Search

Dissolved organic matter (DOM) released from biochar may impact antibiotic mobility and environmental fate in subsurface environments. Here, DOM samples derived from biochars (BDOM) generated by pyrolyzing corn straw at 300, 450, and 600 °C were employed to elucidate the mobility characteristics of these organic substances and their influences on the transport of sulfamerazine (SMZ, a typical sulfonamide antibiotic) in soil porous media. The results demonstrated that BDOM produced at a lower pyrolysis temperature exhibited greater mobility owing to the weaker hydrophobic and H-bonding interactions between BDOM and soil particles. Additionally and importantly, BDOM facilitated the promotion of SMZ mobility owing to the increased electrostatic repulsion between SMZ - forms and soil grains, the steric hindrance effect induced by the deposition of organic matter, and the competitive retention between SMZ molecules and BDOM. Meanwhile, the promotion effects of BDOM enhanced with improving pyrolysis temperature owing to the promoted deposition of organic matter on soil surfaces and the strengthened electrostatic repulsion. Moreover, the facilitated effects of BDOM on SMZ mobility declined as the solution pH values were raised from 5.0 to 9.0 or the flow rate increased from 0.18 to 0.51 cm min -1 . This trend was due to decreased deposition competition and the steric effect caused by decreased retention of BDOM on soil particles. Furthermore, the cation-bridging effect emerged as an important mechanism contributing to the promotion effects of BDOM when the solution contained divalent cations (Cu 2+ or Ca 2+ ). Moreover, a two-site non-equilibrium model was used to interpret the controlling mechanisms for the effects of BDOM on the transport of SMZ. Findings from this work highlight that biochar-derived dissolved organic matter can remarkably affect the environmental behaviors of antibiotics in aquatic environments.

The deposition of biomass-burning smoke water-soluble organic matter (BBS-WSOM) significantly affects the environmental behavior of heavy metals in aqueous environments. However, the interactions between BBS-WSOM and heavy metals at the molecular level remain unknown. This study combined FT-ICR-MS, fluorescence spectrum, FTIR, and two-dimensional correlation spectroscopy to anatomize the molecular characteristics of BBS-WSOM binding with Cd(II). The results show that CHO and CHOP compounds were responsible for the fluorescence response of BBS-WSOM at Ex: 225 nm and 275 nm/Em: 325 nm, and abundant proteins or CHON compounds were responsible for the fluorescence response of BBS-WSOM at Ex: 225-250 nm/Em: 350-450 nm and Ex: 300-350 nm/Em: 350-450 nm, which was very different from the fluorescence molecules in natural organic matters. Fluorescence change after Cd(II) addition indicated that CHOP and CHOS compounds enhanced BBS-WSOM binding with Cd(II). Differently, the CHON compounds could weaken the binding of other compounds with Cd(II). Different compounds binding with Cd(II) generally followed the order: CHON/CHOS compounds>CHOP compounds>CHO compounds, and the chemical groups binding with Cd(II) generally followed the prioritization: -COO - > -NH/SO>P = O/P-O>aromatic ring>CO>C-OH of phenol/alcohol>C-O-C. This study provides a profound insight into the interaction between BBS-WSOM and Cd(II) at the molecular level., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The environmental effects of biochar-derived organic carbon (BDOC) have attracted increasing attention. Nevertheless, it is unknown how BDOC might affect the natural attenuation of widely distributed chloroalkanes (e.g., 1,1,2,2-tetrachloroethane (TeCA)) in aqueous environments. We firstly observed that the kinetic constants (k e ) of TeCA dehydrochlorination in the presence of BDOC samples or their different molecular size fractions (<1 kDa, 1∼10 kDa, and >10 kDa) ranged from 9.16×10 3 to 26.63×10 3 M -1 h -1 , which was significantly greater than the k e (3.53×10 3 M -1 h -1 ) of TeCA dehydrochlorination in the aqueous solution at pH 8.0, indicating that BDOC samples and their different molecular size fractions all could promote TeCA dehydrochlorination. For a given BDOC sample, the kinetic constants (k e ) of TeCA dehydrochlorination in the initial pH 9.0 solution was 2∼3 times greater than that in the initial pH 8.0 solution due to more formation of conjugate bases. Interestingly, their DOC concentration normalized kinetic constants (k e /[DOC]) were negatively correlated with SUVA 254 , and positively correlated with A 220 /A 254 and the abundance of aromatic protein-like/polyphenol-like matters. A novel mechanism was proposed that the CH dipole of BDOC aliphatic structure first bound with the CCl dipole of TeCA to capture the TeCA molecule, then the conjugate bases (-NH-/-NH 2 and deprotonated phenol-OH of BDOC) could attack the H atom attached to the β-C atom of bound TeCA, causing a CCl bond breaking and the trichloroethylene formation. Furthermore, a fraction of >1 kDa had significantly greater k e /[DOC] values of TeCA dehydrochlorination than the fraction of <1 kDa because >1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

There is little information on how widespread surfactants affect the adsorption of norfloxacin (NOR) onto iron oxide minerals. In order to elucidate the effects of various surfactants on the adsorption characteristics of NOR onto typical iron oxides, we have explored the different influences of sodium dodecylbenzene sulfonate (SDBS), an anionic surfactant, and didodecyldimethylammonium bromide (DDAB), a cationic surfactant, on the interactions between NOR and ferrihydrite under different solution chemistry conditions. Interestingly, SDBS facilitated NOR adsorption, whereas DDAB inhibited NOR adsorption. The adsorption-enhancement effect of SDBS was ascribed to the enhanced electrostatic attraction, the interactions between the adsorbed SDBS on ferrihydrite surfaces and NOR molecules, and the bridging effect of SDBS between NOR and iron oxide. In comparison, the adsorption-inhibition effect of DDAB owning to the adsorption site competitive adsorption between NOR and DDAB for the effective sites as well as the steric hindrance between NOR-DDAB complexes and the adsorbed DDAB on ferrihydrite surfaces. Additionally, the magnitude of the effects of surfactants on NOR adsorption declined with increasing pH values from 5.0 to 9.0, which was related to the amounts of surfactant binding to ferrihydrite surfaces. Moreover, when the background electrolyte was Ca 2+ , the enhanced effect of SDBS on NOR adsorption was caused by the formation of NOR-Ca 2+ -SDBS complexes. The inhibitory effect of DDAB was due to the DDAB coating on ferrihydrite, which undermined the cation-bridging effect. Together, the findings from this work emphasize the essential roles of widely existing surfactants in controlling the environmental fate of quinolone antibiotics.

This study aims to understand how surfactants affect the mobility of tetracycline (TC), an antibiotic, through different aquifer media. Two anionic and cationic surfactants, sodium dodecylbenzene sulfonate (SDBS) and cetyltrimethyl ammonium bromide (CTAB), were used to study their influence on TC mobility through clean sand and humic acid (HA)-coated sand. HA coating inhibits TC mobility due to its strong interaction with TC. Both surfactants promoted TC mobility at pH 7.0 due to competitive deposition, steric effect, and increased hydrophilicity of TC. CTAB had a more substantial effect than SDBS, related to the surfactants' molecular properties. Each surfactant's promotion effects were greater in HA-coated sand than in quartz sand due to differences in surfactant retention. CTAB inhibited TC transport at pH 9.0 due to its significant hydrophobicity effect. Furthermore, in the presence of Ca 2+ , SDBS enhanced TC transport by forming deposited SDBS-Ca 2+ -TC complexes. On the other hand, CTAB increased TC mobility due to its inhibition of cation bridging between TC and porous media. The findings highlight surfactants' crucial role in influencing the environmental behaviors of tetracycline antibiotics in varied aquifers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Biochar as an effective adsorbent can be used for the removal of triclocarban from wastewater. Biochar-derived dissolved organic carbon (BC-DOC) is an important carbonaceous component of biochar, nonetheless, its role in the interaction between biochar and triclocarban remains little known. Hence, in this study, sixteen biochars derived from pine sawdust and corn straw with different physico-chemical properties were produced in nitrogen-flow and air-limited atmospheres at 300-750 °C, and investigated the effect of BC-DOC on the interaction between biochar and triclocarban. Biochar of 600∼750 °C with low polarity, high aromaticity, and high porosity presented an adsorption effect on triclocarban owing to less BC-DOC release as well as the strong π-π, hydrophobic, and pore filling interactions between biochar and triclocarban. In contrast and intriguingly, biochar of 300∼450 °C with low aromaticity and high polarity exhibited a significant solubilization effect rather than adsorption effect on triclocarban in aqueous solution. The maximum solubilization content of triclocarban in biochar-added solution reached approximately 3 times its solubility in biochar-free solution. This is mainly because the solubilization effect of BC-DOC surpassed the adsorption effect of biochar though the BC-DOC only accounted for 0.01-1.5 % of bulk biochar mass. Furthermore, the high solubilization content of triclocarban induced by biochar was dependent on the properties of BC-DOC as well as the increasing BC-DOC content. BC-DOC with higher aromaticity, larger molecular size, higher polarity, and more humic-like matters had a greater promoting effect on the water-solubility of triclocarban. This study highlights that biochar may promote the solubility of some organic pollutants (e.g., triclocarban) in aqueous environment and enhance their potential risk., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Identification of the transport of sulfonamide antibiotics in soils facilitates a better understanding of the environmental fate and behaviors of these ubiquitous contaminants. In this study, the mobility properties of sulfanilamide (SNM, a typical sulfonamide antibiotic) through saturated soils with different physicochemical characteristics were investigated. The results showed that the physicochemical characteristics controlled SNM mobility. Generally, the mobility of SNM was positively correlated with CEC values and soil organic matter content, which was mainly related to the interactions between the organic matter in soils and SNM molecules via π-π stacking, H-bonding, ligand exchange, and hydrophobic interaction. Furthermore, higher clay mineral content and lower sand content were beneficial for restraining SNM transport in the soils. Unlike Na + , Cu 2+ ions could act as bridging agents between the soil grains and SNM molecules, contributing to the relatively weak transport of SNM. Furthermore, the trend of SNM mobility in different soil columns was unaffected by solution pH (5.0-9.0). Meanwhile, for a given soil, the SNM mobility was promoted as the solution pH values increased, which was caused by the enhanced electrostatic repulsion between SNM - species and soil particles as well as the declined hydrophobic interaction between SNM and soil organic matter. The obtained results provide helpful information for the contribution of soil physicochemical characteristics to the transport behaviors of sulfonamide antibiotics in soil-water systems., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Empirical information about the transport properties of neonicotinoid pesticides through the soil as affected by the ubiquitous low molecular weight organic acids (LMWOAs) is lacking. Herein, the impacts of three LMWOAs with different molecular structures, including citric acid, acetic acid, and malic acid, on the mobility characteristics of two typical neonicotinoid pesticides (Dinotefuran (DTF) and Nitenpyram (NTP)) were explored. Interestingly, under acidic conditions, different mechanisms were involved in transporting DTF and NTP by adding exogenous LMWOAs. Concretely, acetic acid and malic acid inhibited DTF transport, ascribed to the enhanced electrostatic attraction between DTF and porous media and the additional binding sites provided by the deposited LMWOAs. However, citric acid slightly enhanced DTF mobility due to the fact that the inhibitory effect was weakened by the steric hindrance effect induced by the deposited citric acid with a large molecular size. In comparison, all three LMWOAs promoted NTP transport at pH 5.0. Because the interaction between NTP with soil organic matter (e.g., via π-π stacking interaction) was masked by the LMWOAs coating on soil surfaces. Nevertheless, LMWOAs could promote the mobility of both neonicotinoid pesticides at pH 7.0 due to the steric hindrance effect caused by the deposited organic acids and the competitive retention between LMWOAs and pesticides for effective surface deposition sites of soil particles. Furthermore, the extent of the promotion effects of LMWOAs generally followed the order of citric acid > malic acid > acetic acid. This pattern was highly related to their molecular structures (e.g., number and type of functional groups and molecular size). Additionally, when the background solutions contained Ca 2+ , the bridging effect of cations also contributed to the transport-enhancement effects of LMWOAs. The findings provide valuable information about the mobility behaviors of neonicotinoid pesticides co-existing with LMWOAs in soil-water systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Low-molecular-weight aromatic acids (LWMAAs), a ubiquitous organic substance in natural systems, are important in controlling the environmental fate of potentially toxic metals. However, little is known about the effects of LWMAAs on the interactions between biochars and potentially toxic metals. Herein, the influences of three aromatic acids, including benzoic acid (BA), p-hydroxy benzoic acid (PHBA), and syringic acid (SA), on the adsorption of Cd 2+ onto biochars generated at three different pyrolysis temperatures under acidic and neutral conditions were examined. Generally, the adsorption ability of biochars for Cd 2+ improved with the increase of pyrolysis temperature, which was ascribed to the increased inorganic element contents (e.g., P, S, and Si) and aromaticity, increasing the complexation between mineral anions and metal ions, and the enhanced cation-π interaction. Interestingly, aromatic acids considerably inhibited the adsorption of Cd 2+ onto biochars, which was mainly ascribed to multi-mechanisms, including competition of LWMAA molecules and metal ions for adsorption sites, the pore blocking effect, the weakened interaction between mineral anions and Cd 2+ induced by the adsorbed aromatic acids, and the formation of water-soluble metal-aromatic acid complexes. Furthermore, the inhibitory effects of LWMAAs on Cd 2+ adsorption intensively depended on the aromatic acid type and followed the order of SA > PHBA > BA. This trend was related to the differences in the physicochemical features (e.g., the octanol/water partition coefficient (log K ow ) and molecular size) of diverse LMWAAs. The results of this study demonstrate that the effects of coexisting LMWAAs should not be ignored when biochars are applied in soil remediation and wastewater treatment., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In the post-COVID-19 era, extensive quantities of antipyretic drugs are being haphazardly released from households into the environment, which may pose potential risks to ecological systems and human health. Identification of the mobility behaviors of these compounds in the subsurface environment is crucial to understand the environmental fate of these common contaminants. The mobility properties of three broad-spectrum antipyretic drugs, including ibuprofen (IBF), indometacin (IMC), and acetaminophen (APAP), in porous soil media, were investigated in this study. The results showed that the mobility of the three drugs (the background electrolyte was Na + ) through the soil column followed the order of APAP > IBF > IMC. The difference in the physicochemical characteristics of various antipyretic drugs ( e.g. , the molecular structure and hydrophobicity) could explain this trend. Unlike Na + , Ca 2+ ions tended to serve as bridging agents by linking the soil grains and antipyretic molecules, leading to the relatively weak mobility behaviors of antipyretic drugs. Furthermore, for a given antipyretic drug, the antipyretic mobility was promoted when the background solution pH values were raised from 5.0 to 9.0. The phenomenon stemmed from the improved electrostatic repulsion between the dissociated species of antipyretic molecules and soil grains, as well as the weakened hydrophobic interactions between antipyretic drugs and soil organic matter. Furthermore, a two-site non-equilibrium transport model was used to estimate the mobility of antipyretic drugs. The results obtained from this work provide vital information illustrating the transport and retention of various antipyretic drugs in aquifers.

Herein, the influences of rhamnolipid (a typical biosurfactant) on oxytetracycline (OTC) transport in the porous media and their variations with the surface heterogeneities of the media (uncoated sand, goethite (Goe)-, and humic acid (HA)-coated sands) were explored. Compared to uncoated sand, goethite and HA coatings suppressed OTC mobility by increasing deposition sites. Interestingly, rhamnolipid-affected OTC transport strongly depended on the chemical heterogeneities of aquifers and biosurfactant concentrations. Concretely, adding rhamnolipid (1-3 mg/L) inhibited OTC mobility through sand columns because of the bridging effect of biosurfactant between sand and OTC. Unexpectedly, rhamnolipid of 10 mg/L did not further improve the inhibition of OTC transport owing to the fact that the deposition capacity of rhamnolipid reached its maximum. OTC mobility in Goe-coated sand columns was inhibited by 1 mg/L rhamnolipid. However, the inhibitory effect decreased with the increasing rhamnolipid concentration (3 mg/L) and exhibited a promoted effect at 10 mg/L rhamnolipid. This surprising observation was that the increased rhamnolipid molecules gradually occupied the favorable deposition sites (i.e., the positively charged sites). In comparison, rhamnolipid facilitated OTC transport in the HA-coated sand column. The promotion effects positively correlated with rhamnolipid concentrations because of the high electrostatic repulsion and deposition site competition induced by the deposited rhamnolipid. Another interesting phenomenon was that rhamnolipid's enhanced or inhibitory effects on OTC transport declined with the increasing solution pH because of the decreased rhamnolipid deposition on porous media surfaces. These findings benefit our understanding of the environmental behaviors of antibiotics in complex soil-water systems containing biosurfactants., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Biomass-pyrogenic smoke-derived dissolved organic matter (SDOMs) percolating into the underground environment profoundly impacts the transport and fate of environmental pollutants in groundwater systems. Herein, SDOMs were produced by pyrolyzing wheat straw at 300-900 °C to explore their transport properties and effects on Cu 2+ mobility in quartz sand porous media. The results indicated that SDOMs exhibited high mobility in saturated sand. Meanwhile, the mobility of SDOMs was enhanced at a higher pyrolysis temperature due to the decrease in their molecular sizes and the declined H-bonding interactions between SDOM molecules and sand grains. Furthermore, the transport of SDOMs was elevated as pH values were raised from 5.0 to 9.0, which resulted from the strengthened electrostatic repulsion between SDOMs and quartz sand particles. More importantly, SDOMs could facilitate Cu 2+ transport in the quartz sand, which stemmed from forming soluble Cu-SDOM complexes. Intriguingly, the promotional function of SDOMs for the mobility of Cu 2+ was strongly dependent on the pyrolysis temperature. Generally, SDOMs generated at higher temperatures exhibited superior effects. The phenomenon was mainly due to the differences in the Cu-binding capacities of various SDOMs (e.g., cation-π attractive interactions). Our findings highlight that the high-mobility SDOM can considerably affect heavy metal ions' environmental fate and transport., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

To date, little information is available regarding the impacts of the widespread anionic surfactants on the adsorption behaviors of antibiotics onto typical iron oxides. Herein, we have investigated the effects of two typical surfactants (sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS)) on the adsorption of two widely used antibiotics (i.e., levofloxacin (LEV) and ciprofloxacin (CIP)) onto ferrihydrite. Results of kinetic experiments showed that the adsorption of antibiotics was well fitted by the pseudo-second-order kinetic models, indicating that the adsorption process might be controlled by chemisorption. The affinity of ferrihydrite toward CIP was greater than that toward LEV, which was ascribed to the higher hydrophobicity of CIP than LEV. Both surfactants enhanced antibiotic adsorption owing to SDS or SDBS molecules as bridge agents between ferrihydrite particles and antibiotics. Interestingly, the extent of the enhanced effects of surfactants on antibiotic adsorption declined as the background solution pH increased from 5.0 to 9.0, which was mainly due to the weaker hydrophobic interactions between antibiotics and the adsorbed surfactants on the iron oxide surfaces as well as the greater electrostatic repulsion between the anionic species of antibiotics and the negatively charged ferrihydrite particles at higher pH. Together, these findings emphasize the importance of widespread surfactants for illustrating the interactions between fluoroquinolone antibiotics and iron oxide minerals in the natural environment., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Understanding the mobility, retention, and fate of carbon dots (CDs) is critical for the risk management of this emerging carbon material. However, the influences of surfactants on CDs' transport through subsurface media are still poorly understood. Herein, column experiments were conducted to explore the different influences of an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), and a cationic surfactant, cetyltrimethylammonium bromide (CTAB), on the CDs' transport in water-saturated soil. In the Na + background electrolyte, both surfactants facilitated the transport of CDs at pH 7.0. The trend stemmed from steric hindrance, a decline in the straining effect, and competitive deposition between CDs and surfactant molecules. Additionally, SDBS increased the electrostatic repulsion of CDs and soil. Interestingly, in the divalent cation background electrolytes (i.e., Ca 2+ or Cu 2+ ), SDBS suppressed CDs' mobility, whereas CTAB had the opposite effect. The transport-inhibited effect of SDBS was mainly due to anionic surfactant ion (DBS - ) precipitation with metal cations and the formation of adsorbed SDBS-Cu 2+ /Ca 2+ -CDs complexes. The enhanced effect of CTAB resulted from the CTAB coating on soil grains, which suppressed the cation bridging between CDs and soil. Furthermore, the magnitude of the SDBS promotion effect was pH-dependent. Surprisingly, CTAB could inhibit CDs' mobility at pH 9.0, owing to the binding cationic surfactant's strong hydrophobicity effect on the soil surface. Moreover, the experimental breakthrough curves of CDs were well described using a two-site transport model. Overall, the observations obtained from this study shed light on the relative mobility of CDs with different surfactants in typical groundwater conditions., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The current state of knowledge on the transport behaviors of oxytetracycline (OTC, a typical tetracycline antibiotic) in porous media with heterogeneous chemical surfaces is inadequate. In this work, the mobility properties of OTC through saturated porous media with different chemical heterogeneities ( i.e. , quartz sand, montmorillonite (MMT)-, humic acid (HA)-, and goethite (Goe)-coated sands) were investigated. In comparison with the mobility of OTC in the quartz sand, HA and goethite coatings inhibited the mobility of OTC, whereas montmorillonite coating enhanced OTC mobility. HA coating inhibited the transport of OTC that stemmed from the strong interactions between HA and OTC via complexation, π-π stacking, hydrogen bonding, and hydrophobic interaction. The positively charged iron oxide coating on Goe-coated sand provided favorable sites for OTC deposition through complexation and electrostatic attraction. The enhanced transport of OTC through MMT-coated sand was mainly due to the strong electrostatic repulsion between the anionic OTC species ( i.e. , OTC - ) and negatively charged porous media. Solution pH (5.0-9.0) posed a negligible effect on the trend of OTC mobility in different porous media. Furthermore, Ca 2+ inhibited the transport of OTC mobility through various porous media via cation-bridging. The findings of this work contribute significantly to our understanding of the influence of aquifer surface chemical heterogeneities on OTC mobility behaviors in the subsurface environment.

Colloid-mediated contaminant mobility is absolutely critical for the environmental behavior of contaminants such as antibiotics in water resources. In this study, the influences of phosphate (a commonly inorganic ligand in the environment) on the ferrihydrite colloid-mediated transport of tetracycline (TC, a typical antibiotic) in porous media were investigated. In the absence of colloids, phosphate promoted TC mobility due to the competitive deposition of phosphate and TC on the sand surface as well as the electrostatic repulsion. Interestingly, ferrihydrite colloids could inhibit TC transport; however, the inhibitory effect of the colloids was weakened by the addition of phosphate. This phenomenon stemmed from colloid-associated TC mobility, the increased electrostatic repulsion induced by adsorbed phosphate, and deposition site competition effect. Another interesting finding was that the impacts of phosphate on the colloid-mediated mobility of TC were pH-dependent. That is, phosphate exhibited a weaker effect on the inhibitory role of ferrihydrite colloids in TC mobility at pH 5.0 than that at pH 7.0; specially, ferrihydrite colloids acted as possible carriers of TC and facilitated antibiotic transport at pH 9.0. The observations were ascribed to different influences of phosphate on the binding affinity of ferrihydrite toward TC and the mobility of free TC under different pH conditions. Therefore, the findings of this study provide useful information about the fate and co-transport of antibiotics and natural mineral colloids in the presence of inorganic ligands in the aquatic environment., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

There is currently a lack of scientific understanding regarding how bio-surfactants influence the mobility of graphene oxide (GO) through saturated porous media. In this study, the transport characteristics of GO through porous media with different heterogeneities ( i.e. , quartz sand and goethite-coated sand) after the addition of saponin (a representative bio-surfactant) were investigated. The results demonstrated that saponin (3-10 mg L -1 ) promoted GO mobility in both types of porous media at pH 7.0. This trend was attributed to the competitive deposition between nanoparticles and bio-surfactant molecules for attachment sites, the enhanced electrostatic repulsion, the decreased strain, the presence of steric effects induced by the adsorbed saponin, and the increase in the hydrophilicity of nanoparticles. Intriguingly, saponin promoted GO mobility in goethite-coated sand ( i.e. , chemically heterogeneous porous media) to a greater extent than that in sand ( i.e. , relatively homogeneous porous media) when saponin concentrations increased, which stemmed from the differences in the extent of the deposition site competition for saponin on the two porous media and the electrostatic repulsion between GO and the porous media. Furthermore, a cation-bridging mechanism was also involved in the ability of saponin to increase GO mobility when the electrolyte solution was 0.1 mM Cu 2+ . Moreover, the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and the colloid transport model were applicable to elucidate the mobility properties of GO with or without saponin in porous media. The findings from this work highlight the important status of bio-surfactants in the fate of colloidal carbon-based nanomaterials in subsurface systems.

Water-soluble aerosol organic matters (WSAOMs) produced by biomass pyrolysis/burning can penetrate subsurface environment, and are anticipated to have a profound effect on the fate of contaminants in aquatic ecosystems. Herein, WSAOMs derived from corn straw (CS-WSAOMs) and pinewood sawdust (PW-WSAOMs) pyrolysis at 300-900 °C were utilized to investigate their mobility characteristics and impacts on the transport of heavy metal ions (i.e., Cd 2+ ) in saturated quartz sand with or without soil colloids. This study clearly demonstrated that WSAOMs in subsurface systems exhibited high mobility, which increased as WSAOMs molecular sizes decreased and hydrogen-bond interactions between WSAOMs and sand grains declined. WSAOMs significantly improved heavy metal (i.e., Cd 2+ ) and soil colloid-mediated Cd 2+ mobility in the porous media, which stemmed from the increased binding affinities of colloids toward metal ions and the high mobility of WSAOMs. Interestingly, in terms of the mobility and colloid-facilitated transport of Cd 2+ , WSAOMs from higher pyrolysis temperatures exhibited enhanced effects; meanwhile, the PW-WSAOMs demonstrated stronger effects than the CS-WSAOMs. The trends were mainly attributed to the differences in the metal-binding affinities (e.g., cation-π interactions) and transport abilities of WSAOMs, as well as diverse Cd 2+ adsorption capacities of colloids induced by various WSAOMs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Knowledge of the mobility of tetracycline (TC) antibiotics in porous media is critical to understand their potential environmental influences. The transport characteristics of TC in sand columns with three different surfactants, including Tween 80, sodium dodecylbenzene sulfonate (SDBS), and didodecyldimethylammonium bromide (DDAB) under various conditions were investigated in this study. Results demonstrated that all surfactants enhanced TC transport under neutral conditions (10 mM NaCl at pH 7.0). The observation was attributed mostly to deposition site competition, higher electrostatic repulsion between TC molecules and sand grains, steric hindrance, and the increase of TC hydrophilicity. Furthermore, the order of the transport-enhancement effects was generally observed as follows: DDAB > SDBS > Tween 80. The trend was controlled by the variation in the physicochemical properties of surfactants. It was noticed that the presence of Cu 2+ (a model divalent cation) in the background solution, the cation-bridging contributed to the promotion effects of DDAB or Tween 80 on TC mobility. Interestingly, SDBS considerably suppressed TC transport due to the precipitation of SDBS-Cu 2+ complexes onto sand surfaces. Moreover, the enhancement order of surfactants at pH 5.0 was similar to that pH 7.0. However, DDAB could inhibit TC transport in sand columns at pH 9.0, which were mainly caused by the decrease of electrostatic repulsion and the hydrophobicity induced by the binding cationic surfactant. Findings from this work provide novel insight into involvement of surfactants in antibiotic transport behaviors in the subsurface environment., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

To date, there is still very little knowledge about the combined effects of typical inorganic ligands and solution pH values on mobility characteristics of tetracycline (TC) through saturated aquifer media. In this work, three typical inorganic ligands ( i.e. , phosphate, silicate, and iodate) were employed in the transport experiments. Generally, all the ligands promoted TC mobility over the pH range of 5.0-9.0 owing to the enhanced electrostatic repulsion between sand grains and TC anionic forms ( i.e. , TC - and TC 2- ) as well as the competitive deposition between ligands and antibiotic molecules for attachment sites. Furthermore, the transport-enhancement effects of ligands on TC intensively depended on ligand type and followed the sequence of phosphate > silicate > iodate. This phenomenon was ascribed to their different molecular sizes and binding abilities to sand grains. Interestingly, the differences in extents of enhanced effects of various inorganic ligands on TC transport varied with background solution pH due to pH-induced different extents of deposition site competition effects. Moreover, the two-site nonequilibrium model (which accounts for an equilibrium site and a kinetic site) as well as adsorption and kinetic studies were performed to help interpret the controlling mechanisms for the synergistic effects of inorganic ligands and solution pH on TC transport in saturated quartz sand. The findings of our study clearly demonstrate that inorganic ligands may be critical factors in assessing the fate and transport of antibiotics in groundwater systems.

This study systemically investigated the characteristics of biochars derived from thermo-conversion of pine sawdust and wheat straw in air-limitation, CO 2 , and N 2 atmospheres at the temperatures of 300-750 °C. Meanwhile, their energy and C stability parameters were also evaluated here. The results showed that biochar produced in air-limitation had less yield, fixed C and bulk C, as well as more volatile matter and inorganic elements than that produced in CO 2 and N 2 . Biochars derived from thermo-conversion of pine sawdust in CO 2 and N 2 at 450-750 °C had the greatest energy densification ratios (EDR) (range: 1.40-1.61), because pine sawdust contained more lignin than wheat straw, and the thermo-conversion of lignin in N 2 and CO 2 at 450-750 °C benefited for the formation of fixed C. Recalcitrance potential (R 50 ) results showed that the biochars produced in CO 2 and N 2 at 600-750 °C had the highest carbon stability (R 50 : 0.54-0.64) for given biomass, owing to the thermo-conversion of biomass in CO 2 and N 2 at 600-750 °C preferring to form the organic C with high aromaticity and low polarity. Nonetheless, thermo-conversion of biomass in CO 2 and N 2 at 300 °C presented the greatest C sequestration potential, owing to high biochar yields under these conditions. Generally, the temperature-variability for the composition, EDR, and C sequestration potential followed the order: air-limitation > CO 2  > N 2 , whereas carbon stability presented an opposite order. Our results contributed to selecting the appropriate atmosphere to optimize the properties and performances of biochars., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Environment-ubiquitous low-molecular-weight organic acids (LMWOAs) can interact with heavy metal ions and thus affect their mobility in subsurface aquifers. Herein, the effects of LMWOAs (including acetic acid, tartaric acid, malonic acid, oxalic acid, and citric acid) on the mobility of heavy metal ions (including Cd 2+ , Zn 2+ , Ni 2+ , Mn 2+ , and Co 2+ ) in porous media were investigated to reveal the role of the stability constants of metal-LMWOA complexes in the mobility of heavy metal ions in porous media. The results showed that the mobility of different metal ions followed the order of Cd 2+  < Zn 2+  < Ni 2+  < Mn 2+  < Co 2+ despite of LMWOAs-free or LMWOAs-addition. For each heavy metal, all the organic acids enhanced its transport by forming stable non-adsorbing metal-LMWOA complexes and the enhanced ability followed the order of citric acid > oxalic acid > malonic acid > tartaric acid > acetic acid. An interesting finding was that there was a significantly positive correlation between the enhanced abilities of LMWOAs to metal mobility and the complex stability constants (log K) (R 2  = 0.801-0.961, p < 0.05), indicating that the complex stability of metal-LMWOA was the dominant factor responsible for the enhanced transport of heavy metal ions. Meanwhile, the linear slope indicated the intensity of enhancement of LMWOAs on heavy metal mobility was heavy metal type-dependent. This study proposed that the complex stability of metal-LMWOA could be an indicator to quantify and predict the impact of LMWOAs on the mobility of heavy metals., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Inorganic ligands, ubiquitous in the natural environment, can interact with iron oxide minerals. To date, our knowledge regarding the effects of inorganic ligands on the adsorption properties of antibiotics onto iron oxides is still limited. In this work, the influences of different inorganic ligands (chosen iodate, silicate, and phosphate as the model ligands) on the adsorption of tetracycline (TC) onto hematite were examined. Adsorption isotherms indicated that inorganic ligands inhibited TC adsorption. The observations were attributed to the increase of electrostatic repulsion between anionic species (i.e., TC - ) and negatively charged hematite particles as well as the competition between TC - species and inorganic ligand anions for the adsorption sites on hematite surfaces. Interestingly, the inhibitory effects of the three inorganic ligands were in the order of phosphate > silicate > iodate; the trend was stemmed from their differences in the binding affinities to hematite and the molecular size. When the background solutions contained divalent cations (e.g., Ca 2+ ), surface precipitation of Ca-inorganic ligand compounds on hematite was another important mechanism for the inhibitory effects. Furthermore, adsorption of TC onto hematite with or without inorganic ligands was strongly affected by solution pH, which was due to the combination of the amphoteric behavior of TC and highly pH-dependent surface charges of the hematite mineral. Current results highlight the critical roles of ubiquitous inorganic ligands in revealing the fate of tetracycline antibiotics in natural systems., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The transport of tetracycline possessed a great challenge in its environmental applications. This study looked at how various low-molecular-weight organic acids (LMWOAs) affect the transport of tetracycline in environments. To that end, four LMWOAs were employed in experiments; acetic acid, malonic acid, malic acid, and citric acid. It was observed that LMWOAs promoted the tetracycline passage in presence of various experimental environments. The LMWOAs steric hindrance and deposition competition facilitated tetracycline transport at pH 5.0. The other deposition mechanism for tetracycline was the electrostatic repulsion between tetracycline and sand enhanced by deprotonated LMWOAs at pH 7.0. Moreover, the enhanced effects of LMWOAs on tetracycline mobility were intensively dependent on LMWOA type with more functional groups (e.g. carboxyl and hydroxyl groups) and larger molecular size supported stronger deposition competition, steric hindrance as well as electrostatic repulsion. Additionally, cation-bridging played a vital role for the enhanced effects of LMWOAs on tetracycline transport with divalent cations (e.g., Ca 2+ and Pb 2+ ). Interestingly, tetracycline exhibited a higher mobility in the presence of Ca 2+ relative to Pb 2+ regardless of LMWOAs-free or LMWOAs-addition. This phenomenon was attributed to the fact that Pb 2+ has a greater affinity with tetracycline and LMWOAs than Ca 2+ . Furthermore, under the shadow of numerous LMWOAs, the non-equilibrium two site transportation model was employed to investigate the movement of tetracycline in porous saturated media. The present study suggests that LMWOAs may be important considerations in assessing the antibiotic passage in soil as well as groundwater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Given the ubiquitous mineral (e.g., clays and iron oxides) playing critical roles in impacting the fate of antibiotics in the subsurface environment, the effects of two mineral colloids (i.e., ferrihydrite and montmorillonite) on tetracycline (TC, a representative of antibiotic) transport in sand columns were investigated in this study. Interestingly, the results clearly showed that ferrihydrite colloids inhibited TC transport, while montmorillonite colloids enhanced TC mobility under neutral conditions (pH 7.0). This phenomenon resulted from the positively charged ferrihydrite colloids with weak mobility, which assisted TC deposition; besides, providing additional deposition sites for TC by the deposited ferrihydrite colloids was another important mechanism. In contrast, the transport-enhancement effect of montmorillonite on TC was attributed to the strong binding affinity of TC to clay particles as well as the competition between colloids and TC for deposition sites on sand surfaces. Moreover, the transport-inhibition effect of ferrihydrite at pH 7.0 was greater than that at pH 5.0, mainly due to more colloid-associated TC under neutral conditions. Surprisingly, ferrihydrite colloids could act as carriers of antibiotics and enhanced TC transport at pH 9.0. Because the surface charge of colloids was altered to negative and could break through the column. Meanwhile, the transport-enhancement effect of montmorillonite decreased with increasing pH from 5.0 to 9.0, resulting from the decrease of colloid-adsorbed TC. Furthermore, colloid-mediated transport of TC was influenced by ionic strength, which affected the aggregation characteristics of colloids and the binding affinities of TC to minerals. These findings provide critical information for assessing the risks of antibiotics in aquatic ecosystems where abundant natural minerals are present., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Dissolved organic carbon derived from biomass-pyrogenic smoke (SDOC) can be transported and deposited with atmospheric aerosols, enter aqueous environments, and possibly alter aqueous chemistry and quality. However, the characteristics of SDOC in aqueous environments and their effects on the fate of hydrophobic organic pollutants are poorly understood. In this study, we found that the emitted SDOC is 7.2∼19.6 wt.% of biochar retained in situ after biomass pyrolysis, and the emitted SDOC is approximately 1-3 orders of magnitude greater than dissolved organic carbon (DOC) released from biochar in a short term, which indicates that SDOC is a more important source of DOC in aqueous environments relative to biochar-released DOC after a biomass burning/pyrolysis event. The characteristics of SDOC in aqueous environments are dominated by the <1000 Da fraction, which accounts for >96 wt.% of bulk SDOC. In comparison with DOC in biochar, natural water, and soil, the S 275-295 value of SDOC (0.037-0.053) is significantly greater, further indicating that SDOC has a smaller molecular size. Moreover, fluorescence EEM suggests that a fluorescence component located at the Ex/Em of 205/310 nm and the combinational ranges of fluorescence index (1.28-2.28), humification index (0.07-0.80), and biological index (1.16-1.72) can be used to identify SDOC from DOC in other media. Solubilization experiments indicated that SDOC (20 mg/L) improved the solubility of hydrophobic pollutants (pyrene and triclocarban) by 2-6 folds in aqueous environments, which potentially enhances the mobility of pollutants and enlarges the potential risk region. This study indicates that SDOC may cause a severe harm to aqueous environments in addition to the atmosphere. The results have profound implications for comprehensive assessments of the environmental effects of SDOC while promoting its identification and elucidating its behavior in aqueous environments., (Copyright © 2021. Published by Elsevier Ltd.)

Column experiments were carried out to investigate the transport of TiO 2 nanoparticles (nTiO 2 ) in water-saturated porous media in the presence of various imidazolium-based ionic liquids (ILs) with different alkyl chain lengths and counteranions. The results indicated that the effects of ILs on nTiO 2 transport were considerably dependent upon IL species. In general, the transport-inhibition effects increased with the increasing length of branched alkyl chain on the ILs (i.e., [C 6 mim]Cl > [C 4 mim]Cl > [C 2 mim]Cl). The trend was dominated by the hydrophobicity effects of ILs. Meanwhile, the inhibitory effects of ILs were strongly related to the counteranions and followed the order of [C 4 mim]Cl > [C 4 mim][TOS] > [C 4 mim][PF 6 ], mainly due to different electrostatic repulsion force between nanoparticles and porous media in the presence of various ILs. Furthermore, the inhibitory role of [C 4 mim][TOS] in nTiO 2 transport under acidic conditions (i.e., pH 6.5) was greater than that under alkaline conditions (i.e., pH 8.0). The dominant mechanism was that the differences in the extent of electrostatic repulsion between sand grains and nTiO 2 with or without ILs at pH 6.5 were larger than that at pH 8.0. Moreover, two-site kinetic retention model and DLVO theory provided good descriptions for the transport behaviors of nTiO 2 with different ILs., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this study, transport behaviors of graphene oxide (GO) in saturated uncoated (i.e., clean sand) and goethite-coated sand porous media were examined as a function of the phosphate. We found that phosphate enhanced the transport of GO over a wide range of solution chemistry (i.e., pH 5.0-9.0 and the presence of 10 mmol/L Na + or 0.5 mmol/L Ca 2+ ). The results were mainly ascribed to the increase of electrostatic repulsion between nanoparticles and porous media. Meanwhile, deposition site competition induced by the retained phosphate was another important mechanism leading to promote GO transport. Interestingly, when the phosphate concentration increased from 0.1 to 1.0 mmol/L, the transport-enhancement effect of phosphate in goethite-coated sand was to a much larger extent than that in clean sand. The observations were primarily related to the difference in the total mass of retained phosphate between the iron oxide-coated sand and clean sand columns, which resulted in different degrees of the electrostatic repulsion and competitive effect of phosphate. When the background solution contained 0.5 mmol/L Ca 2+ , phosphate could be bind to sand/ goethite-coated sand surface by cation bridging; and consequently, promoted competition between phosphate and nanoparticles for deposition sites, which was an important mechanism for the enhanced effect of phosphate. Moreover, the DLVO theory was applicable to describe GO transport behaviors in porous media in the absence or presence of phosphate. Taken together, these findings highlight the important status and role of phosphate on the transport and fate of colloidal graphene oxide in the subsurface environment., (Copyright © 2020. Published by Elsevier B.V.)

The effects of Bacillus subtilis inoculation on the growth and Cd uptake of alfalfa were evaluated in this research using pot experiments, and the relevant biochemical mechanisms were first investigated by combined microbial diversity and nontarget metabolomics analyses. The results indicated that inoculation with alfalfa significantly decreased the amount of plant malondialdehyde (MDA) and improved the activities of plant antioxidant enzymes and soil nutrient cycling-involved enzymes, thereby promoting biomass by 29.4%. Inoculation also increased Cd bioavailability in rhizosphere soil by 12.0% and Cd removal efficiency by 139.3%. The biochemical mechanisms included enhanced bacterial diversity, transformed microbial community composition, regulated amounts of amino acids, fatty acids, carbohydrates, flavonoids and phenols in rhizosphere soil metabolites, and modulations of the corresponding Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways. These responses were beneficial to microbial activity, nutrient cycling, and Cd mobilization, detoxification, and decontamination by alfalfa in soil. This study, especially the newly identified differential metabolites and metabolic pathways, provides new insights into mechanism revelation and strategy development in microbe-assisted phytomanagement of heavy metal-contaminated soils., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Given the ubiquity and abundance of the iron oxide minerals and their important roles in affecting the environmental fate of graphene oxide (GO) nanoparticles, the attachment of GO onto three iron oxide minerals (i.e., hematite, goethite, and ferrihydrite) under different solution chemistry conditions was investigated in this study. The main mechanism of the attachment of GO was electrostatic interaction. Calculations based on the DLVO theory showed that the attachment was a favorable process. Interestingly, the affinity of GO towards three iron oxide minerals was in the order of ferrihydrite > goethite > hematite. This result indicates that different characteristics of various iron oxides (e.g., specific surface area, crystal structure, and surface charge, and surface hydroxyl densities) can influence their attachment capacities for GO. The attachment of GO depended on the solution pH and ionic strength. Electrostatic attraction and hydrogen bonding were the important retention mechanisms for GO attachment when pH < pH PZC (the point of zero charge) and pH > pH PZC , respectively. The attachment capacities of iron oxides decreased with increasing ionic strength at lower pH because of the decrease of the electrostatic attraction. Meanwhile, the presence of divalent cations (i.e., Ca 2+ and Cu 2+ ) could significantly promote GO attachment mainly by the surface-bridging mechanism. Meanwhile, the enhancement effect of Cu 2+ was greater than Ca 2+ due to the greater complexation affinity of Cu 2+ . Furthermore, attachment isotherms showed that the presence of phosphate could inhibit the attachment of GO onto minerals obviously. Because phosphate could form inner-sphere surface complex on the iron oxide surface, and consequently decreased the electrostatic attraction between nanoparticles and minerals. Our study has important implications for predicting the fate of GO in natural environment where amounts of iron oxide minerals are present.

Since iron oxide minerals are ubiquitous in natural environments, the release of graphene oxide (GO) into environmental ecosystems can potentially interact with iron oxide particles and thus alter their surface properties, resulting in the change of their transport behaviors in subsurface systems. Column experiments were performed in this study to investigate the co-transport of GO nanoparticles and hematite colloids (a model representative of iron oxides) in saturated sand. The results demonstrated that the presence of hematite inhibited GO transport in quartz sand columns due to the formation of less negatively charged GO-hematite heteroaggregates and additional deposition sites provided by the adsorbed hematite on sand surfaces. Contrarily, GO co-present in suspensions significantly enhanced the transport of hematite colloids through different mechanisms such as the increase of electrostatic repulsion, decreased physical straining, GO-facilitated transport of hematite (i.e., highly mobile GO nanoparticles served as a mobile carrier for hematite). We also found that the co-transport behaviors of GO and hematite depended on solution chemistry (e.g., pH, ionic strength, and divalent cation (i.e., Ca 2+ )), which affected the electrostatic interaction as well as heteroaggregation behaviors between GO nanoparticles and hematite colloids. The findings provide an insight into the potential fate of carbon nanomaterials affected by mineral colloids existing in natural waters and soils., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this study, batch and column tests were performed to investigate the co-transport of graphene oxide (GO) nanoparticles and tetracycline in saturated porous media under various solution chemistry conditions. Research indicated that GO and tetracycline had mutual promotion effect on their transport in the porous media under all the tested conditions, which was ascribed to the high adsorption capacity of tetracycline onto GO and the increased electrostatic repulsion as well as their competition for deposition sites on sand surfaces. Interestingly, the mutually promoting function of GO and tetracycline under acidic conditions was greater than that under alkaline conditions, the dominant mechanism was that the increased solution pH decreased the sorption of tetracycline onto GO and weakened the deposition site competition. Furthermore, the mutually promoting effect of GO and tetracycline was Na + or Ca 2+ concentration-dependent. Specially, increased Ca 2+ concentration weakened the promoting effect of GO on tetracycline transport but magnified the promoting effect of tetracycline on GO transport. This is because higher Ca 2+ concentration could cause a decrease in the adsorption of tetracycline on GO and facilitate more tetracycline molecules to occupy the deposition sites on sand surfaces. Additionally, sodium dodecyl sulfate had enhancement effect on co-transport of GO and tetracycline. Findings from this study clearly indicated that antibiotics and carbon based nanomaterials may transport together under various solution chemistry conditions, and consequently affect their fates in aquatic environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

With the broadly application of antibiotics to treat infectious diseases in humans and animals, antibiotic contaminants such as tetracycline (TC) and ciprofloxacin (CIP) have been detected in soil environments, where iron oxide minerals and phosphate are ubiquitous. To date, the influence of phosphate on the adsorption behaviors of TC/CIP onto iron oxides is still poorly understood. In this study, the effects of phosphate on the adsorptions of TC and CIP onto iron oxide minerals were investigated. Adsorption isotherms showed that the adsorption affinities of TC and CIP onto the three iron oxide minerals were in the order of goethite > hematite > magnetite with or without phosphate, the trend was dominated by different surface area and amount of surface hydroxyl groups of iron oxide minerals. Meanwhile, TC contains more functional groups than CIP for bonding, which resulted in greater adsorption affinity of three iron oxides to TC than that to CIP. Interestingly, phosphate weakened TC adsorption, while enhanced CIP adsorption, on the three iron oxides. This observation was ascribed to that phosphate anion enhanced the surface negative charge of iron oxides, which reinforced the electrostatic repulsion between iron oxides and negatively charged TC, also reinforced the electrostatic attraction between iron oxides and positively charged CIP. Furthermore, the inhibitory effect of phosphate on TC adsorption was dramatically enhanced at high pH, while the promoting effect of phosphate on CIP adsorption was slightly changed with various pH. Our results highlight the importance of phosphate in exploring the environmental fate of antibiotics in natural environment., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Antibiotics, a highly prevalent class of environmental organic pollutants, are becoming a matter of global concern. Clay minerals that are ubiquitous in subsurface environments may play an important role in the fate and transport of antibiotics. Taking ciprofloxacin (CIP) as a model antibiotic, this work explored the role of clay colloids (kaolinite and montmorillonite) on the adsorption and transport of CIP under different chemical solution conditions. The adsorption isotherms showed that montmorillonite colloids had a larger CIP sorption capacity than kaolinite colloids. The results of transport experiments indicated that montmorillonite colloids could promote CIP transport in saturated sand columns, but the addition of kaolinite colloids affected CIP mobility to a much smaller extent. The much stronger transport-enhancement effect of montmorillonite colloids was due to CIP adsorbed strongly to the colloids and desorption hysteresis of colloid-adsorbed CIP, likely stemming from the intercalation of this antibiotic in the interlayer of montmorillonite. Interestingly, transport of clay colloids increased with the increasing pH from 5.0 to 9.0; however, CIP transport decreased with the increasing pH in the presence of clay colloids. The observations were likely attributable to pH-dependent ciprofloxacin adsorption/desorption to clay minerals. Increasing the concentrations of NaCl and CaCl 2 generally decreased the contaminant-mobilizing ability of montmorillonite colloids, mainly by increasing the aggregation of colloids and thus, decreasing the transport of colloid-adsorbed CIP. Moreover, under the test conditions (1 mM NaCl and pH 7.0), the presence of CIP inhibited the transport of clay colloids due to the increase in aggregate size of clay colloids with the addition of CIP. Overall, these findings suggest that clay colloids with high adsorption abilities for antibiotics in the subsurface environment may act as a carrier for certain antibiotic compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Low-molecular-weight organic acids (LMWOAs) are ubiquitous in the aquatic environment and consequently may affect the heavy metal transport in aquifer systems. In this study, the influences of LMWOAs on the transport of Cd 2+ under different pH conditions in saturated porous media were evaluated. For this, three LMWOAs such as acetic acid, tartaric acid, and citric acid were employed. A two-site nonequilibrium transport model was applied to simulate the transport data. Under acidic conditions (pH 5.0), the results indicated that LMWOAs inhibited the transport of Cd 2+ even at the low concentrations of organic acids (i.e., 0.05 and 0.1 mM). The inhibition effects might be attributed to the complexation role of the sand surface-bound organic acids and also electrostatic interaction. Meanwhile, the inhibition effects of LMWOAs on Cd 2+ transport in the following order of citric acid > tartaric acid > acetic acid, which was also in agreement with the decreasing complex stability constants between Cd 2+ and LMWOAs. This order may be dependent on their molecular structures (i.e., amount and type of functional groups) and complexing strength. Interestingly, when the LMWOA concentrations 0.5 mM, tartaric acid and citric acid still inhibited Cd 2+ transport, while acetic acid slightly enhanced the Cd 2+ mobility due to its weaker complexing strength. However, under neutral conditions (pH 7.0), LMWOAs generally enhanced the transport of Cd 2+ . The transport-enhancement of LMWOAs was ascribed to the formation of stable aqueous non-adsorbing Cd-organic acid complexes. In addition, citric acid could obviously inhibit the transport of Cd 2+ under competitive transport conditions (i.e., with competing cations), which is mainly due to different complex affinities of citric acid to Pb 2+ and Cd 2+ . These findings demonstrate that LMWOAs may inhibit or facilitate Cd 2+ transport under different environmental conditions. Thus, environmental assessment concerning the transport of heavy metals should consider the roles of organic acids., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The effects of low-molecular-weight organic acids (LMWOAs) on the transport of graphene oxide nanoparticles in saturated kaolinite- and goethite-coated sand columns were studied. Acetic acid, glycolic acid, malonic acid, and tartaric acid were chosen in the experiments. LMWOAs enhanced the mobility of GO by electrostatic/steric repulsion. In addition, they competed with GO for limited deposition sites on grain surfaces. The effects of organic acids on the transport of GO strongly depended on organic acid species. In general, the transport enhancement effects followed the order of tartaric acid > malonic acid > glycolic acid > acetic acid; this difference may be related to the number and type of functional groups of organic acids. Different LMWOAs enhanced the transport of GO in goethite-coated sand to a larger extent than did in kaolinite-coated sand under the test conditions; this was likely related to the differences of physicochemical characteristics between goethite and kaolinite. Organic acids significantly inhibited the deposition of GO at 0.5 mM Ca 2+ ; this was possible that Ca 2+ enhanced adsorption of organic acids by complexing with the surface O-functionalities of both LMWOAs and sand grain. Consequently, more organic acid molecules competed with GO for deposition sites on grain surfaces. Additionally, a two-site transport model was used to fit the transport data. Our findings have important implications for the understanding of the deposition and fate of GO in soil especially in rhizosphere environments where various low-molecular-weight organic acids are active.

Tetracycline is one of the most commonly used antibiotics in the world. Eventually, large amounts of this contaminant will enter into the subsurface environment, where a variety of ions exist. In this study, the effects of divalent metal cations (Mg2+, Ca2+, Pb2+ and Cu2+) and inorganic anions (Cl-, NO3-, SO42- and H2PO4-) on the transport of tetracycline in saturated porous media were investigated. Both batch and column experiments were conducted to determine the interactions between tetracycline and sand. Batch sorption experimental results showed that the presence of divalent metal cations could increase the sorption of tetracycline onto sand due to the cation-bridging mechanism. When Na+ was the counterion in the background solution, anions caused a significant decrease in tetracycline sorption owing to the occupation of some adsorption sites by anions and the decrease of electrostatic attraction. Column experiments indicated that the inhibition effects of divalent cations followed the order of Cu2+ > Pb2+ > Ca2+ ≈ Mg2+; the regular pattern might be related to their different complexing strengths. The presence of inorganic anions enhanced the mobility of tetracycline following the order of H2PO4- > SO42- > NO3- > Cl-. Transport-enhancement effects of anions were ascribed to competition between inorganic anions and tetracycline for deposition sites on sand surfaces. However, when Ca2+ was the counterion, the differences in the breakthrough curve of tetracycline among three inorganic anions (i.e., SO42-, NO3- and Cl-) were very small. In this case, the transport-inhibiting effects of anions could be counterbalanced by the transport-enhancement effects of the cation-bridging effect. Also, the two-site nonequilibrium transport model was applied to analyze the transport data. Findings from this study improve our understanding of the transport of tetracycline in saturated aquifer materials.

Plastic debris, in particular, microplastics and nanoplastics, is becoming an emerging class of pollutants of global concern. Aging can significantly affect the physicochemical properties of plastics, and therefore, may influence the fate, transport, and effects of these materials. Here, we show that aging by UV or O 3 exposure drastically enhanced the mobility and contaminant-mobilizing ability of spherical polystyrene nanoplastics (PSNPs, 487.3 ± 18.3 nm in diameter) in saturated loamy sand. Extended Derjaguin-Landau-Verwey-Overbeek calculations and pH-dependent transport experiments demonstrated that the greater mobility of the aged PSNPs was mainly the result of surface oxidation of the nanoplastics, which increased not only the surface charge negativity, but more importantly, hydrophilicity of the materials. The increased mobility of the aged PSNPs significantly contributed to their elevated contaminant-mobilizing abilities. Moreover, aging of PSNPs enhanced the binding of both nonpolar and polar contaminants, further increasing the contaminant-mobilizing ability of PSNPs. Interestingly, aging enhanced binding of nonpolar versus polar compounds via distinctly different mechanisms: increased binding of nonpolar contaminants (tested using pyrene) was mainly the result of the modification of the polymeric structure of PSNPs that exacerbated slow desorption kinetics; for polar compounds (4-nonylphenol), aging induced changes in surface properties also resulted in irreversible adsorption of contaminants through polar interactions, such as hydrogen bonding. The findings further underline the significant effects of aging on environmental fate and implications of nanoplastics.

The impact of low-molecular weight organic acids (LMWOAs) on the transport of graphene oxide (GO) nanoparticles in saturated quartz sand was investigated. The different LMWOAs such as acetic acid, glycolic acid, malonic acid, and tartaric acid were used in experiments. The effects of LMWOAs on the transport of GO were markedly dependent upon organic acid species. In general, the transport enhancement effects followed the order of tartaric acid > malonic acid > glycolic acid > acetic acid, the regular pattern might be related to amount and type of functional groups of LMWOAs. Additionally, the different enhanced ability of LMWOAs was determined by their molecular weight. In the presence of Na + , the main deposition mechanism was ascribed to steric hindrance and competition between LMWOA and GO for deposition sites on grain surfaces under acidic conditions (i.e., pH 4.0 and 5.0). Batch adsorption experiments indicated the extents of competitive adsorption between LMWOAs and GO on quartz sand. In addition, the DLVO theory was not applicable to describe the transport of GO in the presence of LMWOAs at pH 5.0. Nevertheless, electrostatic and steric repulsion, existing between GO and sand grains, were the most important deposition mechanisms under the neutral condition (i.e., pH 7.0). When Ca 2+ was the main cation in the background solution, the transport enhancement effects followed quite similar order to those of Na + , mainly due to different complexing strength of organic acids., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The increasing production and use of graphene-based nanomaterials (e.g., graphene oxide (GO) and reduced graphene oxide (RGO)) will lead to their environmental release. To date, transport of RGOs in saturated porous media is poorly understood. Here, we examined the transport behaviors of three RGO materials obtained by reducing a GO product with commonly used reducing agents - N 2 H 4 , NaBH 4 and L-ascorbic acid (referred to as N 2 H 4 -RGO, NaBH 4 -RGO and VC-RGO, respectively). When the dominant background cation was Na + , K + or Mg 2+ , the mobility of the RGOs and GO in saturated quartz sand correlated well with their surface C/O ratio. Interestingly, the lower mobility of the more reduced materials (the ones with higher C/O values) was not only the results of their less negative surface charges and larger particle sizes, but also the outcome of their greater hydrophobicity, in line with the calculated extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) profiles. Counterintuitively, when the background cation was Ca 2+ , the least reduced material among the three RGOs, VC-RGO, exhibited the lowest mobility. Analysis of electrophoretic and aggregation properties, as well as pH-effect experiments, indicated that the surprisingly low mobility of VC-RGO was attributable to the strong cation-bridging effect (primarily Ca 2+ -bridging between RGO and quartz sand) associated with this material, as VC-RGO contained the highest amount of surface carboxyl group (a strong metal-binding moiety). Notably, enhanced attachment (due to increased hydrophobic effect and cation-bridging) and particle aggregation appeared to work synergistically to increase RGO retention, as the attachment of large RGO aggregates significantly enhanced particle straining by narrowing the flow path. These observations reveal a largely overlooked link between the mobility of graphene-based materials and their key physicochemical properties., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The environmental implications of graphene oxide (GO) have received much attention. Transport of GO in subsurface environment is a critical process affecting the migration and potential risks of this important class of carbonaceous nanomaterials. To date, the effects of heterogeneity in porous media, in particular, iron oxides, on GO transport are not well studied. In this study, we investigated the transport properties of GO in saturate quartz sand as affected by the presence of iron oxides, using goethite, hematite and ferrihydrite as the model iron oxide species, and applied a two-site transport model (which accounts for both attachment and straining) to fit the transport data. We found that iron oxide coating on sand surfaces markedly inhibited GO transport, mainly due to increased electrostatic attraction between particles and collectors, as the positively charged iron oxides provided favorable deposition sites for the negatively charged GO nanosheets. Additionally, increased surface roughness was likely an additional mechanism leading to the enhanced GO deposition. The extent of transport inhibition by iron oxides also depended on the morphology iron oxides, in that at the same Fe loading a larger effect was observed when iron oxides existed as the coating on sand surface than as discreet particles. The presence of iron oxide coatings (tested using goethite) could magnify the effects of cations on GO transport. Specifically, the presence of goethite facilitated the accumulation of cations on the surface of sand, and in the case of Ca 2+ , the binding of GO via the cation-bridging mechanism was enhanced, as goethite contained abundant surface hydroxyl groups that are strong metal-complexing moieties., (Copyright © 2018 Elsevier B.V. All rights reserved.)

With the increase in production and wide application of graphene oxide (GO), colloidal GO particles are expectantly released into soil and groundwater, where a large number of mineral particles exist. In addition, the porewater chemistry (e.g. organic acid, valence of cation) is a neglected but important aspect to comprehensively investigate the fate of GO. The interactions of GO with three ubiquitous clay minerals (i.e., montmorillonite, kaolinite and diatomite) have been systematically investigated through batch experiments across different solution chemistry conditions. In general, the affinity towards GO is in the order of montmorillonite > kaolinite > diatomite under the same experimental conditions. This observation can be explained by the characteristics of different clay minerals, such as surface charge and surface area. The results indicated that increasing the ionic strength or decreasing the pH enhanced the attachment of GO nanoparticles onto clay minerals as a result of electrostatic interactions. With the increase in concentration of Ca2+, more GO particles were attached onto clay mineral particles. This is caused by complexation between the surface oxygen functional groups of both GO nanoparticles and clay minerals. The presence of 0.1 mM tartaric acid significantly inhibited the attachment of GO onto clay minerals. This is possibly linked to the increased negative charges of the organic acids and the competition between organic acids and GO. The interaction energies were also calculated by applying the classical DLVO theory. The results of this study have helped to understand the behavior and fate of GO in subsurface formations.

In this work, a sensitive photoelectrochemical aptasensor was developed for kanamycin detection using an enhanced photocurrent response strategy, which is based on the surface plasmon resonance effect of gold nanoparticles deposited on a 3D TiO 2 -MoS 2 flower-like heterostructure. A significant aspect of this development lies in the photoelectrochemical and morphological features of the unique ternary composite, which have contributed to the excellent performance of the sensor. To develop an aptasensor, mercapto-group modified aptamers were immobilised on the photoactive composite as a recognition unit for kanamycin. The TiO 2 -MoS 2 -AuNP composite was demonstrated to accelerate the electron transfer, increase the loading of aptamers and improve the visible light excitation of the sensor. Under optimal conditions, the aptasensor exhibited a dynamic range from 0.2 nM to 450 nM of kanamycin with a detection limit of 0.05 nM. Overall, we have successfully synergised both the electrical and the optical merits from individual components to form a ternary composite, which was then demonstrated as an effective scaffold for the development of PEC biosensors., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + < K + < Cs + , and those of alkaline earth metal ions followed the order of Mg 2+ < Ca 2+ < Ba 2+ . With batch adsorption experiments and microscopic data, we verified that cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

We describe how the reduction of graphene oxide (GO) via environmentally relevant pathways affects its transport behavior in porous media. A pair of sulfide-reduced GOs (RGOs), prepared by reducing 10 mg/L GO with 0.1 mM Na2S for 3 and 5 days, respectively, exhibited lower mobility than did parent GO in saturated quartz sand. Interestingly, decreased mobility cannot simply be attributed to the increased hydrophobicity and aggregation upon GO reduction because the retention mechanisms of RGOs were highly cation-dependent. In the presence of Na(+) (a representative monovalent cation), the main retention mechanism was deposition in the secondary energy minimum. However, in the presence of Ca(2+) (a model divalent cation), cation bridging between RGO and sand grains became the most predominant retention mechanism; this was because sulfide reduction markedly increased the amount of hydroxyl groups (a strong metal-complexing moiety) on GO. When Na(+) was the background cation, increasing pH (which increased the accumulation of large hydrated Na(+) ions on grain surface) and the presence of Suwannee River humic acid (SRHA) significantly enhanced the transport of RGO, mainly due to steric hindrance. However, pH and SRHA had little effect when Ca(2+) was the background cation because neither affected the extent of cation bridging that controlled particle retention. These findings highlight the significance of abiotic transformations on the fate and transport of GO in aqueous systems.

Sewage irrigation is one of the best options to reduce the stress on limited fresh water and to meet the nutrient requirement of crops. Environment pollution caused by volatile halogenated hydrocarbons (VHCs) associated with sewage irrigation has received increasing attention due to the toxicological importance in ecosystem. The aim of this study was to discuss the spatial distribution characteristics of VHCs in unsaturated zone under sewage irrigation and their migration in the environment. Soil samples were collected from XiaoDian district of TaiYuan city and measured for the major VHCs including of chloroform (CHCl3), tetrachloromethane (CCl4), trichloroethylene (C(2)HCl(3)), tetrachloroethylene(C(2)Cl(4)), pentachlorobenzene (C(6)HCl(5)), hexachlorobenzene (C(6)Cl(6)). Results showed that VHCs were accumulated in the unsaturated zone with long-term sewage irrigation. The contents of VHCs in the unsaturated zone of the study area were 34, 2, 3, 1.5, 8.3, 4.8 times higher than the background value respectively. Soils with long-term irrigation of sewage showed higher contents of VHCs than that with short-term irrigation of sewage. Not only the irrigation time, soil physical properties (e.g. soil texture) also played an important role on VHCs accumulation in soil.

With the increasing production and use of graphene oxide, the environmental implications of this new carbonaceous nanomaterial have received much attention. In this study, we found that the presence of low concentrations of graphene oxide nanoparticles (GONPs) significantly enhanced the transport of 1-naphthol in a saturated soil, but affected the transport of phenanthrene to a much smaller extent. The much stronger transport-enhancement effect on 1-naphthol was due to the significant desorption hysteresis (both thermodynamically irreversible adsorption and slow desorption kinetics) of GONP-adsorbed 1-naphthol, likely stemmed from the specific polar interactions (e.g., H-bonding) between 1-naphthol and GONPs. Increasing ionic strength or the presence of Cu(II) ion (a complexing cation) generally increased the transport-enhancement capability of GONPs, mainly by increasing the aggregation of GONPs and thus, sequestering adsorbed contaminant molecules. Interestingly, modifying GONPs with Suwannee River humic acid or sodium dodecyl sulfate had little or essentially no effect on the transport-enhancement capability of GONPs, in contrast with the previously reported profound effects of humic acids and surfactants on the transport-enhancement capability of C60 nanoparticles. Overall, the findings indicate that GONPs in the aquatic environment may serve as an effective carrier for certain organic compounds that can interact with GONPs through strong polar interactions.

The authors conducted column experiments and a modeling study to understand the effects of several environmental factors on the aggregation and transport of graphene oxide nanoparticles (GONPs) in saturated quartz sand. The GONPs were negatively charged and stable under the test conditions (0-50 mM NaCl; pH 4.8-9.0), and the Derjaguin-Landau-Verwey-Overbeek (DLVO) calculation indicated that deposition of GONPs was under unfavorable attachment conditions. The GONPs exhibited high mobility even at an ionic strength of 25 mM NaCl. The transport of GONPs was insensitive to the changes of pH (from 5.1 to 9.0), but the presence of 10 mg/L Suwannee River humic acid (SRHA) considerably enhanced transport at high ionic strength (35 mM NaCl), likely via enhanced steric repulsion and significantly inhibited stacking of GO flakes. Varying flow velocity also enhanced transport at high ionic strength. In general, GONPs exhibit greater mobility compared with other carbon nanoparticles because the aggregation and transport of GONPs are more resilient to changes in solution chemistry and hydrodynamic forces that favor aggregation and deposition of nanoparticles. A 2-site transport model incorporating both the blocking-affected attachment process and straining effects can effectively model the transport of GONPs. The high mobility of GONPs should be given full consideration in assessing their environmental risks., (© 2014 SETAC.)

We examined the transport properties of graphene oxide nanoparticles (GONPs) in saturated sandy soil, under different solution chemistry conditions and flow velocities. GONPs exhibited high mobility in soil, even at 50 mM NaCl. While at relatively high ionic strength GONPs were less mobile in soil than in quartz sand, the differences were not significant. At a concentration of 0.5 mM, Ca(2+) significantly inhibited the transport of GONPs in soil, but only slightly inhibited the transport in quartz sand. This was because by complexing with the surface O-functionalities of both GONPs and soil components, Ca(2+) could enhance the aggregation of GONPs and bridge GONPs and soil grains. Increasing pH from 4 to 9 only slightly enhanced the transport of GONPs in soil, probably because the mobility of GONPs was already high at low pH. The presence of 10 mg L(-1) Suwannee River humic acid significantly enhanced the transport of GONPs in quartz sand at 35 mM, but only had a small effect for the transport in soil. This was possibly linked to the much smaller grain sizes and much more heterogeneous nature of the soil. Flow velocity had marked effects on the transport in soil, but essentially no effects on the transport in quartz sand. A two-site transport model incorporating both the blocking-affected attachment process and straining effects can effectively model the transport of GONPs. The high mobility of GONPs may have important implications for their environmental fate and effects.