High Cl Research Articles

Identifying failure factors due to corrosion erosion on pressured steam pipe elbow in geothermal power plant

This paper presents the findings of a corrosion erosion failure analysis of elbow pipe materials used to flow high-pressure water from underground. The failed elbow pipe material was above the wellhead forming a straight line in the longitudinal direction with a pipe length of 6200 feet below the ground surface. The working fluid in the elbow pipe was 25 % steam and 75 % water, flowing in the elbow pipe with a media flow rate of 180 tons per hour, a pressure of 22 bar, and a temperature of 220 °C. Elbow tubes were made of low carbon steel with Standard ASTM A234 having an outer diameter of 304.8 mm and a wall thickness of 9.271 mm. Macroscopic testing, chemical composition analysis, metallographic testing, hardness testing, X-ray diffraction testing, SEM, and EDS are a few of the test types conducted. The study's findings showed that the elbow tubes experienced a thinning process on the inner wall of the outer curvature side with a rough and wavy surface texture or appearance. This type of failure is known as erosion-corrosion. The level of erosion-corrosion failure that occurs is greatly influenced by the pH of the fluid being flowed reaching 2.67–2.91, this is due to the very high Cl- of 1290 ppm, so the higher the rate of erosion-corrosion that occurs. These materials are the most popular and widely used in the oil and gas sector. However, this pipe has weaknesses because it is susceptible to erosion-corrosion Therefore, it is very important to choose the right material, namely, a material that is resistant to erosion-corrosion

Improving resistance of E690 steel to stress corrosion cracking in high Cl− environments through Sn microalloying

Improving resistance of E690 steel to stress corrosion cracking in high Cl− environments through Sn microalloying

Study on the chloride ion binding rate of sulfoaluminate cement mortars containing different mineral admixtures

In this study, the chloride ion (Cl−) binding rate of sulfoaluminate cement (SAC) mortars containing different mineral admixtures was investigated. This is essential to improve the durability of concrete structures in high Cl− environments, especially where they are susceptible to Cl− attack such as coastlines and marine structures. The effects of Cl− concentration, curing age, and the type and amount of mineral admixture on the Cl− binding rate of SAC mortars were analyzed. It was found that the content of water-soluble Cl− in SAC mortars decreased with the increase of curing age, while the Cl− binding ratio increased accordingly, indicating that its resistance to internal Cl− permeation increased. The addition of fly ash (FA) and ground granulated blast furnace slag (GGBS) can significantly improve the Cl− binding rate of SAC mortars, and the Cl− binding rate increases to 46.6% with 20% of FA and 38.7% with 40% of GGBS. The effects of mineral admixtures on the microstructure and phase composition of SAC mortars were further investigated by X-ray diffraction (XRD) analysis. The results showed that the addition of FA and GGBS promoted the formation of C-S-H (calcium silicate hydrate) gels and improved the resistance of SAC mortars to Cl− penetration. On the other hand, the excessive addition of silica fume (SF) decreased the Cl− binding rate, whereas a moderate amount of limestone powder (LP) improved the Cl− binding rate. The study of the Cl− binding rate of SAC mortars can help to evaluate their resistance to Cl− erosion in real projects, thus guiding the optimization of concrete formulations and the improvement of durability.

Tantalum in hydrothermal fluids

Understanding the behaviour of tantalum (Ta) in hydrothermal systems is pivotal for understanding its geochemical enrichment processes and economic extraction via hydrometallurgy. Yet, its behaviour in hydrothermal systems remains poorly characterised. This study investigates the coordination chemistry, speciation, and solubility of pentavalent Ta(V) in fluoride (F) − and chloride (Cl) −rich hydrothermal solutions up to 413 °C and 800 bar, utilising in-situ High Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy (HERFD-XAS). The results reveal the stability of high order fluoridotantalate complexes in fluoride-rich fluids solutions up to the highest investigated temperature, highlighting fluoride’s paramount role in enhancing Ta solubility through the formation of stable complexes in aqueous solutions. A transition from nonafluoridotantalate tetraanion (TaF94−) to heptafluoridotantalate dianion (TaF72−) complexes was observed as a function of temperature in solutions containing ≥1 m fluoride. Conversely, our findings indicate a negligible role for chloride in Ta complexation even in high Cl (∼6 m) aqueous solutions, suggesting that Ta chloride complexes do not contribute significantly to Ta transport in hydrothermal systems. Existing solubility data were reinterpreted based on an updated speciation model that integrates the in-situ XAS results. This confirms that Ta(OH)5(aq) predominates in solutions containing <0.02 m fluoride; oxyfluoridotantalate anions such as [TaF3(OH)3−] dominate in solutions containing intermediate fluoride concentrations (0.02–1 m), and the fluoridotantalate anions [TaF94− to TaF72−] occur in more concentrated fluoride solutions (>1 m) at hydrothermal conditions (∼100–400 °C). Derived thermodynamic data for these species enable better understanding and geochemical modelling of Ta transport in hydrothermal fluids, highlighting the potential of F-rich fluids to transport significant amounts of Ta.

B–Li differential enrichment of geothermal systems in the Da Qaidam and Gonghe–Guide Basin, northeastern Tibetan Plateau: Evidence from water chemistry and H–O–B–Li isotopes

Typical geothermal systems in the Da Qaidam (DQ) and Gonghe–Guide Basin (GGB) on the northeastern Tibetan Plateau (NETP) discharged different BLi contents. A widely accepted metallogenic model is that the salt–lake type BLi deposits in the TP are recharged by geothermal fluids with B–Li–rich, carried by rivers and enriched in the terminal salt lakes. The B–Li–rich geothermal water is the key source of mineralization in salt lakes, however, enrichment mechanism governing differential BLi contents in DQ and GGB geothermal systems remains ambiguous. This study systematically deciphers water chemistry and isotope characteristics (δD, δ18O, δ11B, δ7Li) of river waters, geothermal waters, sinters and surrounding rocks to discuss the enrichment process of BLi elements in the DQ and GGB geothermal systems. The δD and δ18O values of geothermal systems in the DQ (δD = −79.60 ∼ −82.40 ‰, δ18O = −10.97 ∼ −11.38 ‰) and GGB (δD = −64.00 ∼ −97.10 ‰, δ18O = −8.70 ∼ −13.00 ‰) are close to the GMWL and LMWL, indicating meteoric origin. The δD and high Cl− values (300–900 mg/L) of geothermal waters in the DQ and Qiabuqia, Qunaihai, Zhacangsi along Riyueshan of the GGB imply that these geothermal waters mixed by magmatic fluid and meteoric water. The hot springs in the DQ (B = 38.35–46.29 mg/L, Li = 3.11–3.72 mg/L) and GGB (B = 0.17–8.16 mg/L, Li = 0.08–10.49 mg/L) exhibit differential BLi geochemical characteristics. B and Li contents are higher in DQ hot springs and in hot springs along Riyueshan of the GGB, respectively. Comparison of the BLi contents and δ11B–δ7Li values of geothermal waters, sinters and host rocks reveals that BLi contents of geothermal waters are controlled by B–rich HP-UHP metamorphic rocks formed by metamorphism and Li–rich granites or pegmatites formed by magmatism in the Qilian Shan, respectively. Moreover, metamorphic and magmatic processes, combining with deep circulation reactivated by the thrust or strike–slip faults, create differential enrichment of BLi elements in the geothermal systems, such as DQ and GGB on the NETP. This study highlights into understanding the differential enrichment of BLi in the geothermal system on the TP. Furthermore, the resource elemental abundance of geothermal waters can be applied as an important prospecting indicator of endogenous BLi deposits.

Template-directed strategy synthesis of CoNi-layered double hydroxide nanosheet coated with polypyrrole for enhanced capacitive deionization

Recently, faradic material layered double hydroxide (LDH) has been widely used as an anode for capacitive desalination (CDI), due to its reversible ion insertion/deintercalation process and high anion storage capacity. Unfortunately, the issues of poor conductivity and self-stacking of LDH limit its application in the CDI. Herein, CoNi-LDH coated with polypyrrole (PPy) was meticulously designed and synthesized PPy@CoNi-LDH nanohybrids using ZIF-67 as the precursor by template-directed strategy and in-situ polymerization. The CoNi-LDH has large interlayer distance of 0.91 nm, which is beneficial for ion insertion. Introduced PPy conductive layer improved the interface transfer rate of charges and increased the ion storage capacity of composite. The experimental test results indicate that PPy@CoNi-LDH1:1 electrode has a higher specific capacitance of 223.1F g−1 and lower resistivity of 62.33 Ω·cm compared to CoNi-LDH electrode (35.2F g−1 and 3.39 × 104 Ω·cm). Obtained PPy@CoNi-LDH1:1 also has abundant mesoporous and excellent hydrophilicity, which can promote ions transfer. Meanwhile, the specific surface area of PPy@CoNi-LDH1:1 with the coating structure is 1.78 times that of CoNi-LDH, effectively suppressing the self-stacking of CoNi-LDH and exposing more active sites. When employed PPy@CoNi-LDH1:1 as an anode and the activated carbon as a cathode, the PPy@CoNi-LDH1:1//AC cell exhibited a high Cl− removal capacity (60.20 mg g−1), a swift Cl− removal rate (11.45 mg g−1 min−1) and good cycling stability (the retention rate is 89.67 % after 50 cycles) in NaCl solution of 500 mg L−1 and 1.4 V applied voltage. Additionally, the adsorption mechanism indicated that surface charge attraction, ligand exchange, and ion insertion jointly promote the Cl− removal. This study provides a feasible solution about successful design of high adsorption capacity anode materials for CDI.

Biochars from chlorine-rich feedstock are low in polychlorinated dioxins, furans and biphenyls

Chlorinated aromatic hydrocarbons like polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) and polychlorinated biphenyls (PCB) are omnipresent in the environment due to historic production, use, and (unintended) release. Nowadays, their emission and maximum concentration in environmental compartments is strictly regulated. During biochar production, PCDD/F and PCB may be formed and retained on the solid pyrolysis product. Industrial biochars certified, e.g., under the European Biochar Certificate (EBC), exhibit concentrations that were always well below threshold values for soil application and even animal feed. However, this has not been sufficiently tested for chlorine (Cl) rich organic material such as marine biomass or polyvinyl chloride (PVC) contaminated feedstock. Here, we analyzed PCDD/F and PCB contamination in biochars produced at different temperatures from different biomasses with comparatively high Cl contents in the range from 0.2 % to 3.8 % (w/w, seagrass, two types of saltwater macroalgae, tobacco stalks, and PVC contaminated wood). All of the biochars produced showed PCDD/F and PCB contents well below the applicable threshold values given by the EBC (< 20 ng TEQ kg−1 for PCDD/F and < 2×105 ng kg−1 for PCB). The EBC thresholds were undershot by a minimum of factor 1.5 for PCDD/F (mostly factor 20) and by a minimum of factor 90 for PCB. Between 1 and 27 ppb of feedstock Cl were transformed to Cl bound in PCDD/F and PCB in the biochars. No consistent correlation between biomass Cl contents and contents of PCDD/F and PCB were found but higher Cl contents in the feedstock led to a more diverse PCDD/F congener pattern in the biochars. Pyrolysis of PVC-amended wood resulted in consistently higher contamination of PCDD/F and PCB in the biochars compared to pyrolysis of the other biomasses, potentially due to differences in Cl speciation in the feedstocks i.e., Cl in PVC is already covalently bound to an organic carbon backbone. A high contamination in PCDD/F and PCB in biochar was intentionally triggered by separation of pyrogas and biochar in the reactor at < 300 °C to promote condensation of contaminants on the solid product. Between 20 % and 80 % of feedstock Cl was released via the pyrogas, i.e., neutralization of HCl in burnt pyrogas might be necessary when pyrolyzing Cl-rich feedstock in industrial biochar production. Our results indicate that biochars produced from Cl-rich feedstocks with proper biochar production process control are conform with European certification guidelines for PCDD/F and PCB contamination. The results open the opportunity to exploit and valorize so far non-used marine or otherwise Cl enriched biomasses for the production of biochar and carbon sinks.

Assessing water quality of kazerun county in southwest Iran: Multi-analytical techniques, deterministic vs. probabilistic water quality index, geospatial analysis, fuzzy C-means clustering, and machine learning

Water quality is critical to human health and the environment, especially in arid and semi-arid regions. Hence, the objectives of this study were to assess drinking water quality, identify critical parameters, investigate spatial patterns, and investigate accurate predictive models for the water quality index (WQI) in the Kazerun county in southwest Iran. To address this issue using deterministic and probabilistic WQI, correlation matrix, fuzzy C-Means (FCM) clustering, geostatistics, and adaptive network-based fuzzy inference system (ANFIS) with FIS generation by fuzzy C-Means (FCM-ANFIS) and sub-clustering (SC-ANFIS).Various software tools, including Excel, MATLAB, Python, and GIS were used to analyze groundwater data collected from 25 sampling sites. Water parameters, including pH, Cl−, SO4−2, EC, NO3−, NO2−, Ca2+, Mg2+, and F−, were examined. The results showed that F− levels were within acceptable limits set by the US EPA, but about one-third of sites posed potential health risks based on WHO guidelines. In one-third of regions, the levels of Mg2+ exceeded the recommended guidelines. In deterministic and probabilistic approaches, water quality was excellent in 68% and 81.3% of sites, respectively. Sobol sensitivity analysis identified SO4−2> Mg2+>Cl− > EC > F− > NO3− as significant WQI variables. Spearman correlation matrix shows substantial positive correlations between WQI and EC, F−, SO4−2, Mg2+, and Cl− were shown by the Spearman correlation matrix. Based on the FCM results, the southeast and central sites (56% of sites) have similar water quality. In comparison, the northern and four central sites (28% of sites) have distinct regional features, and the southern sites (16% of sites) had unique water quality characteristics. Geostatistical analyses showed that pH had the most substantial local clustering, while SO4−2 had significant high-value clustering. Furthermore, hot spot research revealed specific sites with high pH, F−, NO3−, and Cl− levels. The FCM-ANFIS model outperformed the SC-ANFIS model, emphasizing FCM clustering's importance in water quality forecasting accuracy.

Deep regolith weathering controls δ30Si composition of groundwater under contrasting landuse in tropical watersheds

Land use changes are known to alter terrestrial silicon cycling and the export of dissolved silicon from soil to fluvial systems, but the impact of such changes on groundwater systems remain unclear. In order to identify the processes responsible for groundwater geochemistry and to assess the impact of agricultural processes, we examined multiple isotopic tracers (δ30Si, oxygen (δ18O) and hydrogen (δ2H) isotopes) in groundwater, soil porewater and surface water from two contrasted watersheds having the same gneissic lithology, one forested (Mule Hole) and one intensely cultivated (Berambadi) in the Kabini basin in South India. In the cultivated watershed, groundwater exhibits high Cl− and NO3− concentrations indicative of fertilizer inputs and solute enrichment from evapotranspiration due to multiple groundwater pumping/recharge cycles. The DSi concentration in groundwater is significantly higher in the cultivated watershed (980 ± 313 μM) than in the forested one (711 ± 154 μM), indicating more intense evapotranspiration due to irrigation cycles. The groundwater δ30Si values ranged from 0.6 ‰ to 3.4 ‰ and exhibit no significant differences between cultivated (1.2 ± 0.5 ‰) and forested (1.0 ± 0.2 ‰) watersheds, indicating limited impact of land use and land cover. Groundwater also shows no significant seasonal differences in DSi and δ30Si within watersheds, indicating a buffer to seasonal recharge during wet season. The δ30Si of a majority of groundwater samples fits a steady-state open flow through system, with an isotopic fractionation factor (30ε) between precipitating phase and groundwater ranging from −1.0 ‰ and − 2.0 ‰, consistent with precipitation of kaolinite-type clays, dominant in the study area. The steady-state flow through system in groundwater can be interpreted as a continuous DSi input from mineral weathering reactions with a dynamic equilibrium between Si supply and precipitation of secondary phases. We also observe, in both watersheds, similar DSi and δ30Si values in local surface water that includes small streams and a river (406 ± 194 μM, 1.6 ± 0.3 ‰) and in soil porewater (514 ± 119 μM, 1.6 ± 0.2 ‰). Compared to soil porewater, groundwater exhibits significantly lower δ30Si signatures and higher DSi, reflecting the contribution of an isotopically light silicon source, resulting from water-rock interaction during percolation through the unsaturated zone. We assign this steady input of DSi to the weathering of primary silicate minerals in the regolith, such as Na-plagioclase, biotite and chlorite, with formation of kaolinite and smectites type clays. A simple isotopic mass balance suggests that deep regolith weathering can contribute to almost half of the DSi in groundwater. We conclude that silicon cycling in soil porewaters, and surface waters are directly impacted by land use, while the isotopic composition of groundwater remains unaffected. Our results indicate that Si isotopic signatures of weathering, adsorption, and plant uptake occurring in the shallow soil and saprolite horizons are partly overprinted and homogenized by the regolith weathering in the deep critical zone, irrespective of land use and seasonality.

Two-stage mineralization of the Jinkeng Sn-Cu deposit in Eastern Guangdong, Southeast China: Response to magmatic activities and tectonic transformation

The Jinkeng Sn-Cu polymetallic deposit in South China consists of two different types of orebodies: 1) NE-striking skarn- and vein-type Cu-Pb-Zn-Sn orebodies in volcanic rocks suffering subsequent ductile shear deformation, and 2) NW-striking quartz-cassiterite-sulfide veins filled in the faults at the porphyritic granodiorite outward from the fine-grained granite which does not exhibit deformation. The relationships among Sn-Cu polymetallic mineralization, regional magmatism, and deformation metamorphism are still controversial. To address it, the geochronological, whole-rock and mineral geochemical research along with the detailed field investigation were conducted in this study. Our zircon U-Pb dating results show that the volcanic rocks formed at 158–162 Ma, earlier than the porphyritic granodiorite which yields the emplacement age of 146–147 Ma. In-situ LA-ICP-MS U-Pb dating of cassiterite from the deformed skarn ores indicates the early-stage mineralization occurred at 146 ∼ 148 Ma, which is similar to the emplacement age of the porphyritic granodiorite, but earlier than the formation of quartz-cassiterite-sulfide veins and the fine-grained granite (141∼144 Ma). Further, the whole-rock and biotite geochemistry, and zircon Hf isotope compositions suggest that the porphyritic granodiorite exhibits a lower degree of magma differentiation, higher oxygen fugacity, higher Cl and lower F contents than the fine-grained granite. The porphyritic granodiorite might provide the most Cu-Pb-Zn budget accompanied by minor Sn for early-stage mineralization. Overall, our study suggests that the Jinkeng Sn-Cu polymetallic deposit formed in two scenarios where the early dominated Cu-Pb-Zn and minor Sn mineralization related to the emplacement of the porphyritic granodiorite is superimposed by the late vein-type Sn-dominated mineralization related to the emplacement of the fine-grained granite. The two isolated mineralizing events (∼147 Ma and ∼141 Ma, respectively) in Jinkeng were probably responded to the regional magmatic activities triggered by the tectonic transformation where two extensional tectonic events were separated by a short contractional event (147–144 Ma).

Interpreting the main effects on the efficiency and morphology for establishing a procedure of electrodepositing Zn from purified chloride SPL solutions

Potentiodynamic and galvanostatic experiments have been used to investigate the electrodeposition of Zn and to develop a reliable recovery method from a purified spent pickling liquor (SPL) of hot dip galvanization. The main bjective was to find the suitable conditions to deposit high-grade Zn from the purified ZnCl2–HCl–NaCl solution in a conventional electrowinning cell holding the stationary electrolyte. The effects of pH (1.5–4.5) in and Zn concentration (30–150 g/dm3) in the stationary electrolytes were studied first by the potentiodynamic method to reveal the major characteristics of the cathodic process and to give reference for further practical examinations by the galvanostatic technique. The electrowinning experiments pointed out the effects of these major parameters, beside other practical factors, like apparent current density (c.d.) and additional NaCl concentration. The long-term galvanostatic experiments proved that the current efficiency (c.e.) increases significantly as the pH and the Zn concentration are increased. A c.e. of ~ 99% can be reached with an electrolyte of pH ~ 5, Zn concentration ~ 50 g/dm3 applying a c.d. in the 300–600 A/m2 range. Increasing the Zn concentration could considerably improve also the deposit morphology. The addition of NaCl can practically improve the c.e. if the Zn concentration is at least around 50 g/dm3. In contrast, this improvement is largely off-set by the negative effects of strong H2 evolution at low (e.g. < 10 g/dm3) Zn concentrations. Extremely high Cl− ion concentrations, however, inhibit the cathodic reaction by stronger chloro-complex formation. In this case the intensive H+ reduction causes hydroxide precipitation.

Earth's longest lava flows erupted from its largest igneous province: The submarine Ontong Java Plateau

We use high-precision analyses of fresh basalt glasses from the submarine, Cretaceous Ontong Java Plateau (OJP) recovered by the Ocean Drilling Programs (ODP) to test for long submarine lava flows. Major elements and Cl show that glasses from ODP Holes 1185B and 1186A, which are 200 km apart, are compositionally identical and must have erupted simultaneously from the same well-mixed magma chamber. Identical CO2 contents show they erupted at the same water depth, but 1185B is directly downslope from 1186A and has a corrected basement depth that is >700 m deeper. Remarkably, <2 °C cooling took place over 200 km, requiring a cooling rate <0.01 °C/km.Further evidence of long flows is the lack of vesicles in OJP's glasses, in contrast to mid-ocean ridge basalt glasses that almost always contain vesicles and are often oversaturated in dissolved CO2. We propose that OJP's lavas degassed to saturation levels of dissolved CO2 +H2O and lost all bubbles because they remained liquid for much longer periods during long distance flow. Dissolved CO2+H2O are used to estimate paleoeruption depths which are compared to current corrected basement depths. Using a fixed value of plateau subsidence (500 m) we reconstruct flow distances of 0 to 900 km for eight lava groups from six drill sites. Eruption depths in Hole 807 C are 3040 m for Kwaimbaita-type lavas but 1110 m for Singgalo-type lavas that directly overlie them suggesting that the Singgalo lavas erupted 900 km away (near Site 1183).Paleoeruption depths for Cretaceous glasses from the Jurassic East Mariana and Nauru Basins adjacent to OJP are shallower than most glasses recovered from OJP even though their reconstructed basement depths are 1500–3800 m deeper. It is very likely that the basins’ lavas were erupted on OJP and flowed up to 1600 km: longer than any lava flow known on Earth. Flow distances are shorter (≤1000 km) if a plateau subsidence of 1500 m is used in the calculations. Extremely high Cl in Nauru Basin glasses also supports eruption from OJP. Long distance flow with minimal cooling was facilitated on OJP by favorable slopes, lack of barriers, insulation of rapidly forming glass, and possibly by flow within lava tubes. Lava effusion rates were probably >100 m/sec and flow rapid: >1 m/sec.

Technical note: Optimizing the in situ cosmogenic 36Cl extraction and measurement workflow for geologic applications

Abstract. In situ cosmogenic 36Cl analysis by accelerator mass spectrometry (AMS) is routinely employed to date Quaternary surfaces and assess rates of landscape evolution. However, standard laboratory preparation procedures for 36Cl dating require the addition of large amounts of isotopically enriched chlorine spike solution; these solutions are expensive and increasingly difficult to acquire from commercial sources. In addition, the typical workflow for 36Cl dating involves measuring both 35Cl/37Cl and 36Cl/Cl concurrently on the high-energy (post-accelerator) end of the AMS system, but 35Cl/37Cl determinations using this technique can be complicated by isotope fractionation and system memory during measurement. The traditional workflow also does not provide 36Cl extraction laboratories with the data needed to calculate native Cl concentrations in advance of 36Cl/Cl measurements. In light of these concerns, we present an improved workflow for extracting and measuring chlorine in geologic materials. Our initial step is to characterize 35Cl/37Cl on sample aliquots of up to ∼1 g prepared in Ag(Cl, Br) matrices, which greatly reduces the amount of isotopically enriched spike solution required to measure native Cl content in each sample. To avoid potential issues with isotope fractionation through the accelerator, 35Cl/37Cl is measured on the low-energy, pre-accelerator end of the AMS line. Then, for 36Cl/Cl measurements, we extract Cl as AgCl or Ag(Cl, Br) in analytical batches with a consistent total Cl load across all samples; this step is intended to minimize source memory effects during 36Cl/Cl measurements and allows the preparation of AMS standards that are customized to match known Cl contents in the samples. To assess the efficacy of this extraction and measurement workflow, we compare chlorine isotope ratio measurements on seven geologic samples prepared using standard procedures and the updated workflow. Measurements of 35Cl/37Cl and 36Cl/Cl are consistent between the two workflows, and 35Cl/37Cl values measured using our methods have considerably higher precision than those measured following standard protocols. The chemical preparation and measurement workflow presented here (1) reduces the amount of isotopically enriched chlorine spike used per rock sample by up to 95 %; (2) identifies rocks with high native Cl concentrations, which may be lower priority for 36Cl surface exposure dating, at an early stage of analysis; and (3) allows laboratory users to maintain control over the total chlorine content within and across analytical batches. These methods can be incorporated into existing laboratory and AMS protocols for 36Cl analyses and will increase the accessibility of 36Cl dating for geologic applications.

Herbal extract dietary supplementation effect on growth performance and meat quality in broiler raised under two stocking densities

The number of birds or their total live weight in relation to a given area is known as stocking density; higher stocking densities will cause more stress to the birds, which may have an impact on their physiological state, productivity, carcass quality, growth performance, immunity, metabolism, and meat quality. The present study aimed to investigate the potential impact of 2 different stocking densities on growth performance, carcass characteristics, meat quality, serum, and expression of Insulin like growth factor-1 (IGF-1), muscle regulatory genes expression and serum biochemical indicators of broilers supplemented with essential oils (EO). In total, 784-day-old chicks of Ross 308 were randomly assigned into 4 different groups with 7 replicates for each: Normal feed (no essential oils [EO] added) and normal stocking as 9 bird/m2, (NSD). Normal feed (no essential oils [EO] added) and high stocking as 14 bird/m2, (HSD). Feed with essential oils (Digestarom DC® 150 g/Ton of feed) and normal stocking as 9 birds/m2, (NSD + EO). Feed with essential oils (Digestarom DC® 150 g/Ton of feed) and high stocking as 14 birds/m2, (HSD + EO) for 35 days. Bodyweight was recorded at the beginning of the trial and then at the end of each week, feed intake was recorded at the end of each week as well. A total of 28 birds (7 birds per treatment) birds were slaughtered at 35 days of age to evaluate each parameter. The HSD group had the lowest (P < 0.05) feed intake. The NSD groups showed the highest (P < 0.05) body weight gain compared to HSD groups. The HSD + EO had lower adjusted FCR (P < 0.05) compared to HSD. The legs % was the highest (P < 0.05) for NSD group, while HSD + EO had the highest (P < 0.05) Fat Pad percentage. Moreover, HSD had the highest CL%, and the lowest WHC and Warner–Bratzler shear force. For biochemical indicators, (IGF-1) was the lowest (P < 0.05) HSD group. Also, Mammalian Target of Rapamycin (mTOR) and Aspartate Aminotransferase (AST) were higher (P < 0.05) in the EO supplemented groups. Regarding gene expression, the results showed that Myogenin (MyoG) and IGF-1 were lower in HSD while MSTN was higher in the same group, (P < 0.05). In brief, essential oil supplement has improved the performance of broilers under high stocking density situation.

Advanced rigid carbazole-based membranes assembled with flexible piperidine alkyl chains for neutral aqueous organic redox flow battery

Neutral aqueous organic redox flow battery (NAORFB) represents a highly promising energy storage device. However, one of its challenges is the need for high Cl− conductivity, highly stable ion-selective membranes. In this work, N-methylpiperidine-modified carbazole-based long side chain anion exchange membranes (QPCEP-x) were designed and prepared. The rigidity and hydrophobicity provided by the carbazole on the main chain, in conjunction with the flexibility and hydrophilicity provided by the alkyl-piperidine groups on the side chains, resulted in the observed excellent microphase separation properties of the prepared membranes. The prepared membranes exhibited excellent overall performance, with QPCEP-1 achieving a Cl− conductivity of 20.33 mS cm−1 at 25 °C. In NAORFB, the energy efficiency of QPCEP-1 ranges from 91.7 % to 62.4 % at 20–160 mA cm−2, far exceeding the 89.1 %–38.4 % of commercial AMVN. Furthermore, long-term cell cycling tests demonstrate that the energy efficiency of QPCEP-1 remains unchanged at 82.7 % at 60 mA cm−2 after 10,000 complete charge and discharge cycles, exceeding the majority of cycles reported in literatures. These findings suggest that QPCEP-x has significant potential for use in NAORFB.

Canola (Brassica napus) enhances sodium chloride and sodium ion tolerance by maintaining ion homeostasis, higher antioxidant enzyme activity and photosynthetic capacity fluorescence parameters.

Under salt stress, plants are forced to take up and accumulate large amounts of sodium (Na+ ) and chloride (Cl- ). Although most studies have focused on the toxic effects of Na+ on plants, Cl- stress is also very important. This study aimed to clarify physiological mechanisms underpinning growth contrasts in canola varieties with different salt tolerance. In hydroponic experiments, 150mM Na+ , Cl- and NaCl were applied to salt-tolerant and sensitive canola varieties. Both NaCl and Na+ treatments inhibited seedling growth. NaCl caused the strongest damage to both canola varieties, and stress damage was more severe at high concentrations of Na+ than Cl- . High Cl- promoted the uptake of ions (potassium K+ , calcium Ca2+ ) and induced antioxidant defence. Salt-tolerant varieties were able to mitigate ion toxicity by maintaining lower Na+ content in the root system for a short period of time, and elevating magnesium Mg2+ content, Mg2+ /Na+ ratio, and antioxidant enzyme activity to improve photosynthetic capacity. They subsequently re-established new K+ /Na+ and Ca2+ /Na+ balances to improve their salt tolerance. High concentrations of Cl salts caused less damage to seedlings than NaCl and Na salts, and Cl- also had a positive role in inducing oxidative stress and responsive antioxidant defence in the short term.

The Impact of HCl on Alkali-Induced Corrosion of Stainless Steels/FeCrAl Alloy at 600 °C: The Story After Breakaway

The impact of Cl on alkali-induced high-temperature corrosion of stainless steels/FeCrAl alloys after breakaway oxidation was investigated in a simulated biomass- and waste-fired boiler environment at 600 °C. For this investigation, three alloys were exposed to low Cl load environment (H2O+KCl) and to high Cl load (H2O+KCl+HCl). Post-exposure analysis showed that the stainless steel SVM12 experiences fast oxidation and forms thick double-layered Fe-rich oxide scales. The corrosion attack is further accelerated with addition of HCl for this material with the effect being more pronounced in the inward-growing scale. The FeCrAl and FeCrNi alloys exhibit slower oxidation kinetics after the breakaway corrosion compared to SVM12 in the H2O+KCl exposure. Furthermore, in contrast with SVM12, the addition of HCl did not accelerate the corrosion attack on these alloys. It is argued that the properties of the secondary oxide layer formed after breakaway corrosion are important in the continued corrosion resistance against chlorine-induced corrosion attack. Especially, the Cr content in the inner scales is suggested to be important in corrosion mitigation.

Kinetics and mechanisms of non-radically and radically induced degradation of bisphenol A in a peroxymonosulfate-chloride system

Bisphenol A, a hazardous endocrine disruptor, poses significant environmental and human health threats, demanding efficient removal approaches. Traditional biological methods struggle to treat BPA wastewater with high chloride (Cl−) levels due to the toxicity of high Cl− to microorganisms. While persulfate-based advanced oxidation processes (PS-AOPs) have shown promise in removing BPA from high Cl− wastewater, their widespread application is always limited by the high energy and chemical usage costs. Here we show that peroxymonosulfate (PMS) degrades BPA in situ under high Cl− concentrations. BPA was completely removed in 30 min with 0.3 mM PMS and 60 mM Cl−. Non-radical reactive species, notably free chlorine species, including dissolved Cl2(l), HClO, and ClO− dominate the removal of BPA at temperatures ranging from 15 to 60 °C. Besides, free radicals, including •OH and Cl2•−, contribute minimally to BPA removal at 60 °C. Based on the elementary kinetic models, the production rate constant of Cl2(l) (32.5 M−1 s−1) is much higher than HClO (6.5 × 10−4 M−1 s−1), and its degradation rate with BPA (2 × 107 M−1 s−1) is also much faster than HClO (18 M−1 s−1). Furthermore, the degradation of BPA by Cl2(l) and HClO were enlarged by 10- and 18-fold at 60 °C compared to room temperature, suggesting waste heat utilization can enhance treatment performance. Overall, this research provides valuable insights into the effectiveness of direct PMS introduction for removing organic micropollutants from high Cl− wastewater. It further underscores the critical kinetics and mechanisms within the PMS/Cl⁻ system, presenting a cost-effective and environmentally sustainable alternative for wastewater treatment.

Volatile systematics in terrestrial igneous apatite: from microanalysis to decoding magmatic processes

Apatite has been recognized as a robust tool for the study of magmatic volatiles in terrestrial and extraterrestrial systems due to its ability to incorporate various volatile components and its common occurrence in igneous rocks. Most previous studies have utilized apatite to study individual magmatic systems or regions. However, volatile systematics in terrestrial magmatic apatite formed under different geological environments has been poorly understood. In this study, we filtered a large compilation of data for apatite in terrestrial igneous rocks (n > 20,000), categorized the data according to tectonic settings, rock types, and bulk-rock compositions, and conducted statistical analyses of the F–Cl–OH–S–CO2 contents (~ 11,000 data for halogen and less for other volatiles). We find that apatite from volcanic arcs preserves a high Cl signature in comparison to other tectonic settings and the median Cl contents differ between arcs. Apatite in various types and compositions of igneous rocks shows overlapping F–Cl–OH compositions and features in some rock groups. Specifically, apatite in kimberlite is characterized as Cl-poor, whereas apatite in plutonic rocks can contain higher F and lower Cl contents than the volcanic counterparts. Calculation using existing partitioning models indicates that apatite with a high OH (or F) content does not necessarily indicate a H2O-rich (or H2O-poor) liquid because it could be a result of high (or low) magma temperature. Our work may provide a new perspective on the use of apatite to investigate volatile behavior in magma genesis and evolution across tectonic settings, volatile recycling at subduction zones, and the volcanic-plutonic connection.

Albitization related U and Th mobilization under reducing conditions

Hydrothermally altered quartzofeldspathic gneisses, granites and pegmatites of the West Garo Hills, Shillong Plateau (eastern India) preserve alteration assemblages of monazite, xenotime and zircon comprising thorite and coffinite in the altered domains. Albitization of muscovite and K-feldspars, sericitization of K-feldspar and albite, alteration of biotite to hydrobiotite, and crystallization of tourmaline is suggestive of the involvement of acidic fluids. The microtextural relations and the mineral assemblages indicate prevalence of low-temperature (T < 300 °C) conditions during hydrothermal alteration. The light δ11B values of tourmaline (–15.1 to –13.5 ‰) suggests derivation/interaction of the fluids from/with metapelitic rock and/or S-type granite. Low ‘inferred’ Fe3+/Fe2+ ratio in tourmaline (based on high Al content in Y-site, 0.16–0.56 apfu, avg. 0.36 apfu), estimated excess charge (0.22–0.47, avg. 0.35 apfu) and lack of any Fe–Al relation support a reduced nature of the hydrothermal fluid. Mass balance calculations reveal that Th and U required for the formation of thorite and coffinite, respectively were likely derived from monazite and xenotime, and zircon. Significantly lower Cl─ contents in hydrobiotite (avg. 0.03 wt%) compared to the unaltered biotite (avg. 0.13 wt%) suggests release of Cl─ to the hydrothermal fluid during alteration. Textural evidences of albitization together with Cl─ release from biotite suggest increased Cl─ concentrations in the fluid during hydrothermal alteration. Based on solubility calculations for various U and Th species, we propose that high Cl─ content in the fluid aided mobilization of Th and U as ThCl40 and UCl40/UO2Cl20 complexes from accessory radioactive phases under reducing conditions. These results suggest that significant mobility of U and Th can be achieved in acidic high salinity fluid even under reducing conditions. Thermodynamic calculations for the solubility of Th- and U-chloride complexes and stability of monazite/xenotime in a range of pH and temperature suggest that thorite and coffinite precipitation was the result of an increase in pH.