Capturing the global signature of surface ocean acidification during the Palaeocene-Eocene Thermal Maximum.

Geologically abrupt carbon perturbations such as the Palaeocene-Eocene Thermal Maximum (PETM, approx. 56 Ma) are the closest geological points of comparison to current anthropogenic carbon emissions. Associated with the rapid carbon release during this event are profound environmental changes in the oceans including warming, deoxygenation and acidification. To evaluate the global extent of surface ocean acidification during the PETM, we present a compilation of new and published surface ocean carbonate chemistry and pH reconstructions from various palaeoceanographic settings. We use boron to calcium ratios (B/Ca) and boron isotopes (δ11B) in surface- and thermocline-dwelling planktonic foraminifera to reconstruct ocean carbonate chemistry and pH. Our records exhibit a B/Ca reduction of 30-40% and a δ11B decline of 1.0-1.2‰ coeval with the carbon isotope excursion. The tight coupling between boron proxies and carbon isotope records is consistent with the interpretation that oceanic absorption of the carbon released at the onset of the PETM resulted in widespread surface ocean acidification. The remarkable similarity among records from different ocean regions suggests that the degree of ocean carbonate change was globally near uniform. We attribute the global extent of surface ocean acidification to elevated atmospheric carbon dioxide levels during the main phase of the PETM.This article is part of a discussion meeting issue 'Hyperthermals: rapid and extreme global warming in our geological past'.

Fast isotopic separation of 10 B and 11 B boric acid by capillary zone electrophoresis.

Fast isotopic separation of 10 B and 11 B boric acid by CZE was demonstrated. The BGE contained 25 mM phenylalanine and 5 mM putrescine (рН 8.95). The running conditions were +25 kV at 20°C with indirect photometric detection at 210 nm. Baseline separation was achieved in less than 9 min. RSD of migration times and corrected peak areas were less than 0.5 and 3%, respectively (n = 5). Linearity was demonstrated in the range 0.2-2 mM for 11 B and 0.2-0.5 mM for 10 B.

The effect of roasting on boron isotope ratio in coffee beans: Implications for provenance studies of roasted coffee.

We determined δ11B values of green and roasted coffee beans from 20 locations worldwide and conducted laboratory experiments with the aim to investigate boron isotope fractionation during roasting. Authentic single origin roasted coffees were found to be isotopically lighter than their green bean counterparts, with an average difference of 1.5‰. This isotope fractionation can be explained as arising from partial dissociation of boric acid in capillary water of green beans, where 11B isotopes are preferentially partitioned into molecules of undissociated boric acid and are then volatised during roasting. However, boron isotope fractionation induced by roasting was significantly smaller than between-origin variations in δ11B values of green coffee beans that had the range of ∼54‰. This implies that δ11B isotopic composition of roasted coffee retains the geographical origin information within δ11B values of green beans when regional differences in boron isotopic composition of coffee are considered.

Effects of global and climate change on the freshwater-seawater interface movement in a Mediterranean karst aquifer of Mallorca Island.

Karst aquifers are globally prized freshwater sources, posing a significant preservation challenge. These aquifers typically exhibit dual or even triple porosities, encompassing matrix, fractures-fissures and conduits, rendering them highly responsive to variations in chemical characteristics and hydraulic head. In coastal regions, these aquifers often possess extensive subsurface conduit networks intricately linked to the rock matrix, facilitating groundwater discharge into the sea. Therefore, they display acute sensitivity to seawater intrusion, swiftly reacting to changes in precipitation and pumping regimes. This makes them exceptionally vulnerable to short-term meteorological fluctuations and long-term climate change. Their high heterogeneity leads to uneven penetration of the freshwater-seawater interface, causing rapid seawater intrusion inland over significant distances. The Mediterranean region, characterized by water deficit and water stress, faces strong impacts from climate change, featuring a warming atmospheric trend exceeding the global average, along with diminished rainfall exacerbating water scarcity. Increasing water demands for agriculture, urban development, and the growing tourism industry, because of global change, are worsening water stress. Our primary research objectives were analyzing the environmental consequences of global and climate change on seawater intrusion in Mediterranean coastal karst aquifers, with a focus on the role of the double-flow model, thus contributing to the understanding of the processes involved. To achieve this, we selected a study region on Mallorca Island in the western Mediterranean, where a karst aquifer system discharges into the sea. We employed various study methods, notably hydrochemical techniques and multi-isotopic analysis, encompassing the examination of 2H and 18O isotopes in water, 87Sr/86Sr ratio, Sr and B concentrations, and δ11B in water. A key finding is the rebound effect, wherein aquifers recontaminate due to solute molecular back-diffusion following cessation of extractions and the retreat of marine intrusion, providing insight into the impact of climate and global change on Mediterranean karst aquifers.

Process Intensification of Chemical Exchange Method for Boron Isotope Separation Using Micro-Channel Distillation Technology.

A micro-channel distillation device was used for the process intensification method to separate boron isotopes, 10B and 11B. Three-dimensional (3D) printing technology was introduced to manufacture the micro-channel device, which used the chemical exchange method with anisole as the donor to separate the boron isotopes. This device was tested in total reflux mode, and the height of an equivalent theoretical plate of the micro-channel distillation equipment was reduced to 1.56 cm. The accurate control of pressure and temperature, as well as the flow rate of the complex, were factors that affected separation ability. Thus, for process intensification, this micro-channel distillation device can be operated horizontally and connected in series into similar modules to effectively improve separation efficiency and reduce the size of the equipment.

Evolution of groundwater chemistry in coastal aquifers of the Jiangsu, east China: Insights from a multi-isotope (δ2H, δ18O, 87Sr/86Sr, and δ11B) approach.

Groundwater salinization is currently a very serious and challenging issue in many parts of the world. With an increasing demographic pressure and remarkable changes of water and land uses over the last decades, the multilayer coastal aquifer system of Jiangsu province, east China, was affected by increasing salinization. In this study, we investigate the groundwater salinization process and the salinity sources of the aquifer system in Nantong area (southern part of the Jiangsu coastal plain) using a multi-isotope (δ2H, δ18O, 87Sr/86Sr, and δ11B) approach. The results show that the TDS (total dissolved solids) values in most deep groundwater samples are generally lower than those of the shallow groundwater samples. The TDS of both shallow and deep groundwater increase from western Nantong (inland) to the eastern coastal region of the Yellow Sea. The chemical types transform from Ca-Mg-HCO3 or Mg-Ca-HCO3 to NaCl. The stable hydrogen and oxygen isotopes signatures of the groundwater samples indicate that local precipitation likely acts as the main recharge source of both the shallow and deep confined groundwater systems. The deep groundwater shows more depleted isotopes, suggesting recharging by the precipitation under a cold climate before the Holocene period. The shallow groundwater features heavier water isotopes, indicating recharging source from recent precipitation under a warm climate. The variations in δ11B and 87Sr/86Sr of groundwater samples can be explained by the changes of solute sources. In the inland region (western Nantong), shallow groundwater with higher TDS is mainly caused by evaporation-induced concentration, whereas in coastal areas, seawater intrusion exerts a major influence on the chemical composition of the shallow groundwater. Our results show that that seawater intrusion mainly occurs in eastern and southeastern Nantong area. We also find that hydraulic connection between shallow and deep groundwater is strengthened by continuous overexploitation, and deep groundwater is mixed with shallow groundwater at some points. The mixing between upper saline water and deep freshwater, together with water-rock interactions, likely explain the observed low salinity in deep groundwater in coastal areas. Overall, with growing observations of salty seawater intrusion in the estuary region of the Yangtze River, future efforts are needed to prevent further seawater intrusion as sea level rises and groundwater table declines. In this context, our findings provide key information for groundwater management in other coastal aquifers, east China.

A validated analytical procedure for boron isotope analysis in plants by MC-ICP-MS.

Boron (B) is an essential micronutrient for plant growth. Lack of valid methods for pretreatment and measurement of δ11B in plant restrict applications of it in the biosphere. Dry ashing, one step cation exchange and micro-sublimation were combined to separate and purify boron (B) in plant tissues. The low procedure blank, high B recovery and the accurate δ11B values of the plant reference materials demonstrate that this method is suitable and valid for B pretreatment and δ11B measurement in plant samples by MC-ICP-MS. Based on this method, the δ11B in different plants (Brassica napus, Chenopodium album L, moss, lichen, and Nostoc commune) was analyzed. For Brassica napus, δ11B increased gradually from root to leaf, and then decreased to rapeseed. For the same parts, the δ11B increased from the lower parts to the higher parts. This variation may be due to the B(OH)3 transporter of NIP6;1 and the incorporation of B into the cell. The reason for lower δ11B values in shell and rapeseed compared to those in leaves presumably is to the preferred transport of borate in the phloem. The largest δ11B fractionation between leaf and root in Brassica napus and Chenopodium album L was + 24.2‰ and + 26.6‰, respectively. The large variation and fractionation of δ11B within plants indicates that δ11B is a good tracer to study the B translocation mechanisms and metabolism within plants. The δ11B in Nostoc commune, lichen, and moss showed variations of -4.1‰ to + 21.5‰, - 9.4‰ to + 7.3‰, and - 18.3‰ to + 11. 9‰, respectively. In the same site, δ11B in different plants ranked Nostoc commune>moss>lichen and δ11B in mosses growing in different environment ranked soil>tree>rock. Rain and soil available B are the main B sources for these plants. The δ11B in Nostoc commune, lichen, and moss may be a useful tracer to study the atmospheric B input. In the future, plants culture experiments under certain environments and studies from molecular level are necessary to decipher the variation of δ11B and fractionation mechanisms within plants.

Quantification of spatial and seasonal variations in the proportional contribution of nitrate sources using a multi-isotope approach and Bayesian isotope mixing model.

Spatial and seasonal variations in nitrate contamination are a globally concern. While numerous studies have used δ15N-NO3 and δ18O-NO3 to elucidate the dominant sources of nitrate in groundwater, this approach has significant limitations due to the overlap of nitrate isotopic ranges and the occurrence of nitrate isotopic fractionation. This study quantitatively assessed the spatial and seasonal variations in the proportional contributions of nitrate sources from different land uses in the Tarom watershed in North-West Iran. To achieve this aim, orthogonal projection of the hydrochemical and isotopic dataset of the principal component analysis (PCA) as well as correlation coefficient matrix (Corr-PCA) were evaluated to reduce the dimensionality of the inter-correlated dataset. Next, a nitrate isotopic biplot accompanied with a Bayesian isotope mixing model (SIAR) were applied to specify the spatial and seasonal trends in the proportional contribution of three dominant sources of nitrate (fertilizers, animal manure and residential waste) in the watershed. Finally, in order to provide a sensitive framework for nitrate source appointment and overcome the associated limitations of dual nitrate isotope application, the integration of boron isotope (δ11B) and strontium isotopic ratio (87Sr/86Sr) was introduced. The results revealed that the mean contribution of residential sewage increased (17%-27.5%), while the mean contribution of fertilizers decreased (28.3%-19%), from late spring to early autumn. Also, fertilizer was the highest contributor (42.1% ±â€¯3.2) during late spring, especially in regions with more than 75% agricultural land. Meanwhile, the mean contribution of sewage was highest in early autumn (32.1% ±â€¯2.8) in the areas with more than 20% residential land. These results were confirmed by coupled application of δ11B and 87Sr/86Sr. This study provides a useful insight for environmental managers to verify groundwater pollution contributors and to better apply remedial solutions.

Determination of boron content and isotopic composition in gypsum by inductively coupled plasma optical emission spectroscopy and positive thermal ionization mass spectrometry using phase transformation.

As a stable isotope, boron plays an important role in hydrogeology, environmental geochemistry, ore deposit geochemistry and marine paleoclimatology. However, there is no report of boron isotopic composition in gypsum. This is mainly confined to complete dissolution of Gypsum by water or acid. In this study, gypsum was converted to calcium carbonate (CaCO3) with ammonium bicarbonate(NH4HCO3) by two steps at 50°C. In every step, the mass ratio of NH4HCO3/CaSO4·2H2O was twice, and conversion rate reached more than 98%. Converted CaCO3 was totally dissolved with hydrochloric acid (the dissolution rate was over 99%). In order to overcome the difficulties of the matrix interference and the detection limit of Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), we use Amberlite IRA 743 resin to purify and enrichment the boron at first, then eluting boron from the resin with 10mL 0.1mol/L hydrochloric acid at 75°C. The boron isotopic composition of natural gypsum samples was determined using positive thermal ionization mass spectrometry (P-TIMS). The boron isotopic composition of gypsum may be an excellent indicator for the formation environment.

Extraction and Separation of Boron in Anhydrite and Gypsum Minerals and Its Isotopic Measurement by Thermal Ionization Mass Spectrometry / 分析化学

The anhydrite and gypsum are the main sulfate minerals during evaporation of seawater or lake.They record the information about relative hydrogeology and the composition of mother liquor.Boron is diffluent element, and often occurs in all kinds of evaporites.Presently, the boron isotope has been applied widely in mineral deposits forming, geochemistry and palaeoenvironment.However, there is little research about characteristic of boron isotope in anhydrite and gypsum minerals, because of the low content of boron and micro-solubility in water and hydrochloric acid.This study developed a method of extracting and purifying boron in anhydrite and gypsum by phase transformation and ion-exchange.Firstly, the samples were mixed with ammonium hydrogen carbonate to transform the calcium sulfate to calcium carbonate.And diluted hydrochloric acid (1 mol/L) was added to resolve calcium carbonate.The percent conversion was about 85%in the first stage, and up to complete resolution by repeating this process.Secondly, boron specific ion-exchange resin ( Amberlite IRA 743 ) was used to gather the boron ions fully and further refined the samples with more than 1 μg of boron by anionic and cationic resin mixed by Ion Exchange Ⅱ and Dowex 50 W × 8.Finally, according to the modified method by He, the values of boron isotope were determined by TIMS.The boron content is analytically pure gypsum was 3.501 ± 0.128 μg/g ( n=12 , RSD=3.6%) and the average recovery was 100.47%.Besides, the δ11B value of analytically pure gypsum added with NIST SRM 951 was 17.98‰±0.21‰ (n=3, RSD=1.2%).This method has good repeatability and can meet the requirements of boron isotopic measurement of anhydrite and gypsum.