Micropillar with Radial Gradient Modulus Enables Robust Adhesion and Friction.

The gradient modulus in beetle setae plays a critical role in allowing it to stand and walk on natural surfaces. Mimicking beetle setae to create a modulus gradient in microscale, especially in the direction of setae radius, can achieve reliable contact and thus strong adhesion. However, it remains highly challenging to achieve modulus gradient along radial directions in setae-like structures. Here, polydimethylsiloxane (PDMS) micropillar with radial gradient modulus, (termed GM), is successfully constructed by making use of the polymerization inhibitor in the photosensitive resin template. GM gains adhesion up to 84 kPa, which is 2.3 and 4.7 times of soft homogeneous micropillars (SH) and hard homogeneous micropillars (HH), respectively. The radial gradient modulus facilitates contact formation on various surfaces and shifts stress concentration from contact perimeter to the center, resulting in adhesion enhancement. Meanwhile, GM achieves strong friction of 8.1 mN, which is 1.2 and 2.6 times of SH and HH, respectively. Moreover, GM possesses high robustness, maintaining strong adhesion and friction after 400 cycles of tests. The work here not only provides a robust structure for strong adhesion and friction, but also establishes a strategy to create modulus gradient at micron-scale.

Washing antimony and arsenic from agricultural soil with eco-friendly organic acids and the relevant bioavailability assessment.

Antimony (Sb) and arsenic (As) contamination in agricultural soil poses human health risks through agricultural products. Soil washing with degradable low molecular weight organic acids (LMWOAs) is an eco-friendly strategy to remediate agricultural soils. In this study, three eco-friendly LMWOAs, oxalic acid (OA), tartaric acid (TA), and citric acid (CA), were used to treat Sb and As co-contaminated agricultural soil from Xikuangshan mine area. The OA, TA, and CA washed out 18.4, 16.8, and 26.6% of Sb and 15.3, 19.9, and 23.8% of As from the agricultural soil, with CA being the most efficient reagent for the soil washing. These organic acids also led to pH decline and macronutrients losses. Fraction analysis using a sequential extraction procedure showed that the three organic acids targeted and decreased the specifically sorbed (F2) (by 19.3-37.6% and 2.41-23.5%), amorphous iron oxide associated (F3) (by 49.1-61.2% and 51.2-70.2%), and crystallized iron oxide associated (F4) (by 12.3-26.0% and 26.1-29.1%) Sb and As. The leachability of Sb and As, as well as their concentrations and bioconcentration factor (BCF) in vegetables reduced due to the soil washing. It demonstrated that the bioavailability of both the elements was decreased by the organic acids washing. The concentrations of Sb and As in typical vegetable species cultivated in CA washed soil were less than the threshold value for consumption safety, while those in OA and TA washed soils were still higher than the value, suggesting that only CA is a potential washing reagent in soil washing for Sb- and As-contaminated agricultural soil.

Improvement in Mechanical Properties of 3D-Printed PEEK Structure by Nonsolvent Vapor Annealing.

The broad applications of 3D-printed poly-ether-ether-ketone (3D-PEEK) structures are largely hampered by their inadequate mechanical properties that can be improved by post treatments. At present, thermal annealing is generally used to improve the mechanical properties of 3D-PEEK. However, it cannot simultaneously improve strength and ductility. Here, a cost-effective postprocessing method is developed to improve the mechanical properties of 3D-PEEK, based on annealing in nonsolvent vapor at room temperature. The annealing in nonsolvent vapor at room temperature simultaneously improves the strength, ductility, and fracture energy of as-printed 3D-PEEK by 22.6%, 151.3%, and 109.1%, respectively. The improved mechanical properties are attributed to enhanced interfacial bonding, increased crystallinity, decreased pinhole defects, and stress relaxation in the 3D-PEEK. Moreover, the annealing in both polar solvents (such as acetone and chloroform) and nonpolar solvents (such as n-hexane) are demonstrated to be effective for improving the mechanical properties of 3D-PEEK. The nonsolvent vapor-annealed 3D-PEEK can thus have potential applications in the fields of medical implants, automotive, aerospace, and more.

The leaching of antimony and arsenic by simulated acid rain in three soil types from the world's largest antimony mine area.

A simulated acid rain (SAR) experiment on leaching of antimony (Sb) and arsenic (As) in three soil types including paddy soils (PS), vegetable soils (VS) and slag based soils (SS) from Xikuangshan (XKS) Sb mine area was conducted. The SAR at pH 2.5, 3.5, 4.5 and 5.6 were sprayed to soil columns with intermittent pattern in a period of 50 days. Through the spraying duration, leaching Sb in PS, VS and SS showed decreasing trends regardless of pH values in SAR and were in the ranges of 0.026-0.064 mg L-1, 0.19-2.18 mg L-1 and 11.8-32.4 mg L-1, respectively. By contrast, leaching As in these three soil types continuously increased at the initial five spraying times and then deeply decreased afterward, with ranges being 0-0.007 mg L-1, 0.001-0.071 mg L-1 and 0.17-1.07 mg L-1, respectively. The leaching Sb in all the three soil types were extremely higher than the reference value in grade IV (0.01 mg L-1) for groundwater quality of China (GB/T 14,848-2017). For leaching As, peck values in VS and all the values in SS were also greater than the corresponding reference value (0.05 mg L-1). This indicated that leaching Sb and As could pollute the groundwater in XKS Sb mine area, especially those in slag based soils. The total leaching losses of Sb and As were affected by pH ambiguously, such as SAR at pH 2.5, 5.6 and 2.5 induced the greatest losses of Sb in PS, VS and SS, and pH 3.5, 5.6 and 2.5 resulted in the greatest leaching losses of As in these soils. After SAR treatment, the specific sorbed and Fe/Mn oxide-associated Sb and As significantly decreased. It demonstrated that these two fractions of both Sb and As were involved in leaching losses. The present study also found that the SAR treatment resulted in soil acidification in all the three soil types. In addition, available N, P and K in all the SAR treatments decreased regardless of pH values, except for available N and P in PS.

Adhesion Enhancement of Micropillar Array by Combining the Adhesive Design from Gecko and Tree Frog.

It has long been demonstrated the gecko-inspired micropillar array with T-shape tips possesses the best adhesion performance of a given material. The further enhancement of the adhesion performances of T-shape micropillars can offer redundant adhesion to compensate for the inevitable improper contacts. Here, the array of T-shape polydimethylsiloxane (PDMS) micropillars is incorporated with gradient dispersed calcium carbonate nanoparticles in the micropillar stalk, termed as T-shape gradient micropillars (TG), possessing the modulus gradient with stiff tip and soft root. The gradient modulus in TG facilitates the contact formation and regulates the stress at the detaching interface, resulting in a 4.6 times adhesion and 2.4 times friction as compared with the pure PDMS T-shape micropillar arrays. The study here provides a new design strategy for the super-strong structured dry adhesives.

Comparative effectiveness of Ginkgo injections for treating vertebrobasilar insufficiency: A systematic review and network meta-analysis.

WHAT IS KNOWN AND OBJECTIVE: This study sought to assess the clinical effectiveness of Ginkgo injections (GIs) combined with conventional drugs for vertebrobasilar insufficiency (VBI). METHODS: Randomized controlled trials (RCTs) that assessed the adjunctive effects of GIs for patients with VBI were retrieved from several English and Chinese databases from inception to December 2018. The Cochrane risk of bias method was used to evaluate the methodological quality of the eligible trials. The data were analysed by Stata 13.0 and WinBUGS 1.4.3 software. RESULTS: A total of 20 RCTs that included 1710 patients were included. All RCTs had an unclear risk of bias or a high risk of bias. The network meta-analysis (NMA) showed that the use of four kinds of GIs, especially Ginkgo leaf extract and dipyridamole injections (GDs), as adjunctive therapies with drugs for VBI increased the total effectiveness rate. Ginkgo biloba leaf extract injections (EGbs) combined with conventional drugs were more effective than only conventional drugs for improving the results of transcranial Doppler ultrasonography (TCD). Shuxuening injections (SXNs) seemed superior for improving blood viscosity-related indicators. Adverse events were mentioned in nine trials, and there was no difference between the GI group and the control group for the incidence rate of adverse events. WHAT IS NEW AND CONCLUSIONS: GIs showed significant benefits as an add-on therapy for VBI, as GIs increased the total effectiveness rate and improved the results of TCD examinations. Due to the limited sample size and quality of the included trials, the results of this review still need to be tested in larger, rigorous studies in the future.

Switchable Adhesion of Micropillar Adhesive on Rough Surfaces.

Switchable structured adhesion on rough surfaces is highly desired for a wide range of applications. Combing the advantages of gecko seta and creeper root, a switchable fibrillar adhesive composed of polyurethane (PU) as the backing layer and graphene/shape memory polymer (GSMP) as the pillar array is developed. The photothermal effect of graphene (under UV irradiation) changes GSMP micropillars into the viscoelastic state, allowing easy and intimate contact on surfaces with a wide range of roughness. By controlling the phase state of GSMP via UV irradiation during detachment, the GSMP micropillar array can be switched between the robust-adhesion state (UV off) and low-adhesion state (UV on). The state of GSMP micropillars determines the adhesion force capacity and the stress distribution at the detaching interface, and therefore the adhesion performance. The PU-GSMP adhesive achieves large adhesion strength (278 kPa), high switching ratio (29), and fast switching (10 s) at the same time. The results suggest a design principle for bioinspired structured adhesives, especially for reversible adhesion on surfaces with a wide range of roughness.

Continuous Gradient Nanoporous Film Enabled by Delayed Directional Diffusion of Solvent and Selective Swelling.

Nature-inspired porous structures are highly desired in the fields of new materials, sustainable energy, biological and chemical science, and so forth. Here, a new strategy for the fabrication of continuous, gradient nanoporous polystyrene- block-poly(2-vinylpyridine) (PS- b-P2VP) film is established. The continuous nanopore gradient along the direction of film thickness (∼120 µm) is achieved via delayed directional diffusion of dynamic binary solvent of ethanol/water and selective swelling of P2VP domains. Ethanol in binary solvent diffuses into the film from one side to another, which is retarded by the water gate as water is concentrated at the film surface. The delayed diffusion matches the swelling rate of P2VP domains, forming the continuous nanopore gradient normal to the film surface.

Tree frog adhesion biomimetics: opportunities for the development of new, smart adhesives that adhere under wet conditions.

Enlarged adhesive toe pads on the tip of each digit allow tree frogs to climb smooth vertical and overhanging surfaces, and are effective in generating reversible adhesion under both dry and wet conditions. In this review, we discuss the complexities of the structure of tree frog toe pads in relation to their function and review their biomimetic potential. Of particular importance are the (largely) hexagonal epithelial cells surrounded by deep channels that cover the surface of each toe pad and the array of nanopillars on their surface. Fluid secreted by the pads covers the surface of each pad, so the pads adhere by wet adhesion, involving both capillarity and viscosity-dependent forces. The fabrication and testing of toe pad mimics are challenging, but valuable both for testing hypotheses concerning tree frog toe pad function and for developing toe pad mimics. Initial mimics involved the fabrication of hexagonal pillars mimicking the toe pad epithelial structure. More recent ones additionally replicate the nanostructures on their surface. Finally we describe some of the biomimetic applications that have been developed from toe pad mimics, which include both bioinspired adhesives and friction-generating devices. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology (part 2)'.

High drug-loading gold nanoclusters for responsive glucose control in type 1 diabetes.

BACKGROUND: Diabetes is one of the biggest medical challenges worldwide. The key to efficiently treat type 1 diabetes is to accurately inject insulin according to the blood glucose levels. In this study, we aimed to develop an intelligent insulin-releasing gold nanocluster system that responds to environmental glucose concentrations. RESULTS: We employed gold nanoclusters (AuNCs) as a novel carrier nanomaterial by taking advantage of their high drug-loading capacity. We prepared AuNCs in the protection of bovine serum albumin, and we decorated AuNCs with 3-aminophenylboronic acid (PBA) as a glucose-responsive factor. Then we grafted insulin onto the surface to obtain the glucose-responsive insulin-releasing system, AuNC-PBA-Ins complex. The AuNC-PBA-Ins complex exhibited high sensitivity to glucose concentration, and rapidly released insulin in high glucose concentration in vitro. In the type 1 diabetic mouse model in vivo, the AuNC-PBA-Ins complex effectively released insulin and regulated blood glucose level in the normoglycemic state for up to 3 days. CONCLUSIONS: We successfully developed a phenylboronic acid-functionalized gold nanocluster system (AuNC-PBA-Ins) for responsive insulin release and glucose regulation in type 1 diabetes. This nanocluster system mimics the function of blood glucose regulation of pancreas in the body and may have potential applications in the theranostics of diabetes.

Comparative efficacy of Chinese herbal injections for treating acute cerebral infarction: a network meta-analysis of randomized controlled trials.

BACKGROUND: Chinese herbal injections (CHIs) are prepared by extracting and purifying effective substances from herbs (or decoction pieces) using modern scientific techniques and methods. CHIs combined with aspirin + anticoagulants + dehydrant + neuroprotectant (AADN) are believed to be effective for the treatment of acute cerebral infarction (ACI). However, no randomized controlled trial (RCT) has been performed to directly compare the efficacies of different regimens of CHIs. Therefore, we performed a systematic review and network meta-analysis (NMA) to compare the efficacies of different regimens of CHIs for ACI. METHODS: We conducted an overall and systematic retrieval from literature databases of RCTs focused on the use of CHIs to treat ACI up to June 2016. We used the Cochrane Handbook version 5.1.0 and CONSORT statement to assess the risk of bias. The data were analyzed using STATA 13.0 and WinBUGS 1.4.3 software. RESULTS: Overall, 64 studies with 6225 participants involving 15 CHIs were included in the NMA. In terms of the markedly effective rate, Danhong (DH) + AADN had the highest likelihood of being the best treatment. In terms of the improvement of neurological impairment, Shuxuening (SXN) + AADN had the highest likelihood of being the best treatment. Considering two outcomes, injections of SXN, Yinxingdamo (YXDM), DH, Shuxuetong (SXT), HongHuaHuangSeSu (HHHSS), DengZhanXiXin (DZXX) and Shenxiong glucose (SX) plus AADN were the optimum treatment regimens for ACI, especially SXN + AADN and YXDM + AADN. CONCLUSIONS: Based on the NMA, SXN, YXDM, DH, SXT, HHHSS, DZXX and SX plus AADN showed the highest probability of being the best treatment regimens. Due to the limitations of the present study, our findings should be verified by well-designed RCTs.

Green emitting N,S-co-doped carbon dots for sensitive fluorometric determination of Fe(III) and Ag(I) ions, and as a solvatochromic probe.

N,S-co-doped carbon dots (N,S-CDs) were synthesized via a single-step solvothermal process by using sodium lignosulfonate and p-phenylenediamine as carbon/nitrogen/sulfur sources. The N,S-CDs have an average diameter of 2.02 ± 1 nm and display green fluorescence, with excitation/emission peak wavelengths at 380/540 nm for optimal fluorescence. Fluorescence is excitation wavelength-dependent and stable in aqueous salt solutions. The fluorescence of the N,S-CDs is selectively quenched by Fe(III) and Ag(I) ions. These ions can be quantified by fluorometry with a limit of detection of 1.7 µM for Fe(III) ions and 11.6 µM for Ag(I) ions. The N,S-CDs also undergo solvatochromism in that emission is green in water solution but blue in polar organic solvents such as ethanol or N,N-dimethylformamide. The color of fluorescence gradually shifts from green to blue when continuously increasing the fraction of organic solvent in water. Graphical abstract N,S-co-doped carbon dots (N,S-CDs) are synthesized by using sodium lignosulfonate and p-phenylenediamine as C/N/S sources. The N,S-CDs can sensitively detect Fe(III) and Ag(I) ions based on fluorometry, and can be used as a solvatochromic probe.

Uptake and accumulation of potentially toxic elements in colonized plant species around the world's largest antimony mine area, China.

To provide information on reclamation of multi-heavy metal polluted soils with conception of phytostabilization, a field survey on the uptake and accumulation of potentially toxic elements such as antimony (Sb), arsenic (As), lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) in colonized plant species around the world's largest antimony mine area, China, was conducted. Samples including leaves and shoots (including roots and stems) of colonized plants as well as rhizospheric soils were collected from eight sampling zones in the studied area. The results showed that the contents of Cu, Zn, and Pb in rhizospheric soils below plants were comparable to the corresponding background values of Hunan province, otherwise Sb, Cd, and As contents were extremely high (17-106, 17-87, and 3-7 times of the corresponding background values). The highest concentration of Sb was found in Aster subulatus (410 mg kg-1); Cd, As, and Zn were in Herba bidentis bipinnatae (10.9, 264, and 265 mg kg-1, respectively); and Cu was in Artemisia lavandulaefolia (27.1 mg kg-1). It also exhibited that all the contents of As in leaves were several times of those in shoots of plants, Cd and other heavy metals showed in a similar pattern in several studied species, implying that the uptake route of these heavy metals via foliar might contribute to the accumulation. With high bioconcentration factors of heavy metals (more than 1, except for Zn), together with the growth abundance, Herba bidentis bipinnatae was considered as the most suitable colonized species for phytostabilization of the multi-heavy metal pollution in soils on this antimony mine area.

Smart-Adhesive, Breathable and Waterproof Fibrous Electronic Skins.

For the need of direct contact with the skin, electronic skins (E-skins) should not only fulfill electric functions, but also ensure comfort during wearing, including permeability, waterproofness, and easy removal. Herein, the study has developed a self-adhesive, detach-on-demand, breathable, and waterproof E-skin (PDSC) for motion sensing and wearable comfort by electrospinning styrene-isoprene block copolymer rubber with carbon black nanosheets as the sensing layer and liner copolymers of N, N-dimethylacrylamide, n-octadecyl acrylate and lauryl methacrylate as the adhesive layer. The high elasticity and microfiber network structure endow the PDSC with good sensitivity and high linearity for strain sensing. The hydrophobic and crystallizable adhesive layer ensures robust, waterproof, and detaching-on-demand skin adhesion. Meanwhile, the fiber structure enables the PDSC good air and water permeability. The integration of electric and wearable functions endows the PDSC with great potential for motion sensing during human activities as both the sensing and wearable performances.

Boosting Zn-Ion Storage Behavior of Pre-Intercalated MXene with Black Phosphorus toward Self-Powered Systems.

MXene-based Zn-ion capacitors (ZICs) with adsorption-type and battery-type electrodes demonstrate high energy storage and anti-self-discharge capabilities, potentially being paired with triboelectric nanogenerators (TENGs) to construct self-powered systems. Nevertheless, inadequate interlayer spacing, deficient active sites, and compact self-restacking of MXene flakes pose hurdles for MXene-based ZICs, limiting their applications. Herein, black phosphorus (BP)-Zn-MXene hybrid is formulated for MXene-based ZIC via a two-step molecular engineering strategy of Zn-ion pre-intercalation and BP nanosheet assembly. Zn ions as intercalators induce cross-linking of MXene flakes with expandable interlayer spacing to serve as scaffolds for BP nanosheets, thereby providing sufficient accessible active sites and efficient migration routes for enhanced Zn-ion storage. The density functional theory calculations affirm that zinc adsorption and diffusion kinetics are significantly improved in the hybrid. A wearable ZIC with the hybrid delivers a competitive areal energy of 426.3 µWh cm-2 and ultra-low self-discharge rate of 7.0 mV h-1, achieving remarkable electrochemical matching with TENGs in terms of low energy loss, matched capacity, and fast Zn-ion storage. The resultant self-powered system efficiently collects and stores energy from human motion to power microelectronics. This work advances the Zn-ion storage of MXene-based ZICs and their synergy with TENG in self-powered systems.

Naturally Crosslinked Biocompatible Carbonaceous Liquid Metal Aqueous Ink Printing Wearable Electronics for Multi-Sensing and Energy Harvesting.

Achieving flexible electronics with comfort and durability comparable to traditional textiles is one of the ultimate pursuits of smart wearables. Ink printing is desirable for e-textile development using a simple and inexpensive process. However, fabricating high-performance atop textiles with good dispersity, stability, biocompatibility, and wearability for high-resolution, large-scale manufacturing, and practical applications has remained challenging. Here, water-based multi-walled carbon nanotubes (MWCNTs)-decorated liquid metal (LM) inks are proposed with carbonaceous gallium-indium micro-nanostructure. With the assistance of biopolymers, the sodium alginate-encapsulated LM droplets contain high carboxyl groups which non-covalently crosslink with silk sericin-mediated MWCNTs. E-textile can be prepared subsequently via printing technique and natural waterproof triboelectric coating, enabling good flexibility, hydrophilicity, breathability, wearability, biocompatibility, conductivity, stability, and excellent versatility, without any artificial chemicals. The obtained e-textile can be used in various applications with designable patterns and circuits. Multi-sensing applications of recognizing complex human motions, breathing, phonation, and pressure distribution are demonstrated with repeatable and reliable signals. Self-powered and energy-harvesting capabilities are also presented by driving electronic devices and lighting LEDs. As proof of concept, this work provides new opportunities in a scalable and sustainable way to develop novel wearable electronics and smart clothing for future commercial applications.

Touch initiated on-demand adhesion on rough surfaces.

Reversible adhesion with on-demand attachment and detachment is used by many animals for their locomotion. However, achieving robust and switchable adhesion on rough surfaces in artificial adhesives remains a significant challenge. Here, we present a snail mucus-inspired touch-initiate adhesive (TIA), showing robust adhesions on various surfaces. TIA is a polymeric hydrogel photo-cured with the presence of supersaturated sodium acetate (NaAc) in the precursor solution. TIA is soft and flexible at room temperature, allowing it to form conformal contact with objects with various surfaces. The contact with the target surface immediately initiates the crystallization of TIA, increasing the elastic modulus of TIA by an order of magnitude. The increased modulus and the interlocking with the target surfaces thus results in an adhesion strength up to 465.56 ± 84.05 kPa. TIA can be easily detached from the surface by heating to a temperature above 58 °C, showing an adhesion strength of 12.71 ± 2.73 kPa. The detached TIA, even cooled down to and kept at room temperature, is readily used for the subsequent adhesion. The study here not only provides a highly adhesive material for on-demand attachment to various surfaces, but also proposes a new design strategy to compose smart materials.

Bioinspired Touch-Responsive Hydrogels for On-Demand Adhesion on Rough Surfaces.

Reversible adhesives are widely needed in our daily lives and industrial applications. However, robust and switchable adhesion on rough surfaces with on-demand attachment and detachment remains highly challenging. Here, we report a snail-mucus-inspired touch-responsive hydrogel (TRH), whose universal and robust adhesion is triggered by simple contact with the attaching surface. TRH is composed of a polymeric hydrogel and saturated sodium acetate (NaAc) and is prepared by one-pot synthesis. At room temperature, TRH remains in an amorphous and soft state, which allows it to conformally adapt to rough surfaces. The contact with the target surface triggers the crystallization of NaAc, which increases the modulus of TRH by an order of magnitude and interlocks with the target surfaces, achieving an adhesion of up to 204.84 ± 53.98 kPa. Upon heating, TRH returns to a soft state, facilitating easy detachment with adhesion of 5.12 ± 1.34 kPa. Meanwhile, the detached TRH is ready for the next adhesion without the need to be maintained at high temperature. TRH finds applications as a smart material for light-triggered adhesion switching, information encryption, and temperature sensors.

Natural Silkworm Cocoon-Based Hierarchically Architected Composite Triboelectric Nanogenerators for Biomechanical Energy Harvesting.

Silk-based triboelectric nanogenerators (TENGs) have been demonstrated as an ideal platform for self-powered systems. The source of silk, Bombyx mori, entails a valuable ingredient, sericin (SS), viewed as a binder in composites. Interestingly, SS is rich in the amorphous region, possibly resulting in triboelectrification enhancement between the amorphous region and the crystallization region when subject to external pressure. However, most researchers remove the SS component when designing silk-TENGs to eliminate immunological responses as implantation in vivo through complicated degumming, rehydration, and dialysis procedures. Herein, integral SS retention was utilized to fabricate silk-TENGs without affecting the output performance. We designed, for the first time, an ultra-robust and natural silkworm cocoon layer (SCL)/polydimethylsiloxane (PDMS)-TENG as an energy harvester to scavenge waste energy from human motions. The working mechanisms and influence of operational parameters are explored and studied. Working in the contact-separation mode, the electrical outputs of the SCL/PDMS-TENG in terms of open-circuit voltage, short-circuit current, and power density reaches 126 V, 3 µA, and 216 mW/m2, respectively. The integrated self-charging TENG is demonstrated to power small electronic electronics and monitor human motions. This work widens a new dielectric material selection with SS retention to boost the output performance of TENGs for practical applications.

The non-coevolution of DIC and alkalinity and the CO2 degassing in a karst river affected by acid mine drainage in Southwest China.

Dissolved inorganic carbon (DIC) in mine water generated during coal mining is a large and potential source of atmospheric CO2, however its geochemical behaviors under the influence of AMD in relation to CO2 degassing and carbonate buffering are not well known. In this study, water temperature, pH, DO, alkalinity, Ca2+ concentration, and the carbon isotope of DIC were measured monthly from November 2020 to November 2021 and carbonate chemistry and CO2 emission flux were calculated to reveal the processes of DIC evolution and CO2 degassing from the Chetian River draining a karst region, which is materially affected by the input of large quantities of AMD. The results showed that carbonate erosion, the mineralization of terrestrial organic matter, and domestic sewage input are all identified to contribute DIC to different degrees to the river. Throughout the year, the Chetian River undergoes high-intensity CO2 degassing, which is dominated by HCO3--neutralized degassing and proton-enhanced degassing in different reaches. The pCO2 in the river under the influence of AMD is as high as 237,482 µatm, while the F-CO2 approaches 316.9 g C m-2 d-1. Meanwhile, the carbonate system in the downstream karst river buffers an average of 85.2 % of DIC release at the river's outlet. The input of AMD significantly altered the carbon cycle of the surface watershed in the headwaters of tributaries, and greatly enhanced the release of CO2 from surface water to the atmosphere; meanwhile, the buffering of carbonates on acidity in the water of main streams causes pCO2 to rapidly reduce over a short distance. Obviously, the carbon emission effect generated by the interaction between AMD and carbonate mainly occurs in the tributary water system. Considering the huge amount of AMD worldwide, this large potential source of atmospheric CO2 requires a specific and precise quantitative analysis based on actual observations.