Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

Interrogation of Ecotoxic Elements Distribution in Slag and Precipitated Calcite through a Machine Learning‐Based Approach Aided by Mass Spectrometry

AbstractCO2 mineralization in slag has been widely investigated as a potential solution for offsetting steelmaking industry emissions. However, it can be associated with ecotoxic elements release (e.g., V and Cr). The presence of such elements in heterogenous slag at the micro‐scale remains difficult for analysis since microstructural features can be missed during microscopy data inspection, thereby presenting a challenge in understanding how ecotoxic elements exist in slag. Here, an unsupervised machine learning‐based technique is used to analyze slag's microstructural features. Energy Dispersive Spectroscopy (EDS) data are analyzed through Hierarchical Density‐Based Spatial Clustering of Applications with Noise (HDBSCAN) method. Results show that passive CO2 mineralization has occurred in situ in the studied samples, on the surface, and within their pores. Additionally, V and Cr regions with equivalent diameters < 42 µm can exist within slag, potentially making such elements prone to mobilization due to slag pulverization. Interrogation of the samples with Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA‐ICP‐MS) confirms the distribution of the elements obtained from the clustering algorithm and further demonstrates that up to 84 and 9 ppm of V and Cr are incorporated in the precipitated calcite, respectively. This implies that ecotoxic elements may be immobilized through calcite precipitation.

Slips, films, and material choice: Long-distance hydrothermal pigments on Middle Mississippian red ware

Using laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) and Raman spectroscopy, we investigate red pigment applied to ceramic vessels as a slip or film (pigment + liquid + binder mixture) in the midcontinental United States. We find that during the CE 1000–1200 period, potters at Cahokia and nearby sites in the American Bottom region of the Middle Mississippi Valley used pigments originating from hydrothermal deposits. The closest hydrothermal deposits are located over 50 km away in the Ozark Highlands and the pigments may have been collected from areas already exploited for other resources. Approaching slips or films as pigment + liquid + binder mixtures integrates ceramic raw materials research with pigment research and encourages us to consider a variety of pigment options, some of which require binders for use on ceramics.

Microdistribution and Mode of Rare Earth Element Occurrence in the Zhijin Rare Earth Element-Bearing Phosphate Deposit, Guizhou, China

Rare-earth elements (REEs) are often highly concentrated in sedimentary phosphate deposits, and the microdistribution characteristics and occurrence state of rare earth in these deposits play a crucial role in the overall development and utilization of mineral resources. This study aims to analyze the microdistribution of REEs in REE-bearing phosphate deposits in the Zhijin region of Guizhou at the microstructural level and investigate their occurrence modes. Specifically, rock and mineral identification, X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive X-ray spectroscopy (SEM-EDS), and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) were utilized to analyze the samples. The correlation between the distribution of REEs and phosphorus was examined. In addition, the microdistribution of REEs in specific mineral phases and the locations of their occurrence were investigated. The analysis revealed that no REEs existed independently in the deposit. Instead, the distribution of REEs was highly consistent and significantly positively correlated with that of phosphorus. In the microarea structure, REEs were predominantly found both in particles, such as bioclasts, sand debris, and agglomerates, and in phosphate cement, where the main mineral components were collophane and apatite. Conversely, the content of REEs in dolomitized sand debris edges, sparry dolomitic cement, and siliceous cement was considerably lower. Based on these findings, it is speculated that REEs primarily occur within the lattice defects of apatite or on the surface of collophanite. There is a notable contrast in the REE content between the unaltered sand debris at the periphery and the dolomitized sand debris, indicating that the dolomitization in the diagenetic stage resulted in a depletion of REE abundance in the ore. Obviously, the dominant gangue mineral, dolomite, does not serve as the primary host for REEs. Furthermore, the highest concentration of REEs was inside organisms. This finding suggests that the high content of REEs in biological soft tissue may remain under the influence of waves and tides, and REE-bearing apatite may be preferentially separated and fill the cavities of deceased organisms. The second highest content of REEs was found in the shells of organisms, indicating that small shelly organisms absorb phosphorus materials through their life activities to construct their shells, resulting in REE enrichment. Quantitative analysis through sequential extraction procedures displayed that most REEs were present in the residual state, with a smaller portion combined with organic matter. These results confirm that REEs in the Zhijin phosphate deposits primarily exist as isomorphic substitutions in the lattice defects of apatite, with a secondary occurrence as organic matter-bound REEs.

Age and fluid source constraints of the Haoyaoerhudong orogenic gold deposit, North China: Evidence from geochronology and noble gas isotopes

The Haoyaoerhudong gold deposit, located in the northwestern part of the North China craton (NCC), has produced over 120 metric tonnes (t) of gold since 2007. It has a total reserve of > 240 t at average gold grade of 0.62 g/t, making it one of the largest open pit gold mines in China. The steeply dipping, large-tonnage, low-grade, vein- or veinlet-type gold orebodies are hosted in strongly-deformed Mesoproterozoic carbonaceous schist of the Bayan Obo Group. The laminated/boudinaged veins/veinlets in the sinistral ductile–brittle shear zones are dominated by quartz, biotite, gold-bearing löllingite, pyrrhotite, (arseno)pyrite, with minor native gold, titanite and xenotime. In this paper, we present new in situ U–Pb geochronological data on magmatic zircon from the pre-ore dikes, on metamorphic and hydrothermal xenotime, and on hydrothermal titanite from the hydrothermally altered carbonaceous schist and auriferous quartz–sulfides veins/veinlets, as well as He-Ar isotopic analysis on gold-bearing (arseno)pyrite in the syn-ore stage. The metamorphic xenotime U–Pb age of 426 ± 6.0 Ma (2σ) records a regional metamorphic event, possibly related to the accretion of the Bainaimiao arc onto the NCC. Two pre-ore andesitic dikes yielded similar emplacement ages at ∼ 278 Ma constrained by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U–Pb zircon data. Hydrothermal xenotime grains from the altered carbonaceous schist and auriferous quartz–sulfides veins yielded U–Pb ages of 256.0 ± 4.1 Ma (2σ) and 254.4 ± 2.1 Ma (2σ), respectively, overlapping with that of the hydrothermal titanite at 255.4 ± 0.8 Ma (2σ) from the laminated quartz–sulfides veinlets. This indicates that the gold mineralization occurred at ca. 255 Ma. The ∼ 255 Ma gold mineralization age is much younger than the previously reported Early–Middle Permian regional magmatic activity (ca. 291 Ma to 268 Ma), and may be associated with the regional sinistral strike-slip event in the late orogenic cycle related to the collision between the Siberian craton and the NCC. The 3He/4He (R/Ra) and 40Ar/36Ar values of the gold-bearing (arseno)pyrite are 0.04 to 0.09 (average = 0.07) and 375.8 to 2023 (average = 1045), which reveal the ore-forming fluids dominantly originated from the crustal rocks, with limited involvement from the mantle. Collectively, our new geochronological data, noble gas isotopic analyses, and geological evidence support a typical orogenic gold deposit model at Haoyaoerhudong.

Coupled Microstructural EBSD and LA-ICP-MS Trace Element Mapping of Pyrite Constrains the Deformation History of Breccia-Hosted IOCG Ore Systems

Electron backscatter diffraction (EBSD) methods are used to investigate the presence of microstructures in pyrite from the giant breccia-hosted Olympic Dam iron–oxide copper gold (IOCG) deposit, South Australia. Results include the first evidence for ductile deformation in pyrite from a brecciated deposit. Two stages of ductile behavior are observed, although extensive replacement and recrystallization driven by coupled dissolution–reprecipitation reaction have prevented widespread preservation of the earlier event. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) element maps of pyrite confirm that many pyrite grains display compositional zoning with respect to As, Co, and Ni, but that the zoning is often irregular, patchy, or otherwise disrupted and are readily correlated with observed microstructures. The formation of ductile microstructures in pyrite requires temperatures above ~260 °C, which could potentially be related to heat from radioactive decay and fault displacements during tectonothermal events. Coupling EBSD methods with LA-ICP-MS element mapping allows a comprehensive characterization of pyrite textures and microstructures that are otherwise invisible to conventional reflected light or BSE imaging. Beyond providing new insights into ore genesis and superimposed events, the two techniques enable a detailed understanding of the grain-scale distribution of minor elements. Such information is pivotal for efforts intended to develop new ways to recover value components (precious and critical metals), as well as remove deleterious components of the ore using low-energy, low-waste ore processing methods.

Quantified retrospective biomonitoring of fetal and infant elemental exposure using LA-ICP-MS analysis of deciduous dentin in three contrasting human cohorts.

Spatial elemental analysis of deciduous tooth dentin combined with odontochronological estimates can provide an early life (in utero to ~2 years of age) history of inorganic element exposure and status. To demonstrate the importance of data normalization to a certified reference material to enable between-study comparisons, using populations with assumed contrasting elemental exposures. We used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of dentin to derive a history of elemental composition from three distinct cohort studies: a present day rural cohort, (the New Hampshire Birth Cohort Study (NHBCS; N = 154)), an historical cohort from an urban area (1958-1970), (the St. Louis Baby Tooth Study (SLBT; N = 78)), and a present-day Nigerian cohort established to study maternal HIV transmission (Dental caries and its association with Oral Microbiomes and HIV in young children-Nigeria (DOMHaIN; N = 31)). We report Li, Al, Mn, Cu, Zn, Sr, Ba and Pb concentrations (µg/g) and qualitatively examine As, Cd and Hg across all three cohorts. Rates of detection were highest, both overall and for each cohort individually, for Zn, Sr, Ba and Li. Zinc was detected in 100% of samples and was stably present in teeth at a concentration range of 64 - 86 µg/g. Mercury, As and Cd detection rates were the lowest, and had high variability within individual ablated spots. We found the highest concentrations of Pb in the pre- and postnatal dentin of the SLBT cohort, consistent with the prevalent use of Pb as an additive to gasoline prior to 1975. The characteristic decline in Mn after the second trimester was observed in all cohorts. Spatially resolved elemental analysis of deciduous teeth combined with methods for estimating crown formation times can be used to reconstruct an early-life history of elemental exposure inaccessible via other biomarkers. Quantification of data into absolute values using an external standard reference material has not been conducted since 2012, preventing comparison between studies, a common and highly informative component of epidemiology. We demonstrate, with three contrasting populations, that absolute quantification produces data with the lowest variability, compares well with available data and recommends that future tooth biomarker studies report data in this way.

Copper skarn mineralization related to reduced monzodioritic magma at the Huanren deposit, northeastern China

Most known copper (Cu) skarns are associated with oxidized intrusions. In this contribution, we report a Cu skarn associated with a reduced monzodioritic intrusion at Huanren, northeastern China, which contains 0.41 Mt of Cu accompanied by economic concentrations of Zn, Pb, Fe, Mo, and Ag. Copper-polymetallic mineralization in the Huanren deposit is concentrated in skarns located between the contacts of the monzodiorite (SiO2 = 52−55 wt%) and the Cambrian carbonate rocks, with minor molybdenite-bearing veinlets/veins and dissimilated chalcopyrite mineralization hosted within the monzodiorite. Laser ablation−inductively coupled plasma−mass spectrometry (LA-ICP-MS) U-Pb zircon geochronology indicates the monzodiorite crystallized at 125.4 ± 0.6 Ma (2σ). Isotope dilution (ID)-ICP-MS Re-Os molybdenite geochronology indicates mineralization at Huanren occurred at 125.3 ± 0.8 Ma (2σ). Whole-rock major- and trace-element and zircon Hf isotopic compositions suggest enriched (subduction metasomatized) lithospheric mantle−derived sources for the parental magma of the monzodiorite without significant crustal assimilation. Zircon trace-element and magmatic apatite major-element compositions indicate the reduced nature of the monzodiorite, as evidenced by low magmatic oxygen fugacity (fayalite-magnetite-quartz [FMQ] buffer = −1.09 ± 0.19) and negligible apatite SO3 contents (<0.05 wt%). A reduced magmatic-hydrothermal system at Huanren is also supported by the predominance of magmatic ilmenite over magnetite in the monzodiorite and by the presence of pyrrhotite and the absence of anhydrite and hematite in the ore. Chalcopyrite from the Huanren deposit has an average δ34S value of 4.34‰ ± 0.88‰ (1σ), which is clearly higher than values from most porphyry-skarn Cu ± Mo ± Au deposits. Accordingly, we suggest that interaction between (1) external oxidized fluids equilibrated with evaporites and (2) reduced Cl-bearing magmas and related exsolved fluids may have played a critical role in the formation of the Huanren Cu skarn by increasing the ability of fluids to scavenge Cu from the reduced magma and subsequently precipitate Cu in the carbonate rocks. This study defines a new type of Cu skarn and thereby opens new potential for Cu skarn exploration proximal to intrusive units previously deemed too reduced to be Cu fertile, especially in non-arc settings. Moreover, we conclude that the availability of Cl and S in magmatic-hydrothermal systems may be as critical as fO2 in facilitating the actual ore-forming event in Cu skarn systems.

Mineralogy and Geochemistry of the Mupane and Shashe Gold Deposits of the Tati Greenstone Belt (NE Botswana): Implications for Mineral Deposit Models and Exploration

Abstract The Archean Tati greenstone belt is located at the southwestern margin of the Zimbabwe craton (northeast Botswana) and hosts numerous Cu-Ni ± platinum group element (PGE) and Au ± Ag occurrences and deposits. Gold occurrences/deposits are poorly studied, and key questions pertaining to their genesis remain unclear, including the mode of occurrence(s) of gold, the relative timing of gold introduction with respect to the evolution of the greenstone belt, the number of gold mineralization events, the alteration patterns, and the relationships between each alteration pattern and gold mineralization. A detailed study that includes sulfide and gold grain chemistry using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and electron probe microanalysis (EPMA), respectively, and X-ray diffraction (XRD) of mineralized rock samples of three Tati greenstone belt gold deposits was carried out to constrain the genesis of gold mineralization and formulate exploration guidelines in the Tati greenstone belt. Gold in the Tati greenstone belt is the result of multiple events, is mainly associated with arsenopyrite, pyrite, and sphalerite, and occurs as (1) microinclusions within sulfides, (2) intergrowth with sulfides, (3) minute particles (<2–10 μm) within the silicate matrix, (4) microfractures and microvug infills, and (5) lattice-bound and sulfide-hosted refractory gold. The first gold event (as electrum) is premetamorphic and associated with sphalerite-quartz veins. The second stage is a postmetamorphic high-grade gold event that is accompanied by extensive carbonatization and propylitization of host rocks. The third stage of gold mineralization is marked by the dissolution of gold in the early formed stages 1 to 2 and subsequent reprecipitation within cracks, fractures, and vugs. Auriferous pyrite composition suggests that Au-bearing mineralizing fluids are predominantly of magmatic origin and that their physicochemical compositions changed during the mineralization process, as supported by chemically zoned Au-bearing arsenopyrite, various alteration types containing gold, and variation in gold fineness across the several gold deposits in the Tati greenstone belt. Gold deposition in the Tati greenstone belt mainly occurred through sulfidation, as indicated by the closest spatial association between gold and Fe-bearing sulfides and ferromagnesian silicates. Gold in the Tati greenstone belt is closely correlated with As, Sb, Pb, Bi, Ni, Hg, Tl, Cd, In, Mo, W, Zn, and Te and moderately to weakly associated with Sn, Se, Cr, Co, Ge, Cd, Mn, V, Ga, and Ag. The correlation between Au and fluid mobile elements, i.e., Te, Sb, Se, As, Hg, and Bi, can be used as a vectoring tool during the exploration of gold within the Tati greenstone belt, as these elements likely form halos that are much broader than the primary footprint of gold mineralization.

Development of matrix-specific standards for LA-ICP-MS zinc analysis in sand flathead (Platycephalus bassensis)

The use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to analyse soft tissues is limited because of the lack of suitable certified reference materials resulting in difficulties with calibration. In this study, several laboratory-prepared thin agarose sections were tested as matrix-specific standards. Our results showed 1 mm thin agarose sections were suitable as calibration standards for LA-ICP-MS Zn analyses in fish muscle, especially when the signal intensity of 66Zn was normalised to 13C. The thin agarose standard sections were used for LA-ICP-MS Zn analyses in the muscle of melanised and non-melanised sand flathead collected from a polluted estuary and assigned with different melanisation scores. Zn levels in melanised regions of fish muscle were determined to be significantly higher than non-melanised regions across all melanisation scores, though Zn levels in the melanised regions of muscle were not significantly different between sand flathead with different melanisation scores. In non-melanised regions of muscle from fish with melanisation and fish unaffected by melanisation, Zn levels were around baseline levels. Overall, this study has successfully developed matrix-specific standards for LA-ICP-MS analysis of soft tissues, thus allowing broader application of this analytical technique in future environmental pollution studies.

Modeling apparent Pb loss in zircon U–Pb geochronology

Abstract. The loss of radiogenic Pb from zircon is known to be a major factor that can cause inaccuracy in the U–Pb geochronological system; hence, there is a need to better characterize the distribution of Pb loss in natural samples. Treatment of zircon by chemical abrasion (CA) has become standard practice in isotope dilution–thermal ionization mass spectrometry (ID-TIMS), but CA is much less commonly employed prior to in situ analysis via laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) or secondary ionization mass spectrometry (SIMS). Differentiating the effects of low levels of Pb loss in Phanerozoic zircon with relatively low-precision in situ U–Pb dates, where the degree of Pb loss is insufficient to cause discernible discordance, is challenging. We show that U–Pb isotopic ratios that have been perturbed by Pb loss may be modeled by convolving a Gaussian distribution that represents random variations from the true isotopic value stemming from analytical uncertainty with a distribution that characterizes Pb loss. We apply this mathematical framework to model the distribution of apparent Pb loss in 10 igneous samples that have both non-CA LA-ICP-MS or SIMS U–Pb dates and an estimate of the crystallization age, either through CA U–Pb or 40Ar/39Ar geochronology. All but one sample showed negative age offsets that were unlikely to have been drawn from an unperturbed U–Pb date distribution. Modeling apparent Pb loss using the logit–normal distribution produced good fits with all 10 samples and showed two contrasting patterns in apparent Pb loss; samples where most zircon U–Pb dates undergo a bulk shift and samples where most zircon U–Pb dates exhibited a low age offset but fewer dates had more significant offset. Our modeling framework allows comparison of relative degrees of apparent Pb loss between samples of different age, with the first and second Wasserstein distances providing useful estimates of the total magnitude of apparent Pb loss. Given that the large majority of in situ U–Pb dates are acquired without the CA treatment, this study highlights a pressing need for improved characterization of apparent Pb-loss distributions in natural samples to aid in interpreting non-CA in situ U–Pb data and to guide future data collection strategies.

Insights into Caribbean tectonics from a detrital zircon U-Pb provenance study of siliciclastic strata in western and central Cuba

The tectonic affinity and origins of the Jurassic, siliciclastic San Cayetano and Constancia formations exposed in western and central Cuba in the Caribbean region remain debated. The scarcity of modern geochronologic studies on these Cuban units hampers both sedimentary provenance and palinspastic reconstructions, resulting in Caribbean models that tend to oversimplify the formation of Cuba and correlate the Jurassic strata to various regions such as North America, South America, the Yucatán margin, or the conceptual Caribeana domain. Using laser ablation−inductively coupled plasma−mass spectrometry (LA-ICP-MS), we conducted a detailed detrital zircon (DZ) U-Pb provenance study of these Cuban siliciclastic strata that provides critical insights into understanding the formation of Cuba during the Early Jurassic rifting stages of Pangea. Results from 19 San Cayetano Formation samples show a dominant Oaxaquia (ca. 1 Ga) and Chiapas batholith (ca. 250 Ma) signature, while six Constancia samples display variable ca. 1 Ga and ca. 250 Ma grains. The Lower Cretaceous Polier Formation and the Paleocene Moncada Formation also display the same ca. 1 Ga and ca. 250 Ma signatures. After comparing these Cuban data with data from other regional DZ studies, we propose that that the San Cayetano and Constancia formations are correlative to the Todos Santos Formation located in the southwestern Yucatán region of Mexico. These Cuban units were predominantly deposited adjacent to the Chiapas batholith during the Early Jurassic in northwest−southeast-trending basins created by Pangean rifting. They were eventually sheared during eastward migration of the Caribbean plate and transported northward until they collided with the North American continent in the Paleogene. This DZ study provides new constraints on the tectonic provenance of western and central Cuba and improves plate tectonic reconstructions of the Caribbean.

Characteristics and evolution of quartz-calcite-sulfide veins in the Nazca-Ocoña belt, Peru

The Nazca-Ocoña metallogenic belt in southern Peru host about 70 recognized Au-Ag and base metal (Pb-Cu-Zn) deposits such as Orión, Caravelí, Ishihuica, Calpa, Arirahua, Mollehuaca, and San Juan de Chorunga. These deposits are spatially associated with Cretaceous intrusive rocks of the coastal Batholith in a zone that extends more than 350 km along the Central to Southern part of Peru. Gold and silver are structurally controlled in mineralized NW-SE, N-S and W-E-trending fault-fill veins that are less than one-meter wide, crosscutting granodiorite and diorite bodies. The origin of the veins is still debated, and they may be classified as intrusion-related gold deposits (IRGD), orogenic or mesothermal deposits. In this study, we focus on two representative deposits in the Nazca-Ocoña metallogenic belt: Mollehuaca and San Juan de Chorunga. At both sites, the mineralization is composed of quartz-calcite sulfide veins hosted in Cretaceous Coastal Batholith intrusions. Petrographic and chemical analyses on pyrite were performed with field-emission scanning electron microscopy (FE-SEM), electron microprobe analysis (EMPA), nano-scale secondary ion mass spectrometry (NanoSIMS), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).Native gold and Au-rich silver are disseminated throughout the veins as micro to sub-micron inclusions in pyrite and chalcopyrite, and in pyrite as cavity and fracture fill. The are three pyrite generations and these have complex internal zonation and are host to precious (Au, Ag) and base metals (Co, Ni, Cu) metals, and also metalloids (As, Sb) as lattice-bound impurities and micron inclusions. The San Juan de Chorunga pyrite has δ34S values ranging from 0.4 to 1.4 ‰, and the Mollehuaca pyrite δ34S from 5.8 to 7.4 ‰. In both San Juan de Chorunga and Mollehuaca, the highest Au concentrations occur in pyrite zones with the heaviest δ34S values. Fluid inclusion petrography of these veins shows recrystallized, wispy quartz with implosion and explosion fluid inclusion textures, indicative of pressure variations during quartz vein formation. The presence of CO2 in these inclusions requires mid-crustal pressure conditions. However, the main stage of gold mineralization occurs with carbonate, chlorite, and euhedral quartz crystals lacking post-entrapment recrystallization textures or CO2. Our observations suggest that most of the gold in these veins formed in association with a shallower hydrothermal event, potentially in association with the emplacement of batholiths and shallower intrusions in the Late Cretaceous.

Geochemical Behavior of Shallow Buried Nodules from Clarion–Clipperton Fracture Zone in the East Pacific: A LA-ICP-MS Mapping Analysis Perspective

The Clarion–Clipperton Fracture Zone of the east Pacific contains numerous shallow buried nodules that are in direct contact with pore water in sediment, providing a direct reflection of the interaction between nodules and sediment. However, research on the geochemical behavior of these shallow-buried nodules is limited. This study used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD) to compare mineral and element distribution in shallow buried nodules with surface nodules. The shallow buried nodules are products of nodules entering the burial stage. In comparison to surface nodules, shallowly buried nodules develop a fourth oxidized-suboxic diagenetic growth layer after entering the burial stage, in addition to the three main growth inner layers (L1, L2, L3). We suggest that L4 is not influenced by the bottom water source and that the presence of todorokite and the high flux of Mn2+ in the sediment pore water compete with other metal elements to enter the lattice of manganate, resulting in significantly higher Mn, W, and Li contents in L4 compared to L2. However, the content of Ni, Mg, and other hydrogenetic elements is much lower in L4 compared to L2. We suggest that the instantaneous change in surface primary productivity results in a sudden shift in the redox environment of the upper sediment layer. This reaction leads to the reduction of solid-phase Mn, providing growth opportunities for the buried nodules. Simultaneously, this may also be the reason why the growth layer of the nodules is jointly controlled by the sedimentary processes of hydrogenetic, oxic diagenetic, and suboxic diagenetic processes.

Copper on the Mississippi coast: Assessing provenance of a copper bead at the Claiborne site (22HA501) through LA-ICP-MS compositional analysis

The Claiborne site (22HA501) is located at the mouth of the Pearl River in southern Mississippi and was occupied sometime between 3990-3340 BP. In this we article, we source a copper bead from Claiborne using employed laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) compositional analysis to assess the provenance of the copper bead to understand the extent, direction, and intensity of trade networks integrated into this site and its connection to both Poverty Point and other copper-holding Archaic-era sites in the region. Specifically, we attempt to determine whether the Claiborne copper object originated from the Great Lakes region, or the Appalachian Mountains/Canadian Maritimes. The compositional results show a significant elemental relationship to copper from the Great Lakes region.

Characteristics and origin of crystalline dolomite: A case from Paleogene lacustrine fine-grained rocks in Jiyang depression, Bohai Bay Basin, China

Crystalline dolomite is a common carbonate mineral in lacustrine fine-grained rocks, but it has a confusing origin that has been a focus of much debate in recent years. In our research, the fine-grained rocks rich in crystalline dolomite were sampled from the upper fourth member (UMbr 4) and lower third member (LMbr 3) of the Shahejie Formation in the Jiyang Depression, and analyzed by a variety of analytical techniques, including field emission scanning electron microscopy (FESEM), cathodoluminescence (CL), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), micro-area carbon, oxygen, strontium isotopes and electron probe analyses. The results show: ①The crystalline dolomites in the lacustrine fine-grained rocks are primarily composed of ferroan-poor dolomite (FeO < 1%), type I ferroan dolomite (FeO ≈ 5%) and type II ferroan dolomite (FeO ≈ 16%); ②The δ18O of ferroan-poor dolomites in mudstone is between −0.89 and 0.32‰, the precipitation temperature is less than 60 °C, and their formation is related to the microbial action during the early diagenetic stage A, while the ferroan-poor dolomites in dolostone are primarily formed by the recrystallization of micritic dolomite; ③The δ18O of type I ferroan dolomites ranges from −3.74 to −3.89‰, the precipitation temperature ranges from 68.4 to 69.4 °C, and they are primarily formed by the microbial action and clay mineral transformation during the early diagenetic stage B; ④The δ18O of type II ferroan dolomites is between −7.78 and −8.33‰, the precipitation temperature is more than 90 °C, and their formation is related to the dissolution of early carbonate and clay mineral transformation during the middle diagenetic stage; ⑤The origin mechanism of crystalline dolomite indicates the diagenetic evolution of fine-grained rocks and the migration path and storage of shale oil.

Whole-Rock Geochemistry and Mica Compositions in Lijiagou Pegmatite Spodumene Deposit, Western Sichuan, China

The Lijiagou pegmatite spodumene deposit, located in the middle of the Songpan–Garze Fold Belt and southeast of the Ke’eryin ore field, is a newly discovered super-large deposit. In order to reveal the metallogenic tectonic environment and evolution process of pegmatite, based on the study of the geological characteristics of pegmatite, we carried out a whole-rock geochemical analysis of Ke’eryin two-mica granite and Lijiagou pegmatite and carried out a detailed electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analysis of mica minerals in each zonal pegmatite. The results show that the Ke’eryin two-mica granite is mainly formed in the transition period from syn-collision to post-collision. After the end of the continental collision, the crust is squeezed and thickened in the post-collision extensional transition tectonic environment. Mica from the microcline pegmatite zone (MP) to the albite spodumene pegmatite zone (ASP) in pegmatite show different compositions and structural characteristics, with the evolution trend in the direction from muscovite to Li-bearing mica. The type of mica from MP to AP is mainly muscovite, and Li-bearing mica appears in ASP, which is secondary and metasomatic at the edge of primary muscovite. From MP to ASP, there was a negative correlation between Nb/Ta, K/Rb and the Li, Rb, and Cs contents of mica, while the contents of Li, Rb, Cs, and F in the Li-bearing mica of ASP increased sharply. This evidence illustrates that the favorable tectonic environment contributed to the formation of the Lijiagou pegmatitic spodumene deposit. Lijiagou pegmatite experienced the magmatic–hydrothermal evolution process and has a high degree of differentiation and evolution from MP to ASP, which gradually increased. Combined with the change in mica type, it is considered that ASP formed from the stage of magmatic transition to hydrothermal and was a hydrothermal environment, and Li, Rb, and Cs mainly began to enrich at the stage of magmatic–hydrothermal transition.

Multiple growth of zirconolite in marble (Mogok metamorphic belt, Myanmar): evidence for episodes of fluid metasomatism and Zr–Ti–U mineralization in metacarbonate systems

Abstract. Fluid infiltration into (meta-)carbonate rocks is an important petrologic process that induces metamorphic decarbonation and potential mineralization of metals or nonmetals. The determination of the infiltration time and the compositional features of reactive fluids is essential to understand the mechanism and process of fluid–rock interactions. Zirconolite (ideal formula: CaZrTi2O7) is an important U-bearing accessory mineral that can develop in metasomatized metacarbonate rocks. In this study, we investigate the occurrence, texture, composition, and chronology of various types of zirconolite from fluid-infiltrated reaction zones in dolomite marbles from the Mogok metamorphic belt, Myanmar. Three types of zirconolite are recognized: (1) the first type (Zrl-I) coexists with metasomatic silicate and oxide minerals (forsterite, spinel, phlogopite) and has a homogeneous composition with high contents of UO2 (21.37 wt %–22.82 wt %) and ThO2 (0.84 wt %–1.99 wt %). (2) The second type (Zrl-II) has textural characteristics similar to those of Zrl-I. However, Zrl-II shows a core–rim zonation with a slightly higher UO2 content in the rims (average of 23.5 ± 0.4 wt % (n=8)) than the cores (average of 22.1 ± 0.3 wt % (n=8)). (3) The third type (Zrl-III) typically occurs as coronas around baddeleyite and coexists with polycrystalline quartz. Zrl-III has obviously lower contents of UO2 (0.88 wt %–5.3 wt %) than those of Zrl-I and Zrl-II. All types of zirconolite have relatively low rare earth element (REE) contents (&lt; 480 µg g−1 for ΣREE). Microtextures and compositions of the three zirconolite types, in combination with in situ zirconolite U–Pb dating using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), reveal episodic fluid infiltration and element mobilization in the dolomite marbles. The first-stage infiltration occurred at ∼ 35 Ma, leading to the formation of Mg-rich silicates and oxides and accessory minerals (Zrl-I, baddeleyite, and geikielite). The reactive fluid was characterized by high contents of Zr, Ti, U, and Th. After that, some Zrl-I grains underwent a local fluid-assisted dissolution–precipitation process, which produced a core–rim zonation (i.e., the Zrl-II type). The final stage of fluid infiltration, recorded by the growth of Zrl-III after baddeleyite, took place at ∼ 19 Ma. The infiltrating fluid of this stage had relatively lower U contents and higher SiO2 activities than the first-stage infiltrating fluid. This study illustrates that zirconolite is a powerful mineral that can record repeated episodes (ranging from 35 to 19 Ma) of fluid influx, metasomatic reactions, and Zr–Ti–U mineralization in (meta-)carbonates. This mineral not only provides key information about the timing of fluid flow but also documents the chemical variation in reactive fluids. Thus, zirconolite is expected to play a more important role in characterizing the fluid–carbonate interaction, orogenic CO2 release, and the transfer and deposition of rare metals.

An exploratory study of “large‐n” detrital zircon geochronology of the Book Cliffs, UT via rapid (3 s/analysis) U–Pb dating

AbstractDetrital zircon (DZ) U–Pb geochronology has improved the way geologists approach questions of sediment provenance and stratigraphic age. However, there is debate about what constitutes an appropriate sample size (i.e., the number of dates in a DZ sample, n), which depends on project objectives, sample complexity, and, critically, analytical budget. Additionally, there is ongoing concern about bias introduced by zircon grain size. We tested a recently developed rapid (3 s/analysis) data acquisition method by multicollector laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) that incorporates an automated selection routine and calculates two‐dimensional grain geometry from polished sample surfaces. Eleven samples were analysed from below and above the Late Cretaceous (Campanian) basal Castlegate unconformity of the Book Cliffs, Utah, in a down‐depositional‐dip transect including Price, Horse, Tusher, and Thompson canyons. 12,448 new concordant dates were generated during two measurement sessions. Results are consistent with recent studies suggesting there is no major provenance change and little time (1–2 Myr) represented across the unconformity. Grain size and sample size both exert a strong control on sample dissimilarity. Age distributions constructed from subsamples of large grains are systematically less similar to whole samples; age distributions composed of small grains are overall more similar to whole samples. As such, North American sediment sources that produce large grains such as the Grenville and Yavapi‐Mazatzal belts can bias age distributions if only large grains are analysed. A sample size of n = 100 is inadequate for characterizing age distributions as complex as those of the Book Cliffs, whereas a sample size of n = 300 provides good characterization. Sample size of n ≈ 1000 or more is unnecessary unless project objectives include scanning for subordinate age groups, such as when identifying the youngest grains for calculating a maximum depositional age (MDA). Dates used in MDA calculations acquired with rapid acquisition are best re‐analysed with longer LA‐ICP‐MS acquisition methods or isotope dilution thermal ionization mass spectrometry for increased accuracy and precision. We include new MATLAB code and open‐source software programs, DZpick and DZmda, for automated spot picking and calculating MDAs.

Imaging of Subcellular Distribution of Platinum in Single Cells Using Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

Laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a well-established and sensitive analytical technique, which provides high-resolution imaging of endogenous elements, element tagged-markers, metal-containing nanoparticles, and metallodrugs within cells. Here we describe a protocol for imaging the subcellular distribution of platinum within A549 cells, following their incubation with the platinum-based anticancer agent, Oxaliplatin. We outline the essential steps in sample preparation and instrumental setup and discuss how the current generation of low-dispersion instruments facilitates new approaches to data acquisition and image processing. The protocol described herein can be easily adapted for other cell lines and metal-containing labeling agents.

Gadolinium Presence in Rat Skin: Assessment of Histopathologic Changes Associated with Small Fiber Neuropathy.

Background The presence of gadolinium traces in the skin after administration of gadolinium-based contrast agents (GBCAs) raised safety concerns regarding a potential association with small fiber neuropathy (SFN). Purpose To investigate signs of SFN in rat foot pads by quantification of the intraepidermal nerve fiber density (IENFD) after multiple GBCA administrations and to evaluate gadolinium concentration, chemical species, and clearance. Materials and Methods Fifty rats received eight intravenous injections of either gadodiamide, gadobutrol, gadoterate, gadoteridol (8 × 0.6 mmol per kilogram of body weight), or saline (1.2 mL per kilogram of body weight), within 2 weeks and were sacrificed 5 days or 5 weeks after the last injection. IENFD was determined with protein gene product (PGP) 9.5 immunofluorescent staining and blinded and automated image analysis. The gadolinium and GBCA concentrations were measured with inductively coupled plasma mass spectrometry (ICP-MS), laser ablation ICP-MS, and matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI). P values were calculated using linear contrasts of model analysis. Results The IENFD (measured as geometric mean [SD] and in number of nerve fibers per millimeter of epidermis) was not significantly altered after 5 days (saline, 8.4 [1.1]; gadobutrol, 9.7 [1.2]; gadoterate, 9.2 [1.2]; gadoteridol, 9.9 [1.3]; gadodiamide, 10.5 [1.2]) or 5 weeks (saline, 19.7 [1.4]; gadobutrol, 16.4 [1.6]; gadoterate, 14.3 [1.6]; gadoteridol, 22.2 [1.8]; gadodiamide, 17.9 [1.4]). Gadolinium skin concentrations were highest for gadodiamide after 5 days (16.0 nmol/g [1.1]) and 5 weeks (10.6 nmol/g [1.2], -33%). Macrocyclic agents were lower at 5 days (gadoteridol, 2.6 nmol/g [1.2]; gadobutrol, 2.7 nmol/g [1.1]; and gadoterate, 2.3 nmol/g [1.2]) and efficiently cleared after 5 weeks (gadoteridol, -95%; gadobutrol and gadoterate, -96%). The distribution of gadolinium and IENF did not visually overlap. For macrocyclic agents, gadolinium was found in sweat glands and confirmed to be intact chelate. Conclusion There were no signs of SFN in rat foot pads using multiple dosing regimens at two time points after administration of GBCAs. Macrocyclic GBCAs exhibited lower levels of gadolinium in the skin and were effectively eliminated within 5 weeks compared with linear gadodiamide, and intact macrocyclic GBCA was detected in sweat glands. © RSNA, 2024 Supplemental material is available for this article. See also the editorial by Clement in this issue.