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.

Low-molecular-weight aromatic acids mediated the adsorption of Cd2+ onto biochars: effects and mechanisms.

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 Cd2+ onto biochars generated at three different pyrolysis temperatures under acidic and neutral conditions were examined. Generally, the adsorption ability of biochars for Cd2+ 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 Cd2+ 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 Cd2+ induced by the adsorbed aromatic acids, and the formation of water-soluble metal-aromatic acid complexes. Furthermore, the inhibitory effects of LWMAAs on Cd2+ 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 Kow) 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.

Transport of sulfanilamide in saturated porous media under different solution chemistry conditions: role of physicochemical characteristics of soils.

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+, Cu2+ 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.

Biochar improved the solubility of triclocarban in aqueous environment: Insight into the role of biochar-derived dissolved organic carbon.

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.

Low-molecular-weight organic acids-mediated transport of neonicotinoid pesticides through saturated soil porous media: Combined effects of the molecular structures of organic acids and the chemical properties of contaminants.

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 Ca2+, 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.

Mobility of antipyretic drugs with different molecular structures in saturated soil porous media.

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+, Ca2+ 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.

Biosurfactant-affected mobility of oxytetracycline and its variations with surface chemical heterogeneity in saturated porous media.

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.

Adsorption of fluoroquinolone antibiotics onto ferrihydrite under different anionic surfactants and solution pH.

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.

Transport of dissolved organic matters derived from biomass-pyrogenic smoke (SDOMs) and their effects on mobility of heavy metal ions in saturated porous media.

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 Cu2+ 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 Cu2+ transport in the quartz sand, which stemmed from forming soluble Cu-SDOM complexes. Intriguingly, the promotional function of SDOMs for the mobility of Cu2+ 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.

Surfactant-mediated mobility of carbon dots in saturated soil: comparison between anionic and cationic surfactants.

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., Ca2+ or Cu2+), 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-Cu2+/Ca2+-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.

Transport of oxytetracycline through saturated porous media: role of surface chemical heterogeneity.

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, Ca2+ 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.

Biosurfactant-mediated mobility of graphene oxide nanoparticles in saturated porous media.

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 Cu2+. 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.

Mobility of water-soluble aerosol organic matters (WSAOMs) and their effects on soil colloid-mediated transport of heavy metal ions in saturated porous media.

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., Cd2+) 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., Cd2+) and soil colloid-mediated Cd2+ 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 Cd2+, 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 Cd2+ adsorption capacities of colloids induced by various WSAOMs.

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.

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.

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 (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 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.

The composition, energy, and carbon stability characteristics of biochars derived from thermo-conversion of biomass in air-limitation, CO2, and N2 at different temperatures.

This study systemically investigated the characteristics of biochars derived from thermo-conversion of pine sawdust and wheat straw in air-limitation, CO2, and N2 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 CO2 and N2. Biochars derived from thermo-conversion of pine sawdust in CO2 and N2 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 N2 and CO2 at 450-750 °C benefited for the formation of fixed C. Recalcitrance potential (R50) results showed that the biochars produced in CO2 and N2 at 600-750 °C had the highest carbon stability (R50: 0.54-0.64) for given biomass, owing to the thermo-conversion of biomass in CO2 and N2 at 600-750 °C preferring to form the organic C with high aromaticity and low polarity. Nonetheless, thermo-conversion of biomass in CO2 and N2 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 > CO2 > N2, whereas carbon stability presented an opposite order. Our results contributed to selecting the appropriate atmosphere to optimize the properties and performances of biochars.

Enhanced transport of heavy metal ions by low-molecular-weight organic acids in saturated porous media: Link complex stability constants to heavy metal mobility.

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 Cd2+, Zn2+, Ni2+, Mn2+, and Co2+) 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 Cd2+ < Zn2+ < Ni2+ < Mn2+ < Co2+ 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) (R2 = 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.

Insight into the inhibitory mechanism of inorganic ligands on the adsorption of tetracycline onto hematite.

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., Ca2+), 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.

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.