impact of MPs on DOM is more pronounced in lower latitudes, and nutrient availability and latitude-related climatic variables are associated with the influence degree of MPs input on soil DOM.

Comparative Toxicity of Vegan Red, E124, and E120 Food Dyes on Three Rapidly Proliferating Model Systems

The abuse of artificial food dyes and the evidence that they harm human health recently prompted a significant effort to introduce vegan substitutes prepared from fruits and vegetables. Not much information, however, has been collected on their possible effects on aquatic and terrestrial ecosystems once released as waste in surface waters. For this purpose, we analyzed the effects of a vegan red (VEG) preparation (concentration 1.2 g/L) on three rapidly proliferating models for terrestrial and aquatic ecosystem contamination. In particular, in vitro cells cultures (exposure for 24 h), Artemia salina nauplii and Cucumis sativus seedlings (exposure 5 days). A comparison was made with the effects exerted by the two dyes that vegan red is intended to replace: an animal dye, cochineal E120 and an artificial dye E124. The analyses of conventional endpoints, indicative of cell proliferation, differentiation, and growth rate, demonstrate that the three dyes affect development and that the vegan substitute is as unsafe as the E124 and E120. Vegan red in fact impairs cell growth in in vitro cells, delays naupliar hatching and early growth in Artemia, and reduces shoot/root biomass in Cucumis. Marked hyperplasia and hypertrophy of mesophyll are also observed in Cucumis leaves. Substitution in food and beverages, therefore, should be carefully reconsidered to avoid unnecessary environmental contamination.

Isotopic and trace element data of Tissint indicate a homogeneous strewn field, mobilization of Sr, REE, and Pb during shock metamorphism, and limits on the incorporation of martian surficial materials in impact melt glass

The Tissint strewn field has produced over 16 kg of material that has minimal terrestrial weathering and/or contamination. Tissint, along with 16 other incompatible trace element (ITE)-depleted shergottite specimens with igneous crystallization ages spanning 327–2403 Ma, were ejected together from Mars 1.1 m.y. ago. Despite the geochemical similarities of fragments from the Tissint strewn field, there are reported discrepancies in age determinations from different fragments that raise the possibility that the strewn field may be heterogenous. There are also questions about whether the shock ejection event incorporated martian soil components into impact glass, and the sources of radiogenic Sr and Pb that have been measured from leachate fractions in previous studies. An impact melt-rich fragment of Tissint was analyzed by LA-ICPMS for rare-earth element (REE) and highly siderophile element (HSE) concentrations and Pb isotopic compositions. Leachate and residues from 8 specimens representing separate individual fragments collected from the strewn field were analyzed for Rb-Sr. Unleached fractions of the 8 specimens were also analyzed for Sm-Nd and Lu-Hf.The measured REE and HSE concentrations of impact melt glass and associated sulfide measured by LA-ICPMS are consistent with bulk rock compositions of Tissint and show no evidence for incorporation of more ITE-enriched martian surface components. Measured Pb isotopic compositions confirm that the impact melt glass and associated sulfide contain no evidence for incorporation of more radiogenic materials than the Pb compositions inherited from the primary magma. In situ Pb isotopic data from sulfide likely represents the most robust method for constraining initial Pb isotopic compositions of shergottites whereas approaches that rely on leaching and digestion may not remove all mineral and/or crack surface contaminants.Rubidium-strontium analyses of the 8 Tissint specimens indicate that labile components hosting HCl-soluble Rb and Sr are not in isotopic equilibrium with the igneous assemblage and that the washed residues are in isotopic equilibrium with the igneous assemblage. The Sr isotopic compositions of the leachate are within the range of ‘more ITE-enriched’ depleted shergottites, perhaps indicating sources from the igneous pile on Mars. The radiogenic Sr component could represent crack and mineral surface coatings of volatilized materials derived from nearby depleted shergottite rock units during the impact ejection process but are not radiogenic enough to represent ITE-enriched crust or mantle components.The Lu-Hf isotopic data from the specimens indicate no evidence of contamination or element mobility, whereas the Rb-Sr and Sm-Nd isotopic systems show evidence for element mobility and potential mixing with an isotopic component not in equilibrium with the igneous phases. The calculated ages using data compiled from Brennecka et al. (2014), and Grosshans (2013) for Lu-Hf, Rb-Sr, and Sm-Nd are 571 ± 84 Ma, 590 ± 49 Ma and 559 ± 39 Ma, respectively. These data indicate that the specimens analyzed here are cogenetic and the Tissint strewn field appears to be homogeneous.

The Los Angeles martian diabase: Phosphate U-Th-Pb geochronology and mantle source constraints

In situ laser ablation inductively coupled mass spectrometry (LA ICP-MS) is used to determine the U-Th-Pb age of the phosphates ferromerrillite and apatite in the Los Angeles shergottitic meteorite. The initial 207Pb/206Pb was refined by analyzing K-rich diaplectic glass. LA ICP-MS mapping was used to document zones of elevated U and Th content and to establish textural controls on isotope ages. By critically assessing dispersion in the U-Th-Pb dataset due to Pb-diffusion in phosphates during high-temperature shock metamorphism, and as a result of subsequent terrestrial contamination, we obtain a best-estimate U-Pb age of 169 ± 5 Ma anchored at an initial 207Pb/206Pb of 0.98390 ± 0.00018. This is statistically indistinguishable from a joint-isochron age of 179 ± 6 with initial 208Pb/206Pb of 2.5151 ± 0.0028. These results complement previously determined Rb-Sr and Sm-Nd isotope ages and provide independent evidence for LA having crystallized as a medium-grained basic rock from a thick lava flow or high-level intrusion in the late Amazonian at ∼170 Ma. In the context of martian mantle evolution, the initial common-Pb values suggest that Los Angeles originated from a source (µ2 ∼ 3.2) that is similar to enriched members of the shergottite meteorite clan. The U-Th-Pb systematics of both ferromerrillite and apatite were locally affected by diffusive Pb-loss in thin U-enriched marginal domains and more profoundly in shock-induced melt pockets where temperatures briefly exceeded 2000 °C. The results reveal: (1) how precise U-Pb ages can be attained from phosphates; (2) the importance of microtextural contextualization of isotope data; (3) that the timescales of cooling from shock conditions were sufficient to promote local diffusive re-equilibration of Pb over 10 s of microns; and (4) that LA ICP-MS mapping can be used to locate domains with the highest U/Pb and Th/Pb, which increases precision on lower intercept ages and isochron regression lines.

Non‐protein amino acids identified in carbon‐rich Hayabusa particles

AbstractAmino acid abundances in acid‐hydrolyzed hot water extracts of gold foils containing five Category 3 (carbon‐rich) Hayabusa particles were studied using liquid chromatography with tandem fluorescence and accurate mass detection. Initial particle analyses using field emission scanning electron microscopy with energy‐dispersive X‐ray spectrometry indicated that the particles were composed mainly of carbon. Prior to amino acid analysis, infrared and Raman microspectroscopy showed some grains possessed primitive organic carbon. Although trace terrestrial contamination, namely l‐protein amino acids, was observed in all Hayabusa extracts, several terrestrially uncommon non‐protein amino acids were also identified. Some Hayabusa particles contained racemic (d≈l) mixtures of the non‐protein amino acids β‐aminoisobutyric acid (β‐AIB) and β‐amino‐n‐butyric acid (β‐ABA) at low abundances ranging from 0.09 to 0.31 nmol g−1. Larger abundances of the non‐protein amino acid β‐alanine (9.2 nmol g−1, ≈4.5 times greater than background levels) were measured in an extract of three Hayabusa particles. This β‐alanine abundance was ≈6 times higher than that measured in an extract of a CM2 Murchison grain processed in parallel. The comparatively high β‐alanine abundance is surprising as asteroid Itokawa is similar to amino acid‐poor LL ordinary chondrites. Elevated β‐alanine abundances and racemic β‐AIB and β‐ABA in Hayabusa grains suggested these compounds have non‐biological and plausibly non‐terrestrial origins. These results are the first evidence of plausibly extraterrestrial amino acids in asteroid material from a sample‐return mission and demonstrate the capabilities of the analytical protocols used to study asteroid Ryugu and Bennu samples returned by the JAXA Hayabusa2 and NASA OSIRIS‐REx missions, respectively.