Microbially Induced Soil Colloidal Phosphorus Mobilization Under Anoxic Conditions.

Understanding the behavior of colloidal phosphorus (Pcoll) under anoxic conditions is pivotal for addressing soil phosphorus (P) mobilization and transport and its impact on nutrient cycling. Our study investigated Pcoll dynamics in acidic floodplain soil during a 30-day flooding event. The sudden oxic-to-anoxic shift led to a significant rise in pore-water Pcoll levels, which exceeded soluble P levels by more than 2.7-fold. Colloidal fractions transitioned from dispersed forms (<220 nm) to colloid-associated microaggregates (>220 nm), as confirmed by electron microscopy. The observed increase in colloidal sizes was paralleled by their heightened ability to form aggregates. Compared to sterile control conditions, anoxia prompted the transformation of initially dispersed colloids into larger particles through microbial activity. Curiously, the 16S rRNA and ITS microbial diversity analysis indicated that fungi were more strongly associated with anoxia-induced colloidal release than bacteria. These microbially induced shifts in Pcoll lead to its higher mobility and transport, with direct implications for P release from soil into floodwaters.

Fog controls biological cycling of soil phosphorus in the Coastal Cordillera of the Atacama Desert.

Soils in hyper-arid climates, such as the Chilean Atacama Desert, show indications of past and present forms of life despite extreme water limitations. We hypothesize that fog plays a key role in sustaining life. In particular, we assume that fog water is incorporated into soil nutrient cycles, with the inland limit of fog penetration corresponding to the threshold for biological cycling of soil phosphorus (P). We collected topsoil samples (0-10 cm) from each of 54 subsites, including sites in direct adjacency (<10 cm) and in 1 m distance to plants, along an aridity gradient across the Coastal Cordillera. Satellite-based fog detection revealed that Pacific fog penetrates up to 10 km inland, while inland sites at 10-23 km from the coast rely solely on sporadic rainfall for water supply. To assess biological P cycling we performed sequential P fractionation and determined oxygen isotope of HCl-extractable inorganic P δ 18 O HCl - P i $$ \mathrm{P}\ \left({\updelta}^{18}{\mathrm{O}}_{\mathrm{HCl}-{\mathrm{P}}_{\mathrm{i}}}\right) $$ . Total P (Pt ) concentration exponentially increased from 336 mg kg-1 to a maximum of 1021 mg kg-1 in inland areas ≥10 km. With increasing distance from the coast, soil δ 18 O HCl - P i $$ {\updelta}^{18}{\mathrm{O}}_{\mathrm{HCl}-{\mathrm{P}}_{\mathrm{i}}} $$ values declined exponentially from 16.6‰ to a constant 9.9‰ for locations ≥10 km inland. Biological cycling of HCl-Pi near the coast reached a maximum of 76%-100%, which could only be explained by the fact that fog water predominately drives biological P cycling. In inland regions, with minimal rainfall (<5 mm) as single water source, only 24 ± 14% of HCl-Pi was biologically cycled. We conclude that biological P cycling in the hyper-arid Atacama Desert is not exclusively but mainly mediated by fog, which thus controls apatite dissolution rates and related occurrence and spread of microbial life in this extreme environment.

Implications of Free and Occluded Fine Colloids for Organic Matter Preservation in Arable Soils.

Colloidal organo-mineral associations contribute to soil organic matter (OM) preservation and mainly occur in two forms: (i) as water-dispersible colloids that are potentially mobile (free colloids) and (ii) as building units of soil microaggregates that are occluded inside them (occluded colloids). However, the way in which these two colloidal forms differ in terms of textural characteristics and chemical composition, together with the nature of their associated OM, remains unknown. To fill these knowledge gaps, free and occluded fine colloids <220 nm were isolated from arable soils with comparable organic carbon (Corg) but different clay contents. Free colloids were dispersed in water suspensions during wet-sieving, while occluded colloids were released from water-stable aggregates by sonication. The asymmetric flow field-flow fractionation analysis on the free and occluded colloids suggested that most of the 0.6-220 nm fine colloidal Corg was present in size fractions that showed high abundances of Si, Al, and Fe. The pyrolysis-field ionization mass spectrometry revealed that the free colloids were relatively rich in less decomposed plant-derived OM (i.e., lipids, suberin, and free fatty acids), whereas the occluded colloids generally contained more decomposed and microbial-derived OM (i.e., carbohydrates and amides). In addition, a higher thermal stability of OM in occluded colloids pointed to a higher resistance to further degradation and mineralization of OM in occluded colloids than that in free colloids. This study provides new insights into the characteristics of subsized fractions of fine colloidal organo-mineral associations in soils and explores the impacts of free versus occluded colloidal forms on the composition and stability of colloid-associated OM.

Significance of Non-DLVO Interactions on the Co-Transport of Functionalized Multiwalled Carbon Nanotubes and Soil Nanoparticles in Porous Media.

Derjaguin-Landau-Verwey-Overbeek (DLVO) theory is typically used to quantify surface interactions between engineered nanoparticles (ENPs), soil nanoparticles (SNPs), and/or porous media, which are used to assess environmental risk and fate of ENPs. This study investigates the co-transport behavior of functionalized multiwalled carbon nanotubes (MWCNTs) with positively (goethite nanoparticles, GNPs) and negatively (bentonite nanoparticles, BNPs) charged SNPs in quartz sand (QS). The presence of BNPs increased the transport of MWCNTs, but GNPs inhibited the transport of MWCNTs. In addition, we, for the first time, observed that the transport of negatively (BNPs) and positively (GNPs) charged SNPs was facilitated by the presence of MWCNTs. Traditional mechanisms associated with competitive blocking, heteroaggregation, and classic DLVO calculations cannot explain such phenomena. Direct examination using batch experiments and Fourier transform infrared (FTIR) spectroscopy, asymmetric flow field flow fractionation (AF4) coupled to UV and inductively coupled plasma mass spectrometry (AF4-UV-ICP-MS), and molecular dynamics (MD) simulations demonstrated that MWCNTs-BNPs or MWCNT-GNPs complexes or aggregates can be formed during co-transport. Non-DLVO interactions (e.g., H-bonding and Lewis acid-base interaction) helped to explain observed MWCNT deposition, associations between MWCNTs and both SNPs (positively or negatively), and co-transport. This research sheds novel insight into the transport of MWCNTs and SNPs in porous media and suggests that (i) mutual effects between colloids (e.g., heteroaggregation, co-transport, and competitive blocking) need to be considered in natural soil; and (ii) non-DLVO interactions should be comprehensively considered when evaluating the environmental risk and fate of ENPs.

Transport and Retention of Poly(Acrylic Acid-co-Maleic Acid) Coated Magnetite Nanoparticles in Porous Media: Effect of Input Concentration, Ionic Strength and Grain Size.

Understanding the physicochemical factors affecting nanoparticle transport in porous media is critical for their environmental application. Water-saturated column experiments were conducted to investigate the effects of input concentration (Co), ionic strength (IS), and sand grain size on the transport of poly(acrylic acid-co-maleic acid) coated magnetite nanoparticles (PAM@MNP). Mass recoveries in the column effluent ranged from 45.2 to 99.3%. The highest relative retention of PAM@MNP was observed for the lowest Co. Smaller Co also resulted in higher relative retention (39.8%) when IS increased to 10 mM. However, relative retention became much less sensitive to solution IS as Co increased. The high mobility is attributed to the PAM coating provoking steric stability of PAM@MNP against homoaggregation. PAM@MNP retention was about 10-fold higher for smaller grain sizes, i.e., 240 µm and 350 µm versus 607 µm. The simulated maximum retained concentration on the solid phase (Smax) and retention rate coefficient (k1) increased with decreasing Co and grain sizes, reflecting higher retention rates at these parameters. The study revealed under various IS for the first time the high mobility premise of polymer-coated magnetite nanoparticles at realistic (<10 mg L−1) environmental concentrations, thereby highlighting an untapped potential for novel environmental PAM@MNP application usage.

Organic Carbon Linkage with Soil Colloidal Phosphorus at Regional and Field Scales: Insights from Size Fractionation of Fine Particles.

Nano and colloidal particles (1-1000 nm) play important roles in phosphorus (P) migration and loss from agricultural soils; however, little is known about their relative distribution in arable crop soils under varying agricultural geolandscapes at the regional scale. Surface soils (0-20 cm depth) were collected from 15 agricultural fields, including two sites with different carbon input strategies, in Zhejiang Province, China, and water-dispersible nanocolloids (0.6-25 nm), fine colloids (25-160 nm), and medium colloids (160-500 nm) were separated and analyzed using the asymmetrical flow field flow fractionation technique. Three levels of fine-colloidal P content (3583-6142, 859-2612, and 514-653 µg kg-1) were identified at the regional scale. The nanocolloidal fraction correlated with organic carbon (Corg) and calcium (Ca), and the fine colloidal fraction with Corg, silicon (Si), aluminum (Al), and iron (Fe). Significant linear relationships existed between colloidal P and Corg, Si, Al, Fe, and Ca and for nanocolloidal P with Ca. The organic carbon controlled colloidal P saturation, which in turn affected the P carrier ability of colloids. Field-scale organic carbon inputs did not change the overall morphological trends in size fractions of water-dispersible colloids. However, they significantly affected the peak concentration in each of the nano-, fine-, and medium-colloidal P fractions. Application of chemical fertilizer with carbon-based solid manure and/or modified biochar reduced the soil nano-, fine-, and medium-colloidal P content by 30-40%; however,the application of chemical fertilizer with biogas slurry boosted colloidal P formation. This study provides a deep and novel understanding of the forms and composition of colloidal P in agricultural soils and highlights their spatial regulation by soil characteristics and carbon inputs.

Evidence on enhanced transport and release of silver nanoparticles by colloids in soil due to modification of grain surface morphology and co-transport.

Natural soils have frequently been considered to decrease the mobility of engineered nanoparticles (NPs) in comparison to quartz sand due to the presence of colloids that provide additional retention sites. In contrast, this study demonstrates that the transport and release of silver nanoparticles (AgNPs) in sandy clay loam and loamy sand soils were enhanced in the presence of soil colloids that altered soil grain surface roughness. In particular, we found that the retention of AgNPs in purified soils (colloid-free and acid-treated) was more pronounced than in raw (untreated) soils or soils treated to remove organic matter (H2O2 or 600 °C treated). Chemical analysis and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy demonstrated that the grain surfaces of raw and organic matter-removed soils were abundant with metal oxides and colloids compared to purified soil. Column transport and release experimental results, SEM images, and interaction energy calculations revealed that a significant amount of concave locations on purified soils hindered AgNP release by diffusion or ionic strength (IS) reduction due to deep primary energy minima. Conversely, AgNPs that were retained in soils in the presence of soil colloids were more susceptible to release under IS reduction because the primary minimum was shallow on the tops of convex locations created by attached soil colloids. Additionally, a considerable fraction of retained AgNPs in raw soil was released after cation exchange followed by IS reduction, while no release occurred for purified soil under the same conditions. The AgNP release was highly associated with soil colloids and co-transport of AgNPs and soil colloids was observed. Our work is the first to show that the presence of soil colloids can inhibit deposition and facilitate the release and co-transport of NPs in soil by alteration of the soil grain surface morphology and shallow primary minimum interactions.

Non-monotonic contribution of nonionic surfactant on the retention of functionalized multi-walled carbon nanotubes in porous media.

The concentration of nonionic surfactants like Triton X-100 (TX100) can influence the transport and fate of emerging contaminants (e.g., carbon nanotubes) in porous media, but limited research has previously addressed this issue. This study investigates the co-transport of functionalized multi-walled carbon nanotubes (MWCNTs) and various concentrations of TX100 in saturated quartz sand (QS). Batch experiments and molecular dynamics simulations were conducted to investigate the interactions between TX100 and MWCNTs. Results indicated that the concentration ratio of MWCNTs and TX100 strongly influences the dispersion of MWCNTs and interaction forces between MWCNTs and QS during the transport. Breakthrough curves of MWCNTs and TX100 and retention profiles of MWCNTs were determined and simulated in column studies. MWCNTs strongly enhanced the retention of TX100 in QS due to the high affinity of TX100 for MWCNTs. Conversely, the concentration of TX100 had a non-monotonic impact on MWCNT retention. The maximum transport of MWCNTs in the QS occurred at an input concentration of TX100 that was lower than the critical micelle concentration. This suggests that the relative importance of factors influencing MWCNTs changed with TX100 sorption. Results from interaction energy calculations and modeling of competitive blocking indicate that the predictive ability of interaction energy calculations and colloid filtration theory may be lost because TX100 mainly altered intermolecular forces between the MWCNT and porous media. This study provides new insights into the co-transport of surfactants and MWCNTs in porous media, which can be useful for environmental applications and risk management.

Influence of Physical-Chemical Soil Parameters on Microbiota Composition and Diversity in a Deep Hyperarid Core of the Atacama Desert.

The extreme environmental conditions and lack of water on the soil surface in hyperarid deserts hamper microbial life, allowing only highly specialized microbial communities to the establish colonies and survive. Until now, the microbial communities that inhabit or have inhabited soils of hyperarid environments at greater depths have been poorly studied. We analyzed for the first time the variation in microbial communities down to a depth of 3.4 m in one of the driest places of the world, the hyperarid Yungay region in the Atacama Desert, and we related it to changes in soil physico-chemical characteristics. We found that the moisture content changed from 2 to 11% with depth and enabled the differentiation of three depth intervals: (i) surface zone A (0-60 cm), (ii) intermediate zone B (60-220 cm), and (iii) deep zone C (220-340 cm). Each zone showed further specific physicochemical and mineralogical features. Likewise, some bacterial phyla were unique in each zone, i.e., members of the taxa Deinococcota, Halobacterota, and Latescibacterota in zone A; Crenarchaeota, Fusobacteriota, and Deltaproteobacterium Sva0485 in zone B; and Fervidibacteria and Campilobacterota in zone C, which indicates taxon-specific preferences in deep soil habitats. Differences in the microbiota between the zones were rather abrupt, which is concomitant with abrupt changes in the physical-chemical parameters. Overall, moisture content, total carbon (TC), pH, and electric conductivity (EC) were most predictive of microbial richness and diversity, while total sulfur (TS) and total phosphorous (TP) contents were additionally predictive of community composition. We also found statistically significant associations between taxa and soil properties, most of which involved moisture and TC contents. Our findings show that under-explored habitats for microbial survival and existence may prevail at greater soil depths near water or within water-bearing layers, a valuable substantiation also for the ongoing search for biosignatures on other planets, such as Mars.

Evidence for the critical role of nanoscale surface roughness on the retention and release of silver nanoparticles in porous media.

Although nanoscale surface roughness has been theoretically demonstrated to be a crucial factor in the interaction of colloids and surfaces, little experimental research has investigated the influence of roughness on colloid or silver nanoparticle (AgNP) retention and release in porous media. This study experimentally examined AgNP retention and release using two sands with very different surface roughness properties over a range of solution pH and/or ionic strength (IS). AgNP transport was greatly enhanced on the relatively smooth sand in comparison to the rougher sand, at higher pH, and lower IS and fitted model parameters showed systematic changes with these physicochemical factors. Complete release of the retained AgNPs was observed from the relatively smooth sand when the solution IS was decreased from 40 mM NaCl to deionized (DI) water and then the solution pH was increased from 6.5 to 10. Conversely, less than 40% of the retained AgNPs was released in similar processes from the rougher sand. These observations were explained by differences in the surface roughness of the two sands which altered the energy barrier height and the depth of the primary minimum with solution chemistry. Limited numbers of AgNPs apparently interacted in reversible, shallow primary minima on the smoother sand, which is consistent with the predicted influence of a small roughness fraction (e.g., pillar) on interaction energies. Conversely, larger numbers of AgNPs interacted in deeper primary minima on the rougher sand, which is consistent with the predicted influence at concave locations. These findings highlight the importance of surface roughness and indicate that variations in sand surface roughness can greatly change the sensitivity of nanoparticle transport to physicochemical factors such as IS and pH due to the alteration of interaction energy and thus can strongly influence nanoparticle mobility in the environment.

Transport and retention of engineered silver nanoparticles in carbonate-rich sediments in the presence and absence of soil organic matter.

The transport and retention behavior of polymer- (PVP-AgNP) and surfactant-stabilized (AgPURE) silver nanoparticles in carbonate-dominated saturated and unconsolidated porous media was studied at the laboratory scale. Initial column experiments were conducted to investigate the influence of chemical heterogeneity (CH) and nano-scale surface roughness (NR) arising from mixtures of clean, positively charged calcium carbonate sand (CCS), and negatively charged quartz sands. Additional column experiments were performed to elucidate the impact of CH and NR arising from the presence and absence of soil organic matter (SOM) on a natural carbonate-dominated aquifer material. The role of the nanoparticle capping agent was examined under all conditions tested in the column experiments. Nanoparticle transport was well described using a numerical model that facilitated blocking on one or two retention sites. Results demonstrate that an increase in CCS content in the artificially mixed porous medium leads to delayed breakthrough of the AgNPs, although AgPURE was much less affected by the CCS content than PVP-AgNPs. Interestingly, only a small portion of the solid surface area contributed to AgNP retention, even on positively charged CCS, due to the presence of NR which weakened the adhesive interaction. The presence of SOM enhanced the retention of AgPURE on the natural carbonate-dominated aquifer material, which can be a result of hydrophobic or hydrophilic interactions or due to cation bridging. Surprisingly, SOM had no significant impact on PVP-AgNP retention, which suggests that a reduction in electrostatic repulsion due to the presence of SOM outweighs the relative importance of other binding mechanisms. Our findings are important for future studies related to AgNP transport in shallow unconsolidated calcareous and siliceous sands.

Co-transport of multi-walled carbon nanotubes and sodium dodecylbenzenesulfonate in chemically heterogeneous porous media.

Multi-walled carbon nanotubes (MWCNTs) are increasing used in commercial applications and may be released into the environment with anionic surfactants, such as sodium dodecylbenzenesulfonate (SDBS), in sewer discharge. Little research has examined the transport, retention, and remobilization of MWCNTs in the presence or absence of SDBS in porous media with controlled chemical heterogeneity, and batch and column scale studies were therefore undertaken to address this gap in knowledge. The adsorption isotherms of SDBS on quartz sand (QS), goethite coated quartz sand (GQS), and MWCNTs were determined. Adsorption of SDBS (MWCNTs ¼â€¯GQS > QS) decreased zeta potentials for these materials, and produced a charge reversal for goethite. Transport of MWCNTs (5 mg L-1) dramatically decreased with an increase in the fraction of GQS from 0 to 0.1 in the absence of SDBS. Conversely, co-injection of SDBS (10 and 50 mg L-1) and MWCNTs radically increased the transport of MWCNTs when the GQS fraction was 0, 0.1, and 0.3, especially at a higher SDBS concentration, and altered the shape of retention profile. Mathematical modeling revealed that competitive blocking was not the dominant mechanism for the SDBS enhancement of MWCNT transport. Rather, SDBS sorption increased MWCNT transport by increasing electrostatic and/or steric interactions, or creating reversible interactions on rough surfaces. Sequential injection of pulses of MWCNTs and SDBS in sand (0.1 GQS fraction) indicated that SDBS could mobilize some of retained MWCNTs from the top to deeper sand layers, but only a small amount of released MWCNTs were recovered in the effluent. SDBS therefore had a much smaller influence on MWCNT transport in sequential injection than in co-injection, presumably because of a greater energy barrier to MWCNT release than retention. This research sheds novel insight on the roles of competitive blocking, chemical heterogeneity and nanoscale roughness, and injection sequence on MWCNT retention and release.

Mechanisms of graphene oxide aggregation, retention, and release in quartz sand.

The roles of graphene oxide (GO) particle geometry, GO surface orientation, surface roughness, and nanoscale chemical heterogeneity on interaction energies, aggregation, retention, and release of GO in porous media were not fully considered in previous studies. Consequently, mechanisms controlling the environmental fate of GO were incompletely or inaccurately quantified. To overcome this limitation, plate-plate interaction energies were modified to account for these factors and used in conjunction with a mathematical model to interpret the results of GO aggregation, retention, and release studies. Calculations revealed that these factors had a large influence on the predicted interaction energy parameters. Similar to previous literature, the secondary minimum was predicted to dominate on smooth, chemically homogeneous surfaces that were oriented parallel to each other, especially at higher ionic strength (IS). Conversely, shallow primary minimum interactions were sometimes predicted to occur on surfaces with nanoscale roughness and chemical heterogeneity due to adsorbed Ca2+ ions, especially when the GO particles were oriented perpendicular to the interacting surface. Experimental results were generally consistent with these predictions and indicated that the primary minimum played a major role in GO retention and the secondary minimum contributed to GO release with IS reduction. Cation exchange (Na+ replacing Ca2+) enhanced GO release with IS reduction when particles were initially deposited in the presence of Ca2+ ions. However, retained GO were always completely recovered into the excess deionized water when the sand pore structure was destroyed during excavation, and this indicates that primary minima were shallow and that the pore structure also played an important role in GO retention. Further evidence for the role of pore structure on GO retention was obtained by conducting experiments in finer textured sand and at higher input concentrations that induced greater aggregation. In both cases, greater GO retention occurred, and retention profiles became more hyperexponential in shape.

Leaching of natural colloids from forest topsoils and their relevance for phosphorus mobility.

The leaching of P from the upper 20cm of forest topsoils influences nutrient (re-)cycling and the redistribution of available phosphate and organic P forms. However, the effective leaching of colloids and associated P forms from forest topsoils was so far sparsely investigated. We demonstrated through irrigation experiments with undisturbed mesocosm soil columns, that significant proportions of P leached from acidic forest topsoils were associated with natural colloids. These colloids had a maximum size of 400nm. By means of Field-flow fractionation the leached soil colloids could be separated into three size fractions. The size and composition was comparable to colloids present in acidic forest streams known from literature. The composition of leached colloids of the three size classes was dominated by organic carbon. Furthermore, these colloids contained large concentrations of P which amounted between 12 and 91% of the totally leached P depending on the type of the forest soil. The fraction of other elements leached with colloids ranged between 1% and 25% (Fe: 1-25%; Corg: 3-17%; Al: <4%; Si, Ca, Mn: all <2%). The proportion of colloid-associated P decreased with increasing total P leaching. Leaching of total and colloid-associated P from the forest surface soil did not increase with increasing bulk soil P concentrations and were also not related to tree species. The present study highlighted that colloid-facilitated P leaching can be of higher relevance for the P leaching from forest surface soils than dissolved P and should not be neglected in soil water flux studies.

Role of rain intensity and soil colloids in the retention of surfactant-stabilized silver nanoparticles in soil.

Undisturbed outdoor lysimeters containing arable loamy sand soil were used to examine the influence of either heavy rain events (high frequency of high rain intensity), steady rain (continuous rainfall of low rain intensity), and natural rainfall on the transport and retention of surfactant-stabilized silver nanoparticles (AgNP). In addition, the AgNP-soil associations within the Ap horizon were analyzed by means of particle-size fractionation, asymmetrical flow field-flow fractionation coupled with UV/Vis-detection and inductively coupled plasma mass spectrometer (AF4-UV/Vis-ICP-MS), and transmission electron microscopy coupled to an energy-dispersive X-ray (TEM-EDX) analyzer. The results showed that AgNP breakthrough for all rain events was less than 0.1% of the total AgNP mass applied, highlighting that nearly all AgNP were retained in the soil. Heavy rain treatment and natural rainfall revealed enhanced AgNP transport within the Ap horizon, which was attributed to the high pore water flow velocities and to the mobilization of AgNP-soil colloid associations. Particle-size fractionation of the soil revealed that AgNP were present in each size fraction and therefore indicated strong associations between AgNP and soil. In particular, water-dispersible colloids (WDC) in the size range of 0.45-0.1 µm were found to exhibit high potential for AgNP attachment. The AF4-UV/Vis-ICP-MS and TEM-EDX analyses of the WDC fraction confirmed that AgNP were persistent in soil and associated to soil colloids (mainly composed of Al, Fe, Si, and organic matter). These results confirm the particularly important role of soil colloids in the retention and remobilization of AgNP in soil. Furthermore, AF4-UV/Vis-ICP-MS results indicated the presence of single, homo-aggregated, and small AgNP probably due to dissolution.

Soil organic phosphorus transformations during 2000 years of paddy-rice and non-paddy management in the Yangtze River Delta, China.

The contents and properties of soil organic phosphorus (Po) largely drive ecosystem productivity with increasing development of natural soil. We hypothesized that soil Po would initially increase with paddy management and then would persist under steady-state conditions. We analyzed soils from a 2000-year chronosequence of a rice-wheat rotation and an adjacent non-paddy 700-year chronosequence in Bay of Hangzhou (China) for their Po composition using solution 31P-NMR after NaOH-EDTA extraction. Land reclamation promoted Po accumulation in both paddy and non-paddy topsoils (depths ≤ 18 cm) until steady-state equilibria were reached within 200 years of land use. Greater Po concentrations were found, however, in the non-paddy subsoils than in those under paddy management. Apparently, the formation of a dense paddy plough pan hindered long-term Po accumulation in the paddy subsoil. The surface soils showed higher proportions of orthophosphate diesters under paddy than under non-paddy management, likely reflecting suppressed decomposition of crop residues despite elevated microbial P compounds stocks under anaerobic paddy-rice management. Intriguingly, the composition of Po was remarkably stable after 194-years of paddy management and 144-years of non-paddy management, suggesting novel steady-state equilibria of P dynamics had been reached in these man-made ecosystems after less than two centuries.

Experimental and Numerical Investigations of Silver Nanoparticle Transport under Variable Flow and Ionic Strength in Soil.

Unsaturated column experiments were conducted with an undisturbed loamy sand soil to investigate the influence of flow interruption (FI) and ionic strength (IS) on the transport and retention of surfactant-stabilized silver nanoparticles (AgNP) and the results were compared to those obtained under continuous flow conditions. AgNP concentrations for breakthrough curves (BTCs) and retention profiles (RPs) were analyzed by ICP-MS. Experimental results were simulated by the numerical code HP1 (Hydrus-PhreeqC) with the DLVO theory, extended colloid filtration theory and colloid release model. BTCs of AgNP showed a dramatic drop after FI compared to continuous flow conditions. Evaporation increased due to FI, resulting in increased electrical conductivity of the soil solution, which led to a totally reduced mobility of AgNP. A reduction of IS after FI enhanced AgNP mobility slightly. Here the strongly increased Al and Fe concentration in the effluent suggested that soil colloids facilitated the release of AgNP (cotransport). The numerical model reproduced the measured AgNP BTCs and indicated that attachment to the air-water interface (AWI) occurring during FI was the key process for AgNP retention.

Roles of cation valance and exchange on the retention and colloid-facilitated transport of functionalized multi-walled carbon nanotubes in a natural soil.

Saturated soil column experiments were conducted to investigate the transport, retention, and release behavior of a low concentration (1 mg L-1) of functionalized 14C-labeled multi-walled carbon nanotubes (MWCNTs) in a natural soil under various solution chemistries. Breakthrough curves (BTCs) for MWCNTS exhibited greater amounts of retardation and retention with increasing solution ionic strength (IS) or in the presence of Ca2+ in comparison to K+, and retention profiles (RPs) for MWCNTs were hyper-exponential in shape. These BTCs and RPs were well described using the advection-dispersion equation with a term for time- and depth-dependent retention. Fitted values of the retention rate coefficient and the maximum retained concentration of MWCNTs were higher with increasing IS and in the presence of Ca2+ in comparison to K+. Significant amounts of MWCNT and soil colloid release was observed with a reduction of IS due to expansion of the electrical double layer, especially following cation exchange (when K+ displaced Ca2+) that reduced the zeta potential of MWCNTs and the soil. Analysis of MWCNT concentrations in different soil size fractions revealed that >23.6% of the retained MWCNT mass was associated with water-dispersible colloids (WDCs), even though this fraction was only a minor portion of the total soil mass (2.38%). More MWCNTs were retained on the WDC fraction in the presence of Ca2+ than K+. These findings indicated that some of the released MWCNTs by IS reduction and cation exchange were associated with the released clay fraction, and suggests the potential for facilitated transport of MWCNT by WDCs.

Co-transport of chlordecone and sulfadiazine in the presence of functionalized multi-walled carbon nanotubes in soils.

Batch and saturated soil column experiments were conducted to investigate sorption and mobility of two 14C-labeled contaminants, the hydrophobic chlordecone (CLD) and the sulfadiazine (SDZ), in the absence or presence of functionalized multi-walled carbon nanotubes (MWCNTs). The transport behaviors of CLD, SDZ, and MWCNTs were studied at environmentally relevant concentrations (0.1-10 mg L-1) and they were applied in the column studies at different times. The breakthrough curves and retention profiles were simulated using a numerical model that accounted for the advective-dispersive transport of all compounds, attachment/detachment of MWCNTs, equilibrium and kinetic sorption of contaminants, and co-transport of contaminants with MWCNTs. The experimental results indicated that the presence of mobile MWCNTs facilitated remobilization of previously deposited CLD and its co-transport into deeper soil layers, while retained MWCNTs enhanced SDZ deposition in the topsoil layers due to the increased adsorption capacity of the soil. The modeling results then demonstrated that the mobility of engineered nanoparticles (ENPs) in the environment and the high affinity and entrapment of contaminants to ENPs were the main reasons for ENP-facilitated contaminant transport. On the other hand, immobile MWCNTs had a less significant impact on the contaminant transport, even though they were still able to enhance the adsorption capacity of the soil.

Do Goethite Surfaces Really Control the Transport and Retention of Multi-Walled Carbon Nanotubes in Chemically Heterogeneous Porous Media?

Transport and retention behavior of multi-walled carbon nanotubes (MWCNTs) was studied in mixtures of negatively charged quartz sand (QS) and positively charged goethite-coated sand (GQS) to assess the role of chemical heterogeneity. The linear equilibrium sorption model provided a good description of batch results, and the distribution coefficients (KD) drastically increased with the GQS fraction that was electrostatically favorable for retention. Similarly, retention of MWCNTs increased with the GQS fraction in packed column experiments. However, calculated values of KD on GQS were around 2 orders of magnitude smaller in batch than packed column experiments due to differences in lever arms associated with hydrodynamic and adhesive torques at microscopic roughness locations. Furthermore, the fraction of the sand surface area that was favorable for retention (Sf) was much smaller than the GQS fraction because nanoscale roughness produced shallow interactions that were susceptible to removal. These observations indicate that only a minor fraction of the GQS was favorable for MWCNT retention. These same observations held for several different sand sizes. Column breakthrough curves were always well described using an advective-dispersive transport model that included retention and blocking. However, depth-dependent retention also needed to be included to accurately describe the retention profile when the GQS fraction was small. Results from this research indicate that roughness primarily controlled the retention of MWCNTs, although goethite surfaces played an important secondary role.