Efficient Catalytic Oxidation of Ethylene at 0 °C on an in Situ Carbon Modified Pt Catalyst Supported on SBA-15.

The design of efficient catalysts for catalytic ethylene (C2H4) oxidation is of crucial importance for extending the shelf life of fruits and vegetables. Herein, a carbon modified SBA-15 supported Pt catalyst (Pt/CSBA-15) was prepared in situ by a facile solid phase grinding-infiltration-inert atmosphere calcination method. Characterization results reveal that in the Pt/CSBA-15 catalysts thin carbon layers are successfully formed in the hexagonal pores of SBA-15. Additionally, Pt particles are well dispersed in the channels of SBA-15, and Pt/CSBA-15 has a smaller Pt particle size than the catalyst without carbon modification (i.e., Pt/SBA-15). O2 is more feasibly adsorbed and activated on small-sized Pt particles, and in situ formed carbon species enhance the hydrophobicity of catalysts. As a result, both 3Pt/CSBA-15 and 5Pt/CSBA-15 are able to maintain 100% conversion of 50 ppm of C2H4 for more than 7 h at 0 °C. 3Pt/CSBA-15 even achieves 81.5% C2H4 conversion and 71.6% CO2 yield after 20 h, exhibiting much more prominent catalytic performances than 3Pt/SBA-15. DFT calculations and in situ FTIR measurements confirm that small-sized Pt particles possess strong O2 affinity to promote O2 adsorption, and in situ formed hydrophobic carbon layers efficiently suppress competitive H2O adsorption. Such a unique one-step catalyst preparation method for regulating the size of metal particles and the hydrophobicity of catalysts can be perfectly utilized to develop simple and efficient hydrophobic catalysts applied in low-temperature oxidation of C2H4.

Pharmacokinetics of the Recalcitrant Drug Lamotrigine: Identification and Distribution of Metabolites in Cucumber Plants.

Treated wastewater is an important source of water for irrigation. As a result, irrigated crops are chronically exposed to wastewater-derived pharmaceuticals, such as the anticonvulsant drug lamotrigine. Lamotrigine is known to be taken up by plants, but its plant-derived metabolites and their distribution in different plant organs are unknown. This study aimed to detect and identify metabolites of lamotrigine in cucumber plants grown for 35 days in a hydroponic solution by using LC-MS/MS (Orbitrap) analysis. Our data showed that 96% of the lamotrigine taken up was metabolized. Sixteen metabolites possessing a lamotrigine core structure were detected. Reference standards confirmed two; five were tentatively identified, and nine molecular formulas were assigned. The data suggest that lamotrigine is metabolized via N-carbamylation, N-glucosidation, N-alkylation, N-formylation, N-oxidation, and amidine hydrolysis. The metabolites LTG-N2-oxide, M284, M312, and M370 were most likely produced in the roots and were translocated to the leaves. Metabolites M272, M312, M314, M354, M368, M370, and M418 were dominant in leaves. Only a few metabolites were detected in the fruits. With an increasing exposure time, lamotrigine leaf concentrations decreased because of continuous metabolism. Our data showed that the metabolism of lamotrigine in a plant is fast and that a majority of metabolites are concentrated in the roots and leaves.

Sorption and Mobility of Charged Organic Compounds: How to Confront and Overcome Limitations in Their Assessment.

Permanently charged and ionizable organic compounds (IOC) are a large and diverse group of compounds belonging to many contaminant classes, including pharmaceuticals, pesticides, industrial chemicals, and natural toxins. Sorption and mobility of IOCs are distinctively different from those of neutral compounds. Due to electrostatic interactions with natural sorbents, existing concepts for describing neutral organic contaminant sorption, and by extension mobility, are inadequate for IOC. Predictive models developed for neutral compounds are based on octanol-water partitioning of compounds (Kow) and organic-carbon content of soil/sediment, which is used to normalize sorption measurements (KOC). We revisit those concepts and their translation to IOC (Dow and DOC) and discuss compound and soil properties determining sorption of IOC under water saturated conditions. Highlighting possible complementary and/or alternative approaches to better assess IOC mobility, we discuss implications on their regulation and risk assessment. The development of better models for IOC mobility needs consistent and reliable sorption measurements at well-defined chemical conditions in natural porewater, better IOC-, as well as sorbent characterization. Such models should be complemented by monitoring data from the natural environment. The state of knowledge presented here may guide urgently needed future investigations in this field for researchers, engineers, and regulators.

Abiotic Transformation of Lamotrigine by Redox-Active Mineral and Phenolic Compounds.

The anticonvulsant drug lamotrigine is a recalcitrant environmental pollutant. It was detected in drinking water, surface water, reclaimed wastewater, arable soils, and even in edible crops. In this work, we studied the mechanisms of lamotrigine transformation by a common redox soil mineral, birnessite, in a single-solute system and in bisolute systems with vanillic acid or o-methoxyphenol. In the single-solute system, 28% of lamotrigine was transformed and 14 transformation products (TPs) were identified. Based on a detailed analysis of the TPs, we suggested that lamotrigine is transformed mainly by oxidation, addition, and dechlorination reactions. In the bisolute systems, the redox-active phenolic compounds enhanced the elimination and transformation of lamotrigine. Vanillic acid was more efficient, generating 92% transformation of lamotrigine (58 TPs were identified), whereas o-methoxyphenol induced 48% transformation (35 TPs were identified). In the bisolute system with phenolic compounds, lamotrigine has possibly been transformed mainly via addition reactions with phenolic compounds and their oxidation products (protocatechuic acid, quinone, and oligomers). Thus, masses of the formed TPs were elevated as compared to the parent compound. The current study demonstrates the important role of redox-active minerals and naturally occurring phenolic compounds in abiotic removal and transformation of a recalcitrant environmental pollutant.

Ecological Risk Dynamics of Pharmaceuticals in Micro-Estuary Environments.

Micro-estuarine ecosystems have a surface area <1 km2 and are abundant in Mediterranean regions. As a result of their small size, these systems are particularly vulnerable to the effects of chemical pollution. Due to the fluctuating flow conditions of base flow dominated by treated wastewater effluents and flood events transporting rural and urban non-point-source pollution, micro-estuaries are under a dynamic risk regime, consequently struggling to provide ecological services. This 2 year study explored the occurrence and risks of pharmaceutical contamination in the Alexander micro-estuary in Israel. Pharmaceuticals were detected in all samples (n = 280) at as high as 18 µg L-1 in flood events and 14 µg L-1 in base flow. The pharmaceutical mixture composition was affected by flow conditions with carbamazepine dominating the base flow and caffeine dominating flood events. The median annual risk quotients for fish, crustaceans, and algae were 19.6, 5.2, and 4.5, respectively, indicating that pharmaceuticals pose a high risk to the ecosystem. Ibuprofen, carbamazepine, and caffeine contributed most to the risk quotients. The current work highlights that micro-estuary ecosystems, like the Alexander estuary, are continuously exposed to pharmaceuticals and most likely to other pollutants, placing these ecologically important systems under an elevated risk in comparison to the more frequently studied large estuarine systems.

Pharmaceutical and Personal Care Products: From Wastewater Treatment into Agro-Food Systems.

Irrigation with treated wastewater (TWW) and application of biosolids introduce numerous pharmaceutical and personal care products (PPCPs) into agro-food systems. While the use of TWW and biosolids has many societal benefits, introduction of PPCPs in production agriculture poses potential food safety and human health risks. A comprehensive risk assessment and management scheme of PPCPs in agro-food systems is limited by multiple factors, not least the sheer number of investigated compounds and their diverse structures. Here we follow the fate of PPCPs in the water-soil-produce continuum by considering processes and variables that influence PPCP transfer and accumulation. By analyzing the steps in the soil-plant-human diet nexus, we propose a tiered framework as a path forward to prioritize PPCPs that could have a high potential for plant accumulation and thus pose greatest risk. This article examines research progress to date and current research challenges, highlighting the potential value of leveraging existing knowledge from decades of research on other chemicals such as pesticides. A process-driven scheme is outlined to derive a short list that may be used to refocus our future research efforts on PPCPs and other analogous emerging contaminants in agro-food systems.

Pharmacokinetics in Plants: Carbamazepine and Its Interactions with Lamotrigine.

Carbamazepine and lamotrigine prescribed antiepileptic drugs are highly persistent in the environment and were detected in crops irrigated with reclaimed wastewater. This study reports pharmacokinetics of the two drugs and their metabolites in cucumber plants under hydroponic culture, testing their uptake, translocation, and transformation over 96 h in single and bisolute systems at varying pH. Ruling out root adsorption and transformations in the nutrient solution, we demonstrate that carbamazepine root uptake is largely affected by the concentration gradient across the membrane. Unlike carbamazepine, lamotrigine is adsorbed to the root and undergoes ion trapping in root cells thus its translocation to the shoots is limited. On the basis of that, carbamazepine uptake was not affected by the presence of lamotrigine, while lamotrigine uptake was enhanced in the presence of carbamazepine. Transformation of carbamazepine in the roots was slightly reduced in the presence of lamotrigine. Carbamazepine metabolism was far more pronounced in the shoots than in the roots, indicating that most of the metabolism occurs in the leaves, probably due to higher concentration and longer residence time. This study indicates that the uptake of small nonionic pharmaceuticals is passive and governed by diffusion across the root membrane.

Transformation and Speciation Analysis of Silver Nanoparticles of Dietary Supplement in Simulated Human Gastrointestinal Tract.

Knowledge of the physicochemical properties of ingestible silver nanoparticles (AgNPs) in the human gastrointestinal tract (GIT) is essential for assessing their bioavailability, bioactivity, and potential health risks. The gastrointestinal fate of AgNPs and silver ions from a commercial dietary supplement was therefore investigated using a simulated human GIT. In the mouth, no dissolution or aggregation of AgNPs occurred, which was attributed to the neutral pH and the formation of biomolecular corona, while the silver ions formed complexes with biomolecules (Ag-biomolecule). In the stomach, aggregation of AgNPs did not occur, but extensive dissolution was observed due to the low pH and the presence of Cl-. In the fed state (after meal), 72% AgNPs (by mass) dissolved, with 74% silver ions forming Ag-biomolecule and 26% forming AgCl. In the fasted state (before meal), 76% AgNPs dissolved, with 82% silver ions forming Ag-biomolecule and 18% forming AgCl. A biomolecular corona around AgNPs, comprised of mucin with multiple sulfhydryl groups, inhibited aggregation and dissolution of AgNPs. In the small intestine, no further dissolution or aggregation of AgNPs occurred, while the silver ions existed only as Ag-biomolecule. These results provide useful information for assessing the bioavailability of ingestible AgNPs and their subsequently potential health risks, and for the safe design and utilization of AgNPs in biomedical applications.

Human Exposure to Wastewater-Derived Pharmaceuticals in Fresh Produce: A Randomized Controlled Trial Focusing on Carbamazepine.

Fresh water scarcity has led to increased use of reclaimed wastewater as an alternative and reliable source for crop irrigation. Beyond microbiological safety, concerns have been raised regarding contamination of reclaimed wastewater by xenobiotics including pharmaceuticals. This study focuses on carbamazepine, an anticonvulsant drug which is ubiquitously detected in reclaimed wastewater, highly persistent in soil, and taken up by crops. In a randomized controlled trial we demonstrate that healthy individuals consuming reclaimed wastewater-irrigated produce excreted carbamazepine and its metabolites in their urine, while subjects consuming fresh water-irrigated produce excreted undetectable or significantly lower levels of carbamazepine. We also report that the carbamazepine metabolite pattern at this low exposure level differed from that observed at therapeutic doses. This "proof of concept" study demonstrates that human exposure to xenobiotics occurs through ingestion of reclaimed wastewater-irrigated produce, providing real world data which could guide risk assessments and policy designed to ensure the safe use of wastewater for crop irrigation.

Transformation Pathways of the Recalcitrant Pharmaceutical Compound Carbamazepine by the White-Rot Fungus Pleurotus ostreatus: Effects of Growth Conditions.

The widely used anticonvulsant pharmaceutical carbamazepine is recalcitrant in many environmental niches and thus poses a challenge in wastewater treatment. We followed the decomposition of carbamazepine by the white-rot fungus Pleurotus ostreatus in liquid culture compared to solid-state fermentation on lignocellulosic substrate where different enzymatic systems are active. Carbamazepine metabolites were identified using liquid chromatography-high-resolution mass spectrometry (LC-Q-TOF-MS). In liquid culture, carbamazepine was only transformed to 10,11-epoxy carbamazepine and 10,11-dihydroxy carbamazepine as a dead-end product. During solid-state fermentation, carbamazepine metabolism resulted in the generation of an additional 22 transformation products, some of which are toxic. Under solid-state-fermentation conditions, 10,11-epoxy carbamazepine was further metabolized via acridine and 10,11-dihydroxy carbamazepine pathways. The latter was further metabolized via five subpathways. When (14)C-carbonyl-labeled carbamazepine was used as the substrate, (14)C-CO2 release amounted to 17.4% of the initial radioactivity after 63 days of incubation. The proposed pathways were validated using metabolites (10,11-epoxy carbamazepine, 10,11-dihydroxy carbamazepine, and acridine) as primary substrates and following their fate at different time points. This work highlights the effect of growth conditions on the transformation pathways of xenobiotics. A better understanding of the fate of pollutants during bioremediation treatments is important for establishment of such technologies.

Electrochemistry Combined with LC-HRMS: Elucidating Transformation Products of the Recalcitrant Pharmaceutical Compound Carbamazepine Generated by the White-Rot Fungus Pleurotus ostreatus.

Transformation products (TPs) of environmental pollutants must be identified to understand biodegradation processes and reaction mechanisms and to assess the efficiency of treatment processes. The combination of oxidation by an electrochemical cell (EC) with analysis by liquid chromatography-high-resolution mass spectrometry (LC-HRMS) is a rapid approach for the determination and identification of TPs generated by natural microbial processes. Electrochemically generated TPs of the recalcitrant pharmaceutical carbamazepine (CBZ) were used for a target screening for TPs formed by the white-rot fungus Pleurotus ostreatus. EC with LC-HRMS facilitates detection and identification of TPs because the product spectrum is not superimposed with biogenic metabolites and elevated substrate concentrations can be used. A group of 10 TPs formed in the microbial process were detected by target screening for molecular ions, and another 4 were detected by screening on the basis of characteristic fragment ions. Three of these TPs have never been reported before. For CBZ, EC with LC-HRMS was found to be more effective than software tools in defining targets for the screening and faster than nontarget screening alone in TP identification. EC with LC-HRMS may be used to feed MS databases with spectra of possible TPs of larger numbers of environmental contaminants for an efficient target screening.

Degradation of plant cuticles in soils: impact on formation and sorptive ability of humin-mineral matrices.

Plant cuticles are important precursors for soil organic matter, in particular for soil humin, which is considered an efficient sorbent for organic pollutants. In this study, we examined degradation and transformation of cuticles isolated from fruit and leaves in loamy sand and sandy clay loessial arid brown soils. We then studied sorption of phenanthrene and carbamazepine to humin-mineral matrices isolated from the incubated soils. Low degradation (22%) was observed for agave cuticle in a sandy clay soil system, whereas high degradation (68-78%) was obtained for agave cuticle in a loamy sand soil system and for loamy sand and sandy clay soils amended with tomato cuticle. During incubation, most of the residual organic matter was accumulated in the humin fraction. Sorption of phenanthrene was significantly higher for humin-mineral matrices obtained from soils incubated with plant cuticles as compared with soils without cuticle application. Sorption of carbamazepine to humin-mineral matrices was not affected by cuticle residues. Cooperative sorption of carbamazepine on humin-mineral matrices isolated from sandy clay soil is suggested. Sorption-desorption hysteresis of both phenanthrene and carbamazepine was lower for humin-mineral matrices obtained from soils incubated with plant cuticles as compared with nonamended soils. Our results show that cuticle composition significantly affects the rate and extent of cuticle degradation in soils and that plant cuticle application influences sorption and desorption of polar and nonpolar pollutants by humin-mineral matrices.

Insights into the uptake processes of wastewater-borne pharmaceuticals by vegetables.

An increasing number of reports on plant uptake of pharmaceutical compounds (PCs) have been recently published, raising concerns of human exposure through dietary intake. In this study, PC uptake and translocation were evaluated in cucumber and tomato plants to elucidate the effects of PC physicochemical properties, soil type, and irrigation-water quality. Nonionic PCs were taken up and accumulated at higher levels in plants grown in soils of lower organic matter and clay content. While the concentration of most PCs in cucumber and tomato leaves were of similar order, their concentrations in the tomato fruit were much lower than in the cucumber fruit. This is related to differences in fruit physiology. Our data suggest that irrigation with treated wastewater reduces the bioavailability of acidic PCs for uptake by cucumber plants as compared to fresh water irrigation. This study sheds light on factors affecting the uptake of PCs by crops irrigated with treated wastewater, the governing role of PCs' physicochemical properties along with the physiological nature of the plant, soil properties and water quality that together determine uptake, translocation, and accumulation within plant organs. Occurrence of metabolites in plant suggests that PC metabolism has to be evaluated to reveal the total uptake.

Irrigation of root vegetables with treated wastewater: evaluating uptake of pharmaceuticals and the associated human health risks.

To meet mounting water demands, treated wastewater has become an important source of irrigation. Thus, contamination of treated wastewater by pharmaceutical compounds (PCs) and the fate of these compounds in the agricultural environment are of increasing concern. This field study aimed to quantify PC uptake by treated wastewater-irrigated root crops (carrots and sweet potatoes) grown in lysimeters and to evaluate potential risks. In both crops, the nonionic PCs (carbamazepine, caffeine, and lamotrigine) were detected at significantly higher concentrations than ionic PCs (metoprolol, bezafibrate, clofibric acid, diclofenac, gemfibrozil, ibuprofen, ketoprofen, naproxen, sulfamethoxazole, and sildenafil). PCs in leaves were found at higher concentrations than in the roots. Carbamazepine metabolites were found mainly in the leaves, where the concentration of the metabolite 10,11-epoxycarbamazepine was significantly higher than the parent compound. The health risk associated with consumption of wastewater-irrigated root vegetables was estimated using the threshold of toxicological concern (TTC) approach. Our data show that the TTC value of lamotrigine can be reached for a child at a daily consumption of half a carrot (∼60 g). This study highlights that certain PCs accumulated in edible organs at concentrations above the TTC value should be categorized as contaminants of emerging concern.

Negligible adsorption and toxicity of microplastic fibers in disinfected secondary effluents.

Wastewater treatment plants play a crucial role in controlling the transport of pollutants to the environment and often discharge persistent contaminants such as synthetic microplastic fibers (MFs) to the ecosystem. In this study, we examined the fate and toxicity of polyethylene terephthalate (PET) MFs fabricated from commercial cloth in post-disinfection secondary effluents by employing conditions that closely mimic disinfection processes applied in wastewater treatment plants. Challenging conventional assumptions, this study illustrated that oxidative treatment by chlorination and ozonation incurred no significant modification to the surface morphology of the MFs. Additionally, experimental results demonstrated that both pristine and oxidized MFs have minimal adsorption potential towards contaminants of emerging concern in both effluents and alkaline water. The limited adsorption was attributed to the inert nature of MFs and low surface area to volume ratio. Slight adsorption was observed for sotalol, sulfamethoxazole, and thiabendazole in alkaline water, where the governing adsorption interactions were suggested to be hydrogen bonding and electrostatic forces. Acute exposure experiments on human cells revealed no immediate toxicity; however, the chronic and long-term consequences of the exposure should be further investigated. Overall, despite the concern associated with MFs pollution, this work demonstrates the overall indifference of MFs in WWTP (i.e., minor effects of disinfection on MFs surface properties and limited adsorption potential toward a mix of trace organic pollutants), which does not change their acute toxicity toward living forms.

Pesticides and pharmaceuticals data collected during two consecutive years in a Mediterranean micro-estuary.

The Alexander micro-estuary, located at the eastern edge of the Mediterranean Sea, is a typical example of small water bodies that suffer from a combination of urban and agricultural pollution, and overuse of its natural water sources. It is∼6.5 km long, with maximum depth of 3 m and maximum width of 45 m. To evaluate the anthropogenic stress on the system and its ability to mitigate pollution, water samples were collected within the framework of Ruppin's Estuarine and Coastal Observatory [1]. Water samples were collected from the estuary head, which drains about 510 km2, and at a point 300 m upstream from the estuary mouth before water flows into the Mediterranean Sea. A total of 236 stormwater and 44 base-flow water samples between December 2016 and December 2018. Stormwater samples were collected every 0.25 - 4 h along the entire course of the flow events using an automated samplers (Sigma 900, Hach Company, Loveland CO, USA; and ISCO 3700 Full-Size Portable Sampler, Teledyne, Lincoln, NE, USA). Base-flow samples were taken once a month using a horizontal grab sampler (5 L, model 110B, OceanTest Equipment, Fort Lauderdale, FL, USA). All samples were filtered using 90mmGF/F filters (nominal pore size of 0.7 µm, MGF, Sartorius, Göttingen, Germany) and immediately frozen (-20°C) before chemical analysis. Chemical analysis was performed using liquid chromatography with high-resolution mass spectrometry (LC-HRMS) analysis using a QExactive Plus hybrid FT mass spectrometer coupled with a Dionex Ultimate 3000 RS UPLC (Thermo Fisher Scientific, Waltham, MA, USA). The targeted analysis, which included 15 fungicides, 25 herbicides, 18 Insecticides, and 19 pharmaceuticals, concluded with a total of 21,142 entries. All entries are organized in a worksheet, along with location, date, flood section duration, discharge rate, and the total water volume discharged during the relevant period. The provided data offers an opportunity to explore the sources, transport, and impact of a large mixture of organic pollutants in a confined aquatic system located in an urbanized coastal environment.

Mitigating risks and maximizing sustainability of treated wastewater reuse for irrigation.

Scarcity of freshwater for agriculture has led to increased utilization of treated wastewater (TWW), establishing it as a significant and reliable source of irrigation water. However, years of research indicate that if not managed adequately, TWW may deleteriously affect soil functioning and plant productivity, and pose a hazard to human and environmental health. This review leverages the experience of researchers, stakeholders, and policymakers from Israel, the United-States, and Europe to present a holistic, multidisciplinary perspective on maximizing the benefits from municipal TWW use for irrigation. We specifically draw on the extensive knowledge gained in Israel, a world leader in agricultural TWW implementation. The first two sections of the work set the foundation for understanding current challenges involved with the use of TWW, detailing known and emerging agronomic and environmental issues (such as salinity and phytotoxicity) and public health risks (such as contaminants of emerging concern and pathogens). The work then presents solutions to address these challenges, including technological and agronomic management-based solutions as well as source control policies. The concluding section presents suggestions for the path forward, emphasizing the importance of improving links between research and policy, and better outreach to the public and agricultural practitioners. We use this platform as a call for action, to form a global harmonized data system that will centralize scientific findings on agronomic, environmental and public health effects of TWW irrigation. Insights from such global collaboration will help to mitigate risks, and facilitate more sustainable use of TWW for food production in the future.

Insight into the role of dissolved organic matter in sorption of sulfapyridine by semiarid soils.

Sorption-desorption behavior of sulfapyridine was studied with three distinct soil types low in organic carbon with or without the introduction of exogenous dissolved organic matter (DOM). Experiments with bulk soils yielded sorption coefficients equivalent to those obtained with soils richer in organic matter, indicating an important sorptive role for soil mineral matrices. Cointroduction of sulfapyridine with DOM significantly reduced sulfapyridine sorption. However, decreasing solution pH from ~9 to ~6 limited the effect of DOM and revealed the effect of ionic speciation of sulfapyridine on the sorption potential. Sulfapyridine sorption to soils precoated with DOM exhibited contrasting trends. Two of the coated soils exhibited decreased sorption of sulfapyridine probably due to blockage of sorption sites by DOM. Conversely, the third soil demonstrated cumulative adsorption of sulfapyridine. Precoating also enhanced sulfapyridine desorption, suggesting that sorption of sulfapyridine to mineral surfaces involves stronger chemisorptive binding as compared with interactions with sorbed DOM. The capacity of soil to sorb DOM as well as the chemical fractionation of DOM during sorption were found to significantly affect binding of sulfapyridine. Competition between preferentially sorbed DOM moieties (e.g., carboxyl, phenol) and sulfapyridine for sorption sites is proposed. This study suggests that the chemical nature of DOM can significantly affect the fate of sulfonamide compounds in soils.

Pulmonary surfactant suppressed phenanthrene adsorption on carbon nanotubes through solubilization and competition as examined by passive dosing technique.

Adsorption of phenanthrene on carbon nanotubes (CNTs) was examined in the presence of pulmonary surfactant (Curosurf) and its main components, dipalmitoyl phosphatidylcholine (DPPC) and bovine serum albumin (BSA). A passive-dosing method based on equilibrium partitioning from a preloaded polymer was successfully employed to measure phenanthrene binding and speciation at controlled freely dissolved concentrations while avoiding phase separation steps. Curosurf, DPPC, and BSA could all linearly solubilize phenanthrene, and phenanthrene solubilization by Curosurf was 4 times higher than individual components (DPPC or BSA). In the presence of Curosurf, DPPC or BSA, adsorption of phenanthrene by multiwalled CNTs (MWCNTs) was suppressed, showing competitive adsorption between pulmonary surfactant (or DPPC, BSA) and phenanthrene. Competitive adsorption between Curosurf and phenanthrene was the strongest. Therefore, when phenanthrene-adsorbed CNTs enter the respiratory tract, phenanthrene can be desorbed due to both solubilization and competition. The bioaccessibility of phenanthrene adsorbed on three MWCNTs in the respiratory tract would be positively related to the size of their outer diameters. Moreover, the contribution of solubilization and competition to desorption of phenanthrene from MWCNTs was successfully separated for the first time. These findings demonstrate the two mechanisms on how pulmonary surfactants can enhance desorption and thus possibly biological absorption of phenanthrene adsorbed on CNTs.