Tetracycline Transport Research Articles

Influence of surfactant molecular features on tetracycline transport in saturated porous media of varied surface heterogeneities

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 Ca2+, SDBS enhanced TC transport by forming deposited SDBS-Ca2+-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.

Cu(II) inhibited the transport of tetracycline in porous media: role of complexation.

Tetracycline (TC) and Cu(II) coexist commonly in various waters, which may infiltrate into the subterranean environment through runoff and leaching, resulting in substantial ecological risks. However, the underlying mechanisms why Cu(II) affects the transport of TC in porous media remain to be further explored and supported by more evidence, especially the role of complexation. In this study, the transport of TC with coexisting Cu(II) was comprehensively explored with column experiments and density functional theory (DFT) calculation. At natural environmental concentrations, Cu(II) significantly inhibited the transport of TC in the quartz sand column. Cu(II) augmented the retention of TC in the column mainly via electrostatic force and complexation. The interaction between TC and TC-Cu complexes on the surface of SiO2 was investigated with first-principles calculations for the first time. There were strong van der Waals forces and coordination bonds on the surface of complexes and SiO2, leading to higher adsorption energy than that of TC and inhibiting its penetration. This study offers novel insights and theoretical framework for the transport of antibiotics in the presence of metal ions to better understand the fate of antibiotics in nature.

Highly porous NiFe-mixed metal oxides derived from calcinated layered double hydroxide for efficient antibiotics removal

Tetracycline (TC), a widely employed broad-spectrum antibiotic with global prevalence, possesses the ability to infiltrate soil matrices and potentially reach groundwater systems, thereby posing a consequential human health risk. To address this concern, a novel NiFe-mixed metal oxides (MMO) composite was synthesized and employed within quartz sand as a strategic measure to regulate the downward migration of TC. In-depth investigations of TC transport behavior in quartz sand, complemented by NiFe-MMO, were conducted via a series of rigorous batch and saturation-filled column experiments. The impacts of NiFe-MMO dosage, ionic strength, cationic types, solution pH, and flow rates on TC transport were systematically and comprehensively scrutinized. Our findings reveal that even minute quantities of NiFe-MMO prompt substantial TC adsorption, facilitated by electrostatic interactions and surface complexation, notably in low-concentration background solutions. Additionally, the presence of Ca2+ engenders a bridging effect, further enhancing TC adsorption onto the sand. These significant observations bear far-reaching implications in elucidating the fate of antibiotics within the intricate interplay of soil and groundwater domains. The strategic amalgamation of NiFe-MMO and quartz sand offers innovative prospects for managing TC dissemination, thereby augmenting endeavors toward sustainable environmental protection.

Interplay of compound pollutants with microplastics transported in saturated porous media: Effect of co-existing graphene oxide and tetracycline

Co-existence of microplastics, nanomaterials, and antibiotics may lead to intensified multifaceted pollution, which may influence their fate in soils. This study investigated the co-transport behavior of polystyrene microplastics (PS) and compound pollutants of graphene oxide (GO) and tetracycline (TC). Packed column experiments for microplastic with or without combined pollutants were performed in KCl (10 and 30 mM) and CaCl2 solutions (0.3 and 1 mM). The results showed transport of PS was facilitated at low ionic strengths and inhibited at high ionic strengths by GO with or without TC under examined conditions. Carrier effect of GO as well as the aggregation of PS in the presence of co-exiting GO or GO-TC could be the contributor. Although the existence of TC relieved the ripening phenomenon of PS and GO deposition due to enhanced electronegativity of sand media, the effect of GO on the PS transport has not been significantly impacted, indicating the dominant role of GO during cotransport process. Furthermore, the transport of PS was increased by TC owing to competition for deposition sites on sand surfaces. In turn, the transport of TC was mainly affected by PS whether graphene was present or not. The increase in electrostatic repulsive force (transport-promoting) and addition adsorption sites (transport-inhibiting) may be responsible for the observations. Our findings could improve understandings of complex environmental behaviors of microplastics and provide insight into investigation on cotransport of emerging contaminants under various conditions relevant to the subsurface environment.

Mobility of tetracycline in saturated porous media: Single and combined functions of ligands and ferrihydrite colloids

Considering that the ubiquitous organic/inorganic ligands and iron oxide minerals play significant roles in antibiotic fate in the aquifers. In this study, the influences of two ligands (i.e., citric acid and phosphate) on the transport of tetracycline (TC, a broad-spectrum antibiotic) with or without ferrihydrite colloids in quartz sand were explored. In the absence of ferrihydrite colloids, column studies indicated that the two ligands promoted TC transport and citric acid exhibited a greater transport-enhancement effect than phosphate. The observation was mainly ascribed to a stronger competition effect, steric hindrance, and electrostatic repulsion in the addition of citric acid compared to phosphate. Moreover, ferrihydrite colloids inhibited TC transport, which was mainly caused by contaminant retention associated with colloid deposition and the additional active sites for TC provided by the deposited iron oxide colloids with positive charges. Another interesting finding was that both ligands weakened the inhibitory influences of ferrihydrite colloids on the mobility of TC. This observation stemmed from the enhanced transport of free TC molecules (i.e., TC unassociated with colloids), colloids acting as carriers of TC, as well as the competitive deposition of TC− species and ferrihydrite colloids. Meanwhile, the extent of ferrihydrite colloid-mediated mobility of TC affected by citric acid was much greater than phosphate. Because citric acid exhibited a much greater influence on the interaction of colloids, TC molecules, and sand grains during the transport process. These results reveal the importance of accounting for the impacts of natural ligands on colloid-mediated transport of antibiotics in the subsurface systems.

Surfactants-mediated the enhanced mobility of tetracycline in saturated porous media and its variation with aqueous chemistry

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 (10mM 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 Cu2+ (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-Cu2+ 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.

Fate and transport of tetracycline and ciprofloxacin and impact on nitrate reduction activity in coastal sediments from the Seine Estuary, France.

Fluoroquinolones and tetracyclines are frequently detected antibiotics in aquatic sediments. In this study, the transport of ciprofloxacin (CIP) and tetracycline (TET) was investigated in sediments from the Seine Estuary (France), under nitrate reducing conditions. Dynamic flow experiments showed that although TET and CIP strongly interacted with the sediment components through adsorption and (bio)-chemical transformation, they kept their antimicrobial activities. Less nitrate reduction was observed during the first period of breakthrough, while TET and CIP were absent in the column effluent. Batch experiments with freeze-dried vs fresh sediments showed that adsorption and abiotic degradation are the major removal processes, while microbe-driven transformation is of less importance. Whereas TET is to a large extent chemically transformed and little adsorbed in the sediment, CIP was less transformed and more adsorbed, most likely due to the great reactivity of TET with redox-active mineral surfaces. Our findings show the strong capacity of natural sediment to retain and transform antibiotics, while still maintaining their antimicrobial activity or inhibitory effect of nitrate reducing activity.

Insight into the effect of phosphate on ferrihydrite colloid-mediated transport of tetracycline in saturated porous media.

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.

Role of Staphylococcus aureus Tet38 in Transport of Tetracycline and Its Regulation in a Salt Stress Environment.

Staphylococcus aureus Tet38 efflux pump has multiple functions, including conferring resistance to tetracycline and other compounds and enabling internalization and survival within epithelial cells. In this study, we evaluated the effects of sodium and potassium on tet38 expression. These monovalent cations are known to play a role in transport by the related S. aureus TetK and B. subtilis TetL transporters. tet38 transcription decreased with increasing sodium concentrations by means of direct repression by the salt stress-dependent KdpD/E regulator. tet38 transcription increased 20-fold and tetracycline minimum inhibitory concentration (MIC) increased 4-fold in a ΔkdpD mutant. KdpE bound specifically to the tet38 promoter. Under extreme salt stress, the survival of S. aureus with intact tet38 was reduced compared to that of a Δtet38 mutant. To study the effect of sodium on Tet38 function, we generated constructs overexpressing tet38 and tetK and introduced them into Escherichia coli TO114, which is deficient in major sodium transporters. Tet38 tetracycline efflux was directly demonstrated in a fluorescence assay, and tetracycline efflux of both Tet38 and TetK was abolished by the protonophore carbonyl cyanide 3-chlorophenylhydrazone (CCCP). In contrast, NaCl inhibited efflux by Tet38 but not TetK, whereas KCl inhibited efflux by TetK but not Tet38. Cell-associated Na increased with heterologous overexpression of Tet38. These data indicate that S. aureus Tet38 is a tetracycline efflux pump regulated by the KdpD/E regulator. Under salt stress, S. aureus adjusted its survival in part by reducing the expression of tet38 through KdpD/E. The mechanisms by which Tet38 is detrimental to salt tolerance in S. aureus and inhibited by sodium remain to be determined. IMPORTANCE This study shows that S. aureus Tet38 is a tetracycline efflux pump regulated by KdpD/E regulator. These findings are the first direct demonstration of Tet38-mediated tetracycline efflux, which had previously been inferred from its ability to confer tetracycline resistance. Under salt stress, S. aureus adjusts its survival in part by reducing the expression of tet38 through KdpD/E. We demonstrated the differences in the respective functions of S. aureus Tet38 and other tetracycline efflux transporters (S. aureus TetK, B. subtilis TetL) regarding their transport of tetracycline and Na+/K+. Notably, sodium selectively reduced tetracycline efflux by Tet38, and potassium selectively reduced tetracycline efflux by TetK. The multiple functions of Tet38 emphasize its importance in bacterial adaptation to and survival in diverse environments.

Accumulation, transportation, and distribution of tetracycline and cadmium in rice

Co-exposure to heavy metal and antibiotic pollution might result in complexation and synergistic interactions, affecting rice growth and further exacerbating pollutant enrichment. Therefore, our study sought to clarify the influence of different Tetracycline (TC) and Cadmium(Cd) concentration ratios (both alone and combined) on rice growth, pollutant accumulation, and transportation during the tillering stage in hydroponic system. Surprisingly, our findings indicated that the interaction between TC and Cd could alleviate the toxic effects of TC/Cd on aerial rice structures and decrease pollutant burdens during root elongation. In contrast, TC and Cd synergistically promoted the accumulation of TC/Cd in rice roots. However, their interaction increased the accumulation of TC in roots while decreasing the accumulation of Cd when the toxicant doses increased. The strong affinity of rice to Cd promoted its upward transport from the roots, whereas the toxic effects of TC reduced TC transport. Therefore, the combined toxicity of the two pollutants inhibited their upward transport. Additionally, a low concentration of TC promoted the accumulation of Cd in rice mainly in the root tip. Furthermore, a certain dose of TC promoted the upward migration of Cd from the root tip. Laser ablation-inductively coupled plasma mass spectrometry demonstrated that Cd mainly accumulated in the epidermis and stele of the root, whereas Fe mainly accumulated in the epidermis, which inhibited the absorption and accumulation of Cd by the rice roots through the generation of a Fe plaque. Our findings thus provide insights into the effects of TC and Cd co-exposure on rice growth.

Understanding flow patterns from the field – Controlled laboratory experiments on the transport behavior of veterinary antibiotics in the presence of liquid manure

The main entry path of veterinary antibiotics to the environment is the application of liquid manure on agricultural land. Along with the manure, they can infiltrate into soils and leach into groundwater. As the environmental behavior of veterinary antibiotics is strongly affected by the process of sorption, the comprehensive knowledge regarding their sorption behavior is key to a reliable risk assessment. However, the flow patterns in field experiments are influenced by several factors that can hardly be distinguished, while most of the sorption studies on veterinary antibiotics were designed without manure or as batch experiments, which means that the effects of manure on the transport behavior of the antibiotic substances remained unaccounted for. In order to understand the results from a previous field experiment and concurrently fill the identified knowledge gap, a column experiment was performed to investigate the effects of manure on the transport of sulfamethazine, sulfadiazine, tetracycline, and lincomycin in soil. Results show that sulfamethazine and sulfadiazine were highly mobile in both the presence and absence of manure, while tetracycline did not appear at the outlet of any column. Despite their high mobility, in the presence of manure the sulfonamides were slightly delayed compared to the conservative tracer as was also seen during the previous field experiment. Lincomycin transport was already delayed in the absence of manure. Furthermore, in the presence of manure, lincomycin was delayed by 4.5 times relative to the tracer, which clearly underlined the influence of manure on the transport of lincomycin and offers an explanation why lincomycin has barely been detected in the long-term field experiment. However, in contrast to the results obtained in the field experiment, the recovery rates were the same in presence and absence of manure for both sulfonamides and lincomycin, probably due to reduced degradation at the applied concentration level.

Transport of tetracycline in saturated porous media: combined functions of inorganic ligands and solution pH

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 TC2-) 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.

Colloid-mediated transport of tetracycline in saturated porous media: Comparison between ferrihydrite and montmorillonite

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.

Insights into the molecular mechanism of tetracycline transport in saturated porous media affected by low-molecular-weight organic acids: Role of the functional groups and molecular size

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., Ca2+ and Pb2+). Interestingly, tetracycline exhibited a higher mobility in the presence of Ca2+ relative to Pb2+ regardless of LMWOAs-free or LMWOAs-addition. This phenomenon was attributed to the fact that Pb2+ has a greater affinity with tetracycline and LMWOAs than Ca2+. 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.

LDPE and HDPE Microplastics Differently Affect the Transport of Tetracycline in Saturated Porous Media.

The accumulation of microplastics (MPs) in soil and sediments may influence the penetration of contaminants into subsurface environments. However, little attention has been paid to comparing the different roles of two common polyethylene (PE) types—low-density polyethylene (LDPE) and high-density polyethylene (HDPE). In this study, the transport behaviors of tetracycline in saturated quartz sand columns in the presence and absence of these two MPs were investigated, respectively. The results showed that both types of PE MPs restrained the mobility of tetracycline at neutral conditions, while such detrimental effects were weak at acid and alkaline conditions. The degree of nonequilibrium adsorption was higher, and tetracycline transferred easier to the kinetic site for the existence of LDPE than of HDPE. The increased roughness and Brunauer-Emmett-Teller (BET) surface areas, more negative zeta potentials and the formation of oxygen function groups on the surface of MPs after UV-weathering intensified the retardation of tetracycline transport. This study revealed that the PE type and weathering should be taken into account in risk assessment, along with the solution chemistry.

Insights into the mutual promotion effect of graphene oxide nanoparticles and tetracycline on their transport in saturated porous media.

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 Ca2+ concentration-dependent. Specially, increased Ca2+ concentration weakened the promoting effect of GO on tetracycline transport but magnified the promoting effect of tetracycline on GO transport. This is because higher Ca2+ 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.

Investigation of the deprotonation of tetracycline using differential absorbance spectra: A comparative experimental and DFT/TD-DFT study

Tetracycline is a type of broad-spectrum, naturally occurring antibiotic that leads to several side effects, such as affecting intestinal flora and increase in bacterial resistance. The affinity of tetracycline for abiotic and biotic surfaces and metal ions is closely related to its deprotonation state and charge distribution; however, its deprotonation-protonation property remains unclear. In this study, the hydrolysis of tetracycline was investigated by combining experiments with quantum-chemical calculations. The molecular structure of the probable deprotonation states were optimized by quantum-chemical calculations, and the corresponding absorbance spectra were predicted based on frontier molecular orbital (FMO) theory. The absorbance spectra showed structure-specific features at the different deprotonation states. In addition, changes in tetracycline absorbance spectra in the pH range of 2.00–12.00 was examined by spectroscopic titration. The deprotonation was found to proceed in the order of site 3, 4, 12, and 10, which was identified by comparing the quantum-chemical calculations and experimental differential absorbance spectra (DAS). The results in this study are of great significance for further studies of the transport and fate of tetracycline in the environment.

Influence of graphene oxide nanosheets on the cotransport of cu-tetracycline multi-pollutants in saturated porous media.

Antibiotic-heavy metal multi-pollutants are produced by intensive livestock farming and become an increasingly prominent problem. In this study, the transport behavior of tetracycline (TC) and its chelate with copper ions (Cu-TC) in saturated sand column with and without graphene oxide (GO) prefilled was investigated by laboratory breakthrough experiments. The effects of pH, ionic strength, and the cotransport with GO were studied detailedly. The results showed that the prepared nano-GO had a single- or multilayered sheet structure with a diameter of several μm. The surface of GO contained abundant oxygen-containing functional groups, which imparted it strong hydrophilicity and electronegativity. Pollutant transport experiments showed that decrease of H+ weakened the transport ability of TC and Cu-TC. Both Na+ and Ca2+ promoted the transport of TC, with Ca2+ having a much greater effect. The presence of Na+ inhibited the transport of Cu-TC, while Ca2+ promoted Cu-TC transport. The addition of Cu2+ was more favorable for the transport of Cu-TC than TC alone. In the GO-prefilled column, the effluent concentrations of TC and Cu-TC greatly decreased due to adsorption onto GO surfaces. The transport of Cu-TC was more related to GO concentration than TC alone due to the high affinity between GO and Cu-TC. Moreover, the transport behavior of GO in the sand column was consistent with that of the corresponding TC or Cu-TC, indicating that GO could cotransport with TC and Cu-TC multi-pollutants. Our study showed that the GO would interact with TC and Cu-TC and thus have significant influences on the fate and transport of these pollutions in porous media.

Coupled effect of colloids and surface chemical heterogeneity on the transport of antibiotics in porous media

Release of antibiotics into the environment has caused ecological and human health concerns in recent years. However, little is known about their transport behaviors in chemically heterogeneous porous media. In this study, we investigated the coupled effects of surface chemistry and soil colloids on the transport of ciprofloxacin and tetracycline through sand under steady state saturated flow conditions. Both antibiotics had a much higher capacity of adsorption on soil colloids (17,500 mg/kg for ciprofloxacin and 8600 mg/kg for tetracycline) than on sand (5.11 mg/kg for ciprofloxacin and 2.80 mg/kg for tetracycline). However, ciprofloxacin adsorption increased to 8.91 mg/kg after the sand was coated with iron oxide and to 8.73 mg/kg after the sand was coated with humic acid. Tetracycline, adsorption increased to 7.99 mg/kg after sand was coated with iron oxide coated sand and to 8.35 mg/kg after the sand was coated with humic acid coated The high adsorption capacity of ciprofloxacin led to a recovery rate of <4% in the effluents of the columns containing 0%, 20% and 50% of iron oxide/humic acid coated sand. The surface coating decreased the recovery rates of tetracycline from 35.4% (in uncoated sand) to 12.0% (in column containing 50% iron oxide coated sand) and 0.010% (in column containing 50% humic acid coated sand), respectively. Once adsorbed to soil colloids, the recovery rate of ciprofloxacin increased by 26.7% in uncoated sand column, 21.1% in iron oxide coated sand column, and 32.7% in humic acid coated sand column. Similarly, the presence of the colloids increased the recovery rate of tetracycline from 13.8% to 33.2% after the sand was coated with humic acid. Colloids did not significantly influence the transport and recovery of tetracycline in the uncoated sand and iron oxide coated sand due likely to its lower adsorption affinity.

Tetracycline-induced effects on the nitrogen transformations in sediments: Roles of adsorption behavior and bacterial activity

Nitrification and denitrification are the most important nitrogen transformation processes in the environment. Recently, due to widespread use, antibiotics have been reported to lead to environmental risks. Tetracycline (TC) is one of the most extensively used antibiotics in many areas. However, its reported effects on nitrogen transformations were conflicting in previous studies. In this study, the effects of TC on nitrogen transformations in sediment were investigated by analyzing TC transport and bacterial activity. It was found that the adsorption of TC onto the sediment was favorable and spontaneous, with adsorption capacity 54.3 mg/kg. The adsorption kinetics of TC onto the sediment and the isotherm fitted the Elvoich and Freundlich models, respectively, indicating that the adsorption was a chemisorption process, including electrostatic interactions and chemical bonding between TC and the sediment. TC showed no effect on nitrification in the sediment, but significantly inhibited the reduction of nitrate and nitrite during denitrification, consistent with observations made for the model denitrifier Paracoccus denitrificans under TC stress. Mechanistic study indicated that TC at 130 μg/g-cell inhibited 50.7% of P. denitrificans growth and 61.6% of cell viability. Meanwhile, the catalytic activities of the key denitrifying enzymes, nitrate reductase (NAR) and nitrite reductase (NIR), decreased to 29.1% and 68.0% of the control levels when the TC concentration was 130 μg/g-cell, suggesting that NAR was more sensitive to the TC than NIR, which contributed to a delay in nitrite accumulation.