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.

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.

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.

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.

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.

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.

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.

Phosphorus Containing Water Dispersible Nanoparticles in Arable Soil.

Due to the limited solubility of phosphorus (P) in soil, understanding its binding in fine colloids is vital to better forecast P dynamics and losses in agricultural systems. We hypothesized that water-dispersible P is present as nanoparticles and that iron (Fe) plays a crucial role for P binding to these nanoparticles. To test this, we isolated water-dispersible fine colloids (WDFC) from an arable topsoil (Haplic Luvisol, Germany) and assessed colloidal P forms after asymmetric flow field-flow fractionation coupled with ultraviolet and an inductively coupled plasma mass spectrometer, with and without removal of amorphous and crystalline Fe oxides using oxalate and dithionite, respectively. We found that fine colloidal P was present in two dominant sizes: (i) in associations of organic matter and amorphous Fe (Al) oxides in nanoparticles <20 nm, and (ii) in aggregates of fine clay, organic matter and Fe oxides (more crystalline Fe oxides) with a mean diameter of 170 to 225 nm. Solution P-nuclear magnetic resonance spectra indicated that the organically bound P predominantly comprised orthophosphate-monoesters. Approximately 65% of P in the WDFC was liberated after the removal of Fe oxides (especially amorphous Fe oxides). The remaining P was bound to larger-sized WDFC particles and Fe bearing phyllosilicate minerals. Intriguingly, the removal of Fe by dithionite resulted in a disaggregation of the nanoparticles, evident in higher portions of organically bound P in the <20 nm nanoparticle fraction, and a widening of size distribution pattern in larger-sized WDFC fraction. We conclude that the crystalline Fe oxides contributed to soil P sequestration by (i) acting as cementing agents contributing to soil fine colloid aggregation, and (ii) binding not only inorganic but also organic P in larger soil WDFC particles.

Do nanoparticles and colloids replenish soil phosphorus in the rhizosphere of winter wheat?

The rhizosphere is generally depleted in nutrients, but as a hotspot of microbial activity it fosters crop P uptake. We hypothesized that P contents of water extractable nanoparticles (<0.1 µm) and small sized colloids (<0.45 µm) differ between non-rhizosphere and rhizosphere soil. To test this hypothesis, rhizosphere and non-rhizosphere soils (Luvisol and Cambisol) were sampled at harvest period of winter wheat near Selhausen (Germany). Microaggregate and colloidal fractions in the size range of 53-250 µm, 20-53 µm, 0.45-20 µm, and <0.45 µm were separated by wet-sieving and centrifugation. Subsequently, the colloids <0.45 µm were further isolated in 0.66-20 nm, 20-100 nm and 100-450 nm fractions using asymmetric flow field flow fractionation (AF4) and directly analyzed by online coupled organic carbon detector (OCD) and inductively coupled plasma mass spectrometry (ICP-MS) for element composition. No significant differences (p > 0.05) were measured between rhizosphere and non-rhizosphere soil P contents of microaggregate fractions. The rhizosphere soil, however, showed ∼26 % depletion of average P content in the 0.66-20 nm fraction, which went along with an enrichment of P content of the 100-450 nm fraction by a factor of two. Apparently, P uptake by plants results in a redistribution of P in the rhizosphere, with small nanoparticles providing available P to plants while excess residual P is bound to fine colloids.

Retention and remobilization of stabilized silver nanoparticles in an undisturbed loamy sand soil.

Column experiments were conducted with undisturbed loamy sand soil under unsaturated conditions (around 90% saturation degree) to investigate the retention of surfactant stabilized silver nanoparticles (AgNPs) with various input concentration (Co), flow velocity, and ionic strength (IS), and the remobilization of AgNPs by changing the cation type and IS. The mobility of AgNPs in soil was enhanced with decreasing solution IS, increasing flow rate and input concentration. Significant retardation of AgNP breakthrough and hyperexponential retention profiles (RPs) were observed in almost all the transport experiments. The retention of AgNPs was successfully analyzed using a numerical model that accounted for time- and depth-dependent retention. The simulated retention rate coefficient (k1) and maximum retained concentration on the solid phase (Smax) increased with increasing IS and decreasing Co. The high k1 resulted in retarded breakthrough curves (BTCs) until Smax was filled and then high effluent concentrations were obtained. Hyperexponential RPs were likely caused by the hydrodynamics at the column inlet which produced a concentrated AgNP flux to the solid surface. Higher IS and lower Co produced more hyperexponential RPs because of larger values of Smax. Retention of AgNPs was much more pronounced in the presence of Ca(2+) than K(+) at the same IS, and the amount of AgNP released with a reduction in IS was larger for K(+) than Ca(2+) systems. These stronger AgNP interactions in the presence of Ca(2+) were attributed to cation bridging. Further release of AgNPs and clay from the soil was induced by cation exchange (K(+) for Ca(2+)) that reduced the bridging interaction and IS reduction that expanded the electrical double layer. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, and correlations between released soil colloids and AgNPs indicated that some of the released AgNPs were associated with the released clay fraction.

Influences of perfluorooctanoic acid on the aggregation of multi-walled carbon nanotubes.

The aggregation of multi-walled carbon nanotubes (MWCNTs) in the aqueous phase not only inhibits their extensive utilization in various aspects but also dominates their environmental fate and transport. The role of surfactants at low concentration in the aggregation of MWCNTs has been studied, however the effect of perfluorinated surfactants at low concentration is uncertain. To understand this interfacial phenomenon, the influences of perfluorooctanoic acid (PFOA), and sodium dodecyl sulfate (SDS) as a control, on MWCNT aggregation in the aqueous phase were examined by the UV absorbency method. Influences of pH and cationic species on the critical coagulation concentration (CCC) value were evaluated. The CCC values were dependent on the concentration of PFOA, however a pronounced effect of SDS concentration on the CCC values was not observed. The CCC values of the MWCNTs were 51.6 mmol/L in NaCl and 0.28 mmol/L in CaCl2 solutions, which suggested pronounced differences in the effects of Na+ and Ca2+ ions on the aggregation of the MWCNTs. The presence of both PFOA and SDS significantly decreased the CCC values of the MWCNTs in NaCl solution. The aggregation of the MWCNTs took place under acidic conditions and was not notably altered under neutral and alkaline conditions due to the electrostatic repulsion of deprotonated functional groups on the surface of the MWCNTs.

Sorption of a branched nonylphenol and perfluorooctanoic acid on Yangtze River sediments and their model components.

Many metabolites of organic surfactants such as nonylphenol (NP) and perfluorooctanoic acid (PFOA) are ubiquitously found in the environment and are toxic if not sorbed on soils and sediments. In this study, we quantified the sorption of the NP isomer with the highest endocrine activity, [4-(1-ethyl-1,3-dimethylpentyl) phenol] (NP111), and that of PFOA on Yangtze River sediments and its model components illite, goethite and natural organic matter. The sorption experiments were performed with (14)C-labeled NP111 and PFOA by batch or dialysis techniques. The results showed that the sorption isotherms of NP111 and PFOA on the sediments were fitted well by the linear adsorption model. The sorption of NP111 depended largely on the organic carbon content of the sediments. The K(OC) values of NP111 ranged from 6 × 10(3) to 1.1 × 10(4) L kg(-1) indicating that hydrophobic interaction between NP and organic carbon is the main mechanism of sorption. The sorption of NP111 on illite was poor. The sorption of PFOA on the sediments was significantly lower than that of NP111. The affinity of PFOA to adsorb on goethite was slightly higher than on the sediments, but was moderate on illite and negligible on a reference natural organic matter. Principal axis component analysis confirmed that various sediment parameters control the binding of PFOA. This analysis grouped the respective K(d) values to the contents of black carbon, iron oxides and clay, and, hence, to the specific surface area of the sediments.

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.

Isomer-specific degradation of branched and linear 4-nonylphenol isomers in an oxic soil.

Using (14)C- and (13)C-ring-labeling, degradation of five p-nonylphenol (4-NP) isomers including four branched (4-NP(38), 4-NP(65), 4-NP(111), and 4-NP(112)) and one linear (4-NP(1)) isomers in a rice paddy soil was studied under oxic conditions. Degradation followed an availability-adjusted first-order kinetics with the decreasing order of half-life 4-NP(111) (10.3 days) > 4-NP(112) (8.4 days) > 4-NP(65) (5.8 days) > 4-NP(38) (2.1 days) > 4-NP(1) (1.4 days), which is in agreement with the order of their reported estrogenicities. One metabolite of 4-NP(111) with less polarity than the parent compound occurred rapidly and remained stable in the soil. At the end of incubation (58 days), bound residues of 4-NP(111) amounted to 54% of the initially applied radioactivity and resided almost exclusively in the humin fraction of soil organic matter, in which chemically humin-bound residues increased over incubation. Our results indicate an increase of specific estrogenicity of the remaining 4-NPs in soil as a result of the isomer-specific degradation and therefore underline the importance of understanding the individual fate (including degradation, metabolism, and bound-residue formation) of isomers for risk assessment of 4-NPs in soil. 4-NP(1) should not be used as a representative of 4-NPs for studies on their environmental behavior.

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.

Pyrene and phenanthrene sorption to model and natural geosorbents in single- and binary-solute systems.

Sorption of pyrene and phenanthrene to model (illite and charcoal) and natural (Yangtze sediment) geosorbents were investigated by batch techniques using fluorescence spectroscopy. A higher adsorption of phenanthrene was observed with all sorbents, which is related to the better accessibility of smaller molecules to micropores in the molecular sieve sorbents. In addition, pyrene sorption in binary-solute systems with a constant initial concentration of phenanthrene (0.1 µmol L(-1) or 2 µmol L(-1)) was studied. A 0.1 µmol L(-1) concentration of phenanthrene causes no competitive effect on the pyrene sorption. A 2 µmol L(-1) concentration of phenanthrene significantly suppresses the sorption of pyrene, especially in the low concentration range; nonlinearity of the pyrene sorption isotherms thus decreases. The competitive effect of 2 µmol L(-1) phenanthrene on the pyrene sorption is overestimated by the ideal adsorbed solution theory (IAST) using the fitted single sorption results of both solutes. An adjustment of the IAST application by taking into account the molecular sieve effect is proposed, which notably improves the IAST prediction for the competitive effect.

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.

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.