Rapid Determination of Tetracyclines in Drinking and Environmental Waters Using Fully Automatic Solid-Phase Extraction with Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry.

The abuse and irrational use of tetracyclines (TCs) in human medicine and animal husbandry has become a serious concern, affecting the ecological environment and human health. The aim of this study was to develop a sensitive and selective method using fully automatic solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for the determination of twelve TCs in water. Four isotope-labeled internal standards for TCs were used to correct matrix effects. Several parameters affecting extraction efficiency were systematically optimized, and the optimum experimental conditions found were 1.0 L water sample with 0.5 g/L Na2EDTA (pH 3.0) extracted and enriched by CNW HLB cartridge and eluted by 4 mL of acetone:methanol (v/v, 1:1). The enrichment factors were up to 798-1059 but only requiring about 60 min per six samples. Under the optimized conditions, the linearity of the method ranged from 0.2 to 100 µg/L for 12 TCs, the detection limits were as low as 0.01-0.15 ng/L, and the recoveries were in the range of 70%-118%, with relative standard deviations less than 15%. The developed method can be successfully utilized for the determination of 12 TCs in pure water, tap water, river water, and mariculture seawater. In summary, three and six TCs were detected in river water and mariculture seawater, respectively, with total concentrations of 0.074-0.520 ng/L (mean 0.248 ng/L) and 0.792-58.369 ng/L (12.629 ng/L), respectively. Tetracycline (TC) and oxytetracycline (OTC) were the dominant TCs in river water, while doxytetracycline (DXC) and OTC were dominant in mariculture seawater.

An Automated Solid-Phase Extraction-UPLC-MS/MS Method for Simultaneous Determination of Sulfonamide Antimicrobials in Environmental Water.

The large-scale use of sulfonamide antimicrobials in human and veterinary medicine has seriously endangered the ecological environment and human health. The objective of this study was to develop and validate a simple and robust method for the simultaneous determination of seventeen sulfonamides in water using ultra-high performance liquid chromatography-tandem mass spectrometry coupled with fully automated solid-phase extraction. Seventeen isotope-labeled internal standards for sulfonamides were used to correct matrix effects. Several parameters affecting extraction efficiency were systematically optimized, and the enrichment factors were up to 982-1033 and only requiring about 60 min per six samples. Under the optimized conditions, this method manifested good linearity (0.05-100 µg/L), high sensitivity (detection limits: 0.01-0.05 ng/L), and satisfactory recoveries (79-118%) with acceptable relative standard deviations (0.3-14.5%, n = 5). The developed method can be successfully utilized for the determination of 17 sulfonamides in pure water, tap water, river water, and seawater. In total, six and seven sulfonamides were detected in river water and seawater, respectively, with a total concentration of 8.157-29.676 ng/L and 1.683-36.955 ng/L, respectively, and sulfamethoxazole was the predominant congener.

Database examination, multivariate analysis, and machine learning: Predictions of vapor intrusion attenuation factors.

Traditional soil vapor intrusion (VI) models usually rely on preset conceptual scenarios, simplifying the influences of limiting environmental covariates in determining indoor attenuation factors relative to subsurface sources. This study proposed a technical framework and applied it to predict VI attenuation factors based on site-specific parameters recorded in the United States Environmental Protection Agency (USEPA)'s and the California Environmental Protection Agency (CalEPA)'s VI databases, which can overcome the limitations of traditional VI models. We examined the databases with multivariate analysis of variance to identify effective covariates, which were then employed to develop VI models with three machine learning algorithms. The results of multivariate analysis show that the effective covariates include soil texture, source depth, foundation type, lateral separation, surface cover, and land use. Based on these covariates, the predicted attenuation factors by these new models are generally within one order of magnitude of the observations recorded in the databases. Then the developed models were employed to generate the generic indoor attenuation factors to subsurface vapor (i.e., the 95th percentile of selected dataset), the values of which are different between the USEPA's and CalEPA's databases by one order of magnitude, although comparable to recommendations by the USEPA and literature, respectively. Such a difference may reflect the significant regional disparity in factors such as building structures or operational conditions (e.g., indoor air exchange rates), which necessitates generating generic VI attenuation factors on a state-specific basis. This study provides an alternative for VI risk screens on a site-specific basis, especially in states with a good collection of datasets. Although the proposed technical framework is used for the VI databases, it can be equally applied to other environmental science problems.

Spectroscopic characterization of dissolved organic matter from macroalgae Ulva pertusa decomposition and its binding behaviors with Cu(II).

Dissolved organic matter (DOM) from macroalgae is regarded a crucial source of autochthonous DOM in coastal ocean. In the present study, the characteristics of DOM from the macroalgae Ulva pertusa decomposition (U. pertusa-DOM) and its binding behaviors with Cu(II) using multiple spectroscopic techniques and chemometric analyses. The labile U. pertusa-DOM could be consumed and transformed by microorganisms. The absorption spectroscopic descriptors indicate that the hydrophobicity, aromaticity, and molecular weight of the U. pertusa-DOM increase during the 27-day incubation period. Fluorescence excitation-emission matrix spectroscopy combined with parallel factor analysis suggests that the relative abundance of the protein-like component (C1) (96.10-84.96%) sequentially decreases, whereas the humic-like components (C2) (2.16-9.73%) and (C3) (1.75-5.31%) in the U. pertusa-DOM increase with the U. pertusa decomposition. The Cu(II) binding properties of the U. pertusa-DOM are dependent on the decomposition time. The order of the conditional stability constant (logKM) is C2 > C1 > C3. The complexation capacity (f) of C1 is higher than those of C2 and C3 at a specific time. Synchronous fluorescence spectroscopy coupled with two-dimensional correlation spectroscopy reveals that the microbial degradation could accelerate the Cu(II) binding to humic-like fractions in the U. pertusa-DOM. These findings will help us better understand the biogeochemical behaviors of macroalgal DOM and heavy metal in coastal ecosystems.

Development and Validation of a Controlled Pressure Method Test Protocol for Vapor Intrusion Pathway Assessment.

Controlled pressure method (CPM) testing is a building-specific diagnostic tool for vapor intrusion (VI) pathway assessment which offers advantages over traditional pathway assessment approaches. By manipulating the building pressure conditions, the CPM creates the worst-case VI impact and provides rapid insight into the type of vapor source(s). The primary barrier to general acceptance and use of this tool is the need for definitive guidance on test design parameters, such as the indoor-outdoor pressure difference (or exhaust fan flow rate), CPM test duration, exhaust fan location, and air sampling location(s) and conditions. This study focused on a systematic evaluation of each of these factors, which then led to the formulation of proposed CPM testing guidelines. The results suggest that CPM tests should be conducted with both negative and positive pressure indoor-outdoor differentials of about 10-15 Pa, and the tests should last for at least nine indoor air exchanges for negative pressure difference testing and four indoor air exchanges for positive pressure difference testing. Although exhaust fan intake sampling is sufficient to provide critical information to assess impacts during negative pressure testing, adding room-specific indoor air sampling to both negative and positive pressure difference testing can provide insight into vapor entry locations and indoor source contributions.

Creation of a Sub-slab Soil Gas Cloud by an Indoor Air Source and Its Dissipation Following Source Removal.

It is accepted that indoor sources of volatile organic compounds can confound vapor intrusion (VI) pathway assessment. When they are discovered during pre-sampling inspection, indoor sources are removed and air sampling is delayed, with the assumption that a few hours to a few days are sufficient for indoor source impacts to dissipate. This assumption was tested through the controlled release of SF6 and its monitoring in indoor air and soil gas at a study house over 2 years. Results show that indoor sources generate subsurface soil gas clouds as a result of fluctuating direction in the exchange between soil gas and indoor air and that it may take days to weeks under natural conditions for a soil gas cloud beneath a building to dissipate following indoor source removal. The data also reveal temporal variability in indoor air and soil gas concentrations, long-term seasonal patterns, and dissipation of soil gas clouds over days to weeks following source removal. Preliminary modeling results for similar conditions are consistent field observations. If representative of other sites, these results suggest that a typical 1-3 day waiting period following indoor source removal may not be sufficient to avoid confounding data and erroneous conclusions regarding VI occurrence.

Determination of 15 polycyclic aromatic hydrocarbons in aquatic products by solid-phase extraction and GC-MS.

We propose a method for the simultaneous determination of 15 kinds of polycyclic aromatic hydrocarbons in marine samples (muscle) employing gas chromatography with mass spectrometry after saponification with ultrasound-assisted extraction and solid-phase extraction. The experimental conditions were optimized by the response surface method. In addition, the effects of different lyes and extractants on polycyclic aromatic hydrocarbons extraction were discussed, and saturated sodium carbonate was first used as the primary saponification reaction and extracted with 10 mL of ethyl acetate and secondly 1 mol/L of sodium hydroxide and 10 mL of n-hexane were used to achieve better results. The average recovery was 67-112%. Satisfactory data showed that the method has good reproducibility with a relative standard deviation of <13%. The detection limits of polycyclic aromatic hydrocarbons were 0.02-0.13 ng/g. Compared with other methods, this method has the advantages of simple pretreatment, low solvent consumption, maximum polycyclic aromatic hydrocarbons extraction, the fast separation speed, and the high extraction efficiency. It is concluded that this method meets the batch processing requirements of the sample and can also be used to determine polycyclic aromatic hydrocarbons in other high-fat (fish, shrimp, crab, shellfish) biological samples.

Primary secondary amine as a sorbent material in dispersive solid-phase extraction clean-up for the determination of indicator polychlorinated biphenyls in environmental water samples by gas chromatography with electron capture detection.

A simple, rapid, and novel method has been developed and validated for determination of seven indicator polychlorinated biphenyls in water samples by gas chromatography with electron capture detection. 1 L of water samples containing 30 g of anhydrous sodium sulfate was first liquid-liquid extracted with an automated Jipad-6XB vertical oscillator using n-hexane/dichloromethane (1:1, v/v). The concentrated extract was cleaned up by dispersive solid-phase extraction with 100 mg of primary secondary amine as sorbent material. The linearity of this method ranged from 1.25 to 100 µg/L, with regression coefficients ranging between 0.9994 and 0.9999. The limits of detection were in the ng/L level, ranging between 0.2 and 0.3 ng/L. The recoveries of seven spiked polychlorinated biphenyls with external calibration method at different concentration levels in tap water, lake water, and sea water were in the ranges of 85-112, 76-116, and 72-108%, respectively, and with relative standard deviations of 3.3-4.5, 3.4-5.6, and 3.1-4.8% (n = 5), respectively. The performance of the proposed method was compared with traditional liquid-liquid extraction and solid-phase extraction clean-up methods, and comparable efficiencies were obtained. It is concluded that this method can be successfully applied for the determination of polychlorinated biphenyls in different water samples.

Determination of volatile chlorinated hydrocarbons in water samples by static headspace gas chromatography with electron capture detection.

A simple, efficient, solvent-free, and commercial readily available approach for determination of five volatile chlorinated hydrocarbons in water samples using the static headspace sampling and gas chromatography with electron capture detection has been described. The proposed static headspace sampling method was initially optimized and the optimum experimental conditions found were 10 mL water sample containing 20% w/v sodium chloride placed in a 20 mL vial and stirred at 50ºC for 20 min. The linearity of the method was in the range of 1.2-240 µg/L for dichloromethane, 0.2-40 µg/L for trichloromethane, 0.005-1 µg/L for perchloromethane, 0.025-5 µg/L for trichloroethylene, and 0.01-2 µg/L for perchloroethylene, with coefficients of determination ranging between 0.9979 and 0.9990. The limits of detection were in the low µg/L level, ranging between 0.001 and 0.3 µg/L. The relative recoveries of spiked five volatile chlorinated hydrocarbons with external calibration method at different concentration levels in pure, tap, sea water of Jiaojiang Estuary, and sea water of waters of Xiaomendao were in the range of 91-116, 96-105, 86-112, and 80-111%, respectively, and with relative standard deviations of 1.9-3.6, 2.3-3.5, 1.5-2.7, and 2.3-3.7% (n = 5), respectively. The performance of the proposed method was compared with traditional liquid-liquid extraction on the real water samples (i.e., pure, tap, and sea water, etc.) and comparable efficiencies were obtained. It is concluded that this method can be successfully applied for the determination of volatile chlorinated hydrocarbons in different water samples.

Identification of Alternative Vapor Intrusion Pathways Using Controlled Pressure Testing, Soil Gas Monitoring, and Screening Model Calculations.

Vapor intrusion (VI) pathway assessment and data interpretation have been guided by an historical conceptual model in which vapors originating from contaminated soil or groundwater diffuse upward through soil and are swept into a building by soil gas flow induced by building underpressurization. Recent studies reveal that alternative VI pathways involving neighborhood sewers, land drains, and other major underground piping can also be significant VI contributors, even to buildings beyond the delineated footprint of soil and groundwater contamination. This work illustrates how controlled-pressure-method testing (CPM), soil gas sampling, and screening-level emissions calculations can be used to identify significant alternative VI pathways that might go undetected by conventional sampling under natural conditions at some sites. The combined utility of these tools is shown through data collected at a long-term study house, where a significant alternative VI pathway was discovered and altered so that it could be manipulated to be on or off. Data collected during periods of natural and CPM conditions show that the alternative pathway was significant, but its presence was not identifiable under natural conditions; it was identified under CPM conditions when measured emission rates were 2 orders of magnitude greater than screening-model estimates and subfoundation vertical soil gas profiles changed and were no longer consistent with the conventional VI conceptual model.

Long-term evaluation of the controlled pressure method for assessment of the vapor intrusion pathway.

Vapor intrusion (VI) investigations often require sampling of indoor air for evaluating occupant risks, but can be confounded by temporal variability and the presence of indoor sources. Controlled pressure methods (CPM) have been proposed as an alternative, but temporal variability of CPM results and whether they are indicative of impacts under natural conditions have not been rigorously investigated. This study is the first involving a long-term CPM test at a house having a multiyear high temporal resolution indoor air data set under natural conditions. Key observations include (a) CPM results exhibited low temporal variability, (b) false-negative results were not obtained, (c) the indoor air concentrations were similar to the maximum concentrations under natural conditions, and (d) results exceeded long-term average concentrations and emission rates under natural conditions by 1-2 orders of magnitude. Thus, the CPM results were a reliable indicator of VI occurrence and worst-case exposure regardless of day or time of year of the CPM test.

A selective biomarker for confirming nitrofurazone residues in crab and shrimp using ultra-performance liquid chromatography-tandem mass spectrometry.

Reliably detecting nitrofurazone (NFZ) residues in farmed crab and shrimp was previously hindered by lack of appropriately specific analytical methodology. Parent NFZ rapidly breaks down in meat, and the commonly used side-chain metabolite, semicarbazide (SEM), is non-specific as it occurs naturally in crustacean shell often leading to 'false positive' detections in meat. Using 5-nitro-2-furaldehyde (NF) as marker metabolite, following pre-column derivatization with 2,4-dinitrophenylhydrazine (DNPH), ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) analysis in negative electrospray ionization mode enabled confirmation of NFZ residues in deliberately treated whole crab, crab meat and shrimp meat, with a limit of detection (LOD) and limit of quantification (LOQ) below 1 ng g(-1). Meanwhile, the derivatives of DNPH-NF were synthesized for the first time, purified by preparative liquid chromatography and structure characterized with nuclear magnetic resonance spectroscopy ((1)H-NMR). The purity of derivative was checked by ultra-performance liquid chromatography-tunable ultraviolet (UPLC-TUV), and the contents were beyond 99.9%. For comparison purposes, crustacean samples were analysed using both NF and SEM marker metabolites. NFZ treatment was revealed by both NF and SEM marker metabolites, but untreated crab also showed measurable levels of SEM which could potentially be misinterpreted as evidence of illegal NFZ use.

Ultrasound-assisted extraction and solid-phase extraction as a cleanup procedure for organochlorinated pesticides and polychlorinated biphenyls determination in aquatic samples by gas chromatography with electron capture detection.

The feasibility of developing a quick, easy, efficient procedure for the simultaneous determination of organochlorinated pesticides and polychlorinated biphenyls in aquatic samples using gas chromatography with electron capture detection based on solid-phase extraction was investigated. The extraction solvent (n-hexane/acetone, cyclohexane/ethyl acetate, n-hexane/dichloromethane, n-hexane) for ultrasound-assisted solid-liquid extraction and solid-phase extraction columns (florisil, neutral alumina, acidic alumina, aminopropyl trimethoxy silane, propyl ethylenediamine, aminopropyl trimethoxy silane/propyl ethylenediamine, graphitized carbon black and silica) for cleanup procedure were optimized. The gas chromatography with electron capture detection method was validated in terms of linearity, sensitivity, reproducibility, and recovery. Mean recoveries ranged from 75 to 115% with relative standard deviations <13%. Quantification limits were 0.20-0.40 ng/g for organochlorinated pesticides and polychlorinated biphenyls. The satisfactory data demonstrated the good reproducibility of the method with relative standard deviations lower than 13%. In comparison to other related methods, this method requires less time and solvent and allows for rapid isolation of the target analytes with high selectivity. This method therefore allows for the screening of numerous samples and can also be used for routine analyses.

Determination of benzene series compounds and chlorobenzenes in water sample by static headspace gas chromatography with flame ionization detection.

A simple, efficient, solvent-free, and readily commercially available approach for the determination of eight benzene series compounds and 12 chlorobenzenes in water samples using the static headspace sampling and gas chromatography with flame ionization detection has been described in this paper. The proposed static headspace sampling method was initially optimized, and the optimum experimental conditions explored were 10 mL water sample containing 20% w/v sodium chloride placed in a 20 mL vial and stirred at 70°C for 43 min. The linearity of the method ranged from 1 to 200 µg/L for 20 analytes, with correlation coefficients ranging between 0.9962 and 0.9994. The limits of detection were in the µg/L level, ranging between 0.15 and 0.4 µg/L. The relative recoveries of spiked benzene series and chlorobenzenes with external calibration method at different concentration levels in pure, tap, and sea water samples were 84-113, 78-115 and 85-119%, respectively, with relative standard deviations of 3.8-6.8, 4.1-5.8, and 4.8-5.4% (n = 5), respectively. That this method can be successfully applied to the determination of benzene series compounds and chlorobenzenes in pure, tap, and sea water samples, simultaneously.

Co-metabolic biodegradation of DBP by Paenibacillus sp. S-3 and H-2.

Two di-n-butyl phthalate (DBP)-degrading strains, designated as S-3 and H-2, were isolated from DBP-polluted soil and both identified as Paenibacillus sp. When DBP was provided as the sole carbon source, about 45.5 and 71.7 % of DBP (100 mg/L) were degraded by strain S-3 and H-2, respectively, after incubation for 48 h. However, DBP (100 mg/L) was degraded completely by co-culture of strain S-3 and H-2 after incubation for 60 h. Four phthalic acid (PA) esters could be utilized by co-metabolism in the study and the degradation rates followed the order of dimethyl phthalate > diethyl phthalate > DBP > dioctyl phthalate. The metabolic pathway of DBP was elucidated based on the results of metabolites identification and enzyme assays. For strain S-3, DBP was degraded into butyl hydrogen phthalate which was degraded to PA by carboxyesterase further. But PA could be not hydrolyzed further because strain S-3 lacked 3,4-phthalate dioxygenase. Different with S-3, strain H-2 could hydrolyze PA into 3,4-dihydroxy-PA by 3,4-phthalate dioxygenase. Then 3,4-dihydroxy-PA was converted to protocatechuate and benzoic acid. Finally, the aromatic ring was cleavage and mineralized to CO2 and H2O. Above all, co-metabolism could increase the activity of 3,4-phthalate dioxygenase and accelerated the degradation of DBP. This study highlights an important potential use of co-metabolic biodegradation for the in situ bioremediation of DBP and its metabolites-contaminated environment.

Municipal pipeline networks as preferential vapor intrusion pathways: A review.

Recent reports show a rise in instances where municipal networks, such as sewer lines, serve as pathways for vapor intrusion (VI), enabling volatile organic compounds (VOCs) vapors to travel along these networks. These VOCs pose potential health risks to occupants of buildings connected to these networks. Currently, there's a lack of specific technical or regulatory guidance on identifying and assessing the VI risk associated with sewer as preferential VI pathways. This critical review summarizes key findings from studies and site investigations related to sewer VI pathways. These findings cover background VOCs concentration levels in sewers, updates to site conceptual models, advances in sewer sampling techniques, innovative tools for identifying and characterizing sewer VI, and practices for assessing and mitigating sewer VI risk. While significant improvements have been made towards understanding how municipal pipeline networks act as VI pathways, more research is still needed to develop strategies for investigating sites and assessing risks associated with "pipeline VI pathways". Future research could focus on the development of "pipeline VI pathways" data set, the improvement and validation of investigation tools, and improving the understanding of VOCs transportation mechanisms within these "pipeline VI pathways".

Determination of Volatile Halogenated Hydrocarbons in Drinking and Environmental Waters by Headspace Gas Chromatography.

Volatile halogenated hydrocarbons (VHHs) are annually produced and released into the environment, posing a threat to public health. In this study, a simple, rapid, sensitive and automated method based on headspace and gas chromatography (GC) with electron-capture detection was described for the determination of VHHs in different concentration levels in water samples. The proposed headspace GC method was initially optimized, and the optimum experimental conditions found were 10-mL water sample containing 20% w/v sodium chloride placed in a 20-mL vial and stirred at 60°C for 35 min, and then 14 VHHs were well separated on DB-35 MS capillary column with a split ratio of 12.5: 1. The limits of detection were in the low µg/L level, ranging between 0.01 and 0.6 µg/L. Finally optimized method was applied for determination 14 VHHs in drinking and environmental waters. The total mean concentrations of VHHs were 34.962, 26.183, 3.228 and 647.344 µg/L in tap water, purified water with 1-year-old filter element, seawater and effluents, respectively. However, no VHHs was detected in purified water with a new filter element. The main composition is different among different water matrix, which may be attributed to their different sources.

Rapid determination of catecholamines in urine samples by nonaqueous microchip electrophoresis with LIF detection.

A method was developed for the rapid separation of catecholamines by nonaqueous microchip electrophoresis with LIF detection, A homemade pump-free negative pressure sampling device was used for rapid bias-free sampling in nonaqueous microchip electrophoresis, the injection time was 0.5 s and the electrophoresis separation conditions were optimized. Under the optimized conditions, the samples were separated completely in less than 1 min. The average migration times of the epinephrine, dopamine, and norepinephrine were 34.26, 43.81, and 50.07 s, with a relative standard deviation of 1.05, 1.26 and 0.89% (n = 7), respectively. The linearity of the method ranged from 0.0125 to 2.0 mg/L for epinephrine and 0.025∼4.0 mg/L for dopamine, and norepinephrine, with correlation coefficients ranging between 0.9978 and 0.9986. The detection limits of epinephrine, dopamine, and norepinephrine were 2.5, 5.0 and 5.0 µg/L, respectively. The recoveries of epinephrine, dopamine, and norepinephrine in spiked urine samples were between 86 and 103%, with relative standard deviations of 4.5∼6.8% (n = 5). The proposed nonaqueous microchip electrophoresis with laser induced fluorescence detection system combined with a pump-free negative pressure sampling device was a simple, inexpensive, energy efficient, miniaturized system that can be successfully applied for the determination of catecholamines in urine samples. This article is protected by copyright. All rights reserved.

Rapid determination of catecholamines in urine samples by nonaqueous microchip electrophoresis with LIF detection.

A method was developed for the rapid separation of catecholamines by nonaqueous microchip electrophoresis (NAMCE) with LIF detection, A homemade pump-free negative pressure sampling device was used for rapid bias-free sampling in NAMCE, the injection time was 0.5 s and the electrophoresis separation conditions were optimized. Under the optimized conditions, the samples were separated completely in <1 min. The average migration times of the epinephrine (E), dopamine (DA), and norepinephrine (NE) were 34.26, 43.81, and 50.07 s, with an RSD of 1.05, 1.26, and 0.89% (n = 7), respectively. The linearity of the method ranged from 0.0125 to 2.0 mg/L for E and 0.025~4.0 mg/L for DA and NE, with correlation coefficients ranging between 0.9978 and 0.9986. The detection limits of E, DA, and NE were 2.5, 5.0, and 5.0 µg/L, respectively. The recoveries of E, DA, and NE in spiked urine samples were between 86 and 103%, with RSDs of 4.5~6.8% (n = 5). The proposed NAMCE with LIF detection combined with a pump-free negative pressure sampling device is a simple, inexpensive, energy efficient, miniaturized system that can be successfully applied for the determination of catecholamines in urine samples.

Biobased epoxidized natural rubber/sodium carboxymethyl cellulose composites with enhanced strength and healing ability.

Conventional vulcanized rubbers cause a non-negligible waste of resources due to the formation of 3D irreversible covalently cross-linked networks. The introduction of reversible covalent bonds, such as reversible disulfide bonds, into the rubber network, is an available solution to the above problem. However, the mechanical properties of rubber with only reversible disulfide bonds cannot meet most practical applications. In this paper, a strengthened bio-based epoxidized natural rubber (ENR) composite reinforced by sodium carboxymethyl cellulose (SCMC) was prepared. SCMC forms a mass of hydrogen bonds between its hydroxyl groups and the hydrophilic groups of ENR chain, which gives the ENR/2,2'-Dithiodibenzoic acid (DTSA)/SCMC composites an enhanced mechanical performance. With 20 phr SCMC, the tensile strength of the composite increases from 3.0 to 10.4 MPa, which is almost 3.5 times that of the ENR/DTSA composite without SCMC. Simultaneously, DTSA covalently cross-linked ENR with the introduction of reversible disulfide bonds, which enables the cross-linked network to rearrange its topology at low temperatures and thus endows the ENR/DTSA/SCMC composites with healing properties. The ENR/DTSA/SCMC-10 composite has a considerable healing efficiency of about 96 % after healing at 80 °C for 12 h.