Eco-friendly hydrogel based on locust bean gum for water retaining in sandy soil.

Sandy soils are suffering from water loss and desertification, which severely restrict the development of local agriculture. In this work, an eco-friendly hydrogel composed of borax and locust bean gum was synthesized to enhance the water retention capacity of sandy soil and support agricultural development in arid regions. Locust bean gum/borax hydrogel with a 3D network structure exhibited great water-absorbing capacity (130.29 g/g) within 30 min. After mixing 0.9 wt% hydrogel with sandy soil, the maximum soil water content, water retention time, soil porosity and soil organic matter were increased by 32.03 %, 14 days, 38.9 % and 8.64 g/kg respectively. Little effect on soil microorganisms revealed barely toxicity. Furthermore, the hydrogel was confirmed to be biodegradable at 43.47 % after 4 weeks. According to the study, locust bean gum/borax hydrogel possesses good water absorbing capacity, soil water retention ability, soil optimization ability and low adverse environmental impact. Together, it is inferred that the hydrogel can improve the water retention capacity of sandy soil in arid areas, promoting plant growth in arid areas.

Effect of calcium sources on enzyme-induced carbonate precipitation to solidify desert aeolian sand.

Enzyme-induced carbonate precipitation (EICP) is a promising technique for soil reinforcement. To select a suitable calcium source and a suitable solution amount for aeolian sand stabilization using EICP, specimens treated with different solution amounts (1.5, 2, 2.5, 3, and 3.5 L/m2). Surface strength, crust thickness, calcium carbonate content (CCC) and water vapor adsorption tests were performed to evaluate the effect of two calcium sources (calcium acetate and calcium chloride) on aeolian sand solidification. The plant suitability of solidified sand was investigated by the sea buckthorn growth test. The suitable calcium source was then used for the laboratory wind tunnel test and the field test to examine the erosion resistance of solidified sand. The results demonstrated that Ca(CH3COO)2-treated specimens exhibited higher strength than CaCl2-treated specimens at the same EICP solution amount, and the water vapor equilibrium adsorption mass of Ca(CH3COO)2-treated specimens was less, indicating that Ca(CH3COO)2-solidified sand was more effective and had better long-term stability. In addition, plants grown in Ca(CH3COO)2-treated sand had greater seedling emergence percentage and higher average height, which indicated that calcium acetate is a more suitable calcium source for EICP treatment. Furthermore, the surface strength and crust thickness of solidified sand increased with increasing the solution amount. For sand treated with 3 L/m2 of solution, the excessive strength and thickness of the crust made plants growth difficult, and the performance of sand treated with more than 2 L/m2 of solution significantly improved. Thus, the solution amount of 2-3 L/m2 is suggested for engineering applications. The sand solidified using EICP in the field could effectively mitigate wind erosion and facilitate the growth of native plants. Therefore, EICP can be combined with vegetative method to achieve long-term wind erosion control in the future.

Comparative study of polystyrene microplastic transport behavior in three different filter media: Quartz sand, zeolite, and anthracite.

Microplastics (MPs) are emerging contaminants that are attracting increasing interest from researchers, and the safety of drinking water is greatly affected by their transportation during filtration. Polystyrene (PS) was selected as a representative MPs, and three filter media (quartz sand, zeolite, and anthracite) commonly found in water plants were used. The retention patterns of PS-MPs by various filter media under various background water quality conditions were methodically investigated with the aid of DLVO theory and colloidal filtration theory. The results show that the different structures and elemental compositions of the three filter media cause them to exhibit different surface roughnesses and surface potentials. A greater surface roughness of the filter media can provide more deposition sites for PS-MPs, and the greater surface roughness of zeolite and anthracite significantly enhances their ability to inhibit the migration of PS-MPs compared with that of quartz sand. However, surface roughness is not the only factor affecting the migration of MPs. The lower absolute value of the surface potential of anthracite causes the DLVO energy between it and PS-MPs to be significantly lower than that between zeolite and PS-MPs, which results in stronger retention of PS-MPs by anthracite, which has a lower surface roughness, than zeolite, which has a higher surface roughness. The transport of PS-MPs in the medium is affected by the combination of the surface roughness of the filter media and the DLVO energy. Under the same operating conditions, the retention efficiencies of the three filter materials for PS-MPs followed the order of quartz sand < zeolite < anthracite. Additionally, the conditions of the solution markedly influenced the transport ability of PS-MPs within the simulated filter column. The transport PS-MPs in the simulated filter column decreased with increasing solution ionic strength and cation valence. Naturally, dissolved organic matter promoted the transfer of PS-MPs in the filter layer, and humic acid had a much stronger facilitating impact than fulvic acid. The study findings might offer helpful insight for improving the ability of filter units ability to retain MPs.

Ferrate as a coagulant prior to sand filters treating secondary wastewater effluent for reuse.

Wastewater reuse is one of the crucial water resources in Egypt due to the ongoing need to increase water resources and close the supply-demand gap. In this study, a new coagulant has been investigated before sand filters as an advanced wastewater treatment method. The sand filter pilot was run at a hydraulic loading rate of 0.75 m/h and two different dosages of three coagulants (Alum, FeCl3, and Ferrate VI) were selected using the jar tests. The sand filter without coagulant removed 12% of BOD5 and 70% of turbidity. Applying in-line coagulation before the sand filter provided effluents with better quality, especially for turbidity, organics, and microorganisms. Ferrate provided the highest removal of turbidity (90%) and BOD5 (93%) at very low dosages and lower costs compared with other coagulants, however, it adversely impacted both conductivity and dissolved solids. A significant effect on reducing bacteria was obtained with 40.0 mg/L of alum. According to the study's findings, the ferrate coagulant enhanced the sand filter's performance producing effluents with high quality, enabling it to meet strict water reuse regulations as well as aquatic environmental and health preservations.

Effect of sand minerals on microbially induced carbonate precipitation by denitrification.

Soil improvement techniques utilizing the metabolic functions of microorganisms, including microbially induced carbonate precipitation (MICP), have been extensively researched over the past few decades as part of bio-inspired geotechnical engineering research. Given that metabolic reactions in microorganisms produce carbonate minerals, an enhanced understanding of microbial interaction with soils could improve the effectiveness of MICP as a soil improvement technique. Therefore, this study investigated the effects of sands on MICP by denitrification to employ MICP for geotechnical soil improvement. Under the coexistence of natural sand and artificial silica sand, nitrate-reducing bacteria were cultured in a mixed liquid medium with nitrate, acetate, and calcium ions at 37 °C. Nitrate reduction occurred only in the presence of natural sand. However, the lack of chemical weathering of the composed minerals likely prevented the progress of bacterial growth and nitrate reduction in artificial silica sands. For natural sand, artificial chemical weathering by acid wash and ferrihydrite coating of the sand improved bacterial growth and accelerated nitrate reduction. The calcium carbonate formation induced by denitrification was also influenced by the state of the minerals in the soil and the nitrate reduction rate. The observed MICP enhancement is due to the involvement of coexisting secondary minerals like ferrihydrite with large specific surface areas and surface charges, which may improve the reaction efficiency by serving as adsorbents for bacteria and electron donors and acceptors in the solid phases, thereby promoting the precipitation and crystallization of calcium carbonate on the surfaces. This crystal formation in the minerals provides valuable insights for improving sand solidification via MICP. Considering the interactions between the target soil and microorganisms is essential to improving MICP processes for ground improvement.

Direct shear behaviors of excavated clay reinforced with geocomposite drainage layer encapsulated in thin sand layers.

The objective of this study is to assess the effectiveness of a novel structure comprising a geocomposite drainage layer and a thin sand layer (GDL + sand) in mitigating the rapid dumping of excavated clay and its associated issues, such as landslides. Two sets of direct shear tests were conducted to investigate the influence of sand layer thickness and compaction degree on the interface shear behavior of the GDL + sand structure. As the sand layer thickness increased, both the interface shear strength and friction angle gradually increased, first more sharply and then at a slower rate toward stability, while the interface cohesion decreased gradually. The optimal sand layer thickness for achieving the most effective reinforcement in stabilizing the clay was identified as 10 mm. A higher sand layer compaction degree was found to result in increased interface shear strength, interface friction angle, and interface cohesion. Building on these findings, the reinforcing efficiency of the GDL + sand structure was investigated through mechanism analysis in comparison to that of a geogrid + sand structure and GDL structure as per the interface friction coefficient. The ranking of interface friction coefficients among the three structures emerged as: geogrid + sand > GDL + sand > GDL. These results suggests that the GDL + sand structure exhibits superior reinforcement efficiency compared to the GDL structure and offers better drainage efficiency than the geogrid + sand structure.

Dry matter concentration, particle size distribution and sand presence in faeces from horses with and without colic.

A study comprising 74 colic and 74 control horses admitted to an animal hospital was performed. Faecal samples were collected and analysed for dry matter concentration, particle size distribution using wet-sieving, and sand presence through a sand sedimentation test. Data on horse breed, age, gender and basic feeding variables was collected and analysed using χ2-tests. Faecal dry matter concentration, particle size distribution and sand score was compared between colic and non-colic horses, and between horses with different colic types, using one-way ANOVA. Results showed that colic and non-colic horse groups were similar in breed, age, gender and basic feeding variables. Faecal dry matter concentration, particle size distribution and sand score were similar among colic and non-colic horses. Horses diagnosed with "unknown colic cause" had higher proportion of particles >0.5 <1.0 mm size compared to horses with colic due to impactions in caecum or colon, torsion or gas accumulation (P<0.05), but this difference was very small and most likely not of biological importance. Faecal dry matter concentration and sand score were similar among horses with different types of colic. Increased knowledge of the composition of particles of different size in equine faeces may enhance our understanding of digesta passage rate in colic and non-colic horses, which is needed to develop preventative measures of certain types of colic.

Polymer Coatings Affect Transport and Remobilization of Colloidal Activated Carbon in Saturated Sand Columns: Implications for In Situ Groundwater Remediation.

Colloidal activated carbon (CAC) is an emerging technology for the in situ remediation of groundwater impacted by per- and polyfluoroalkyl substances (PFAS). In assessing the long-term effectiveness of a CAC barrier, it is crucial to evaluate the potential of emplaced CAC particles to be remobilized and migrate away from the sorptive barrier. We examine the effect of two polymer stabilizers, carboxymethyl cellulose (CMC) and polydiallyldimethylammonium chloride (PolyDM), on CAC deposition and remobilization in saturated sand columns. CMC-modified CAC showed high mobility in a wide ionic strength (IS) range from 0.1 to 100 mM, which is favorable for CAC delivery at a sufficient scale. Interestingly, the mobility of PolyDM-modified CAC was high at low IS (0.1 mM) but greatly reduced at high IS (100 mM). Notably, significant remobilization (release) of deposited CMC-CAC particles occurred upon the introduction of solution with low IS following deposition at high IS. In contrast, PolyDM-CAC did not undergo any remobilization following deposition due to its favorable interactions with the quartz sand. We further elucidated the CAC deposition and remobilization behaviors by analyzing colloid-collector interactions through the application of Derjaguin-Landau-Verwey-Overbeek theory, and the inclusion of a discrete representation of charge heterogeneity on the quartz sand surface. The classical colloid filtration theory was also employed to estimate the travel distance of CAC in saturated columns. Our results underscore the roles of polymer coatings and solution chemistry in CAC transport, providing valuable guidelines for the design of in situ CAC remediation with maximized delivery efficiency and barrier longevity.

Influence of biochar in the calcite precipitation of sandy soil using sporosarcina ureae.

The microbially induced calcium carbonate precipitation (MICP) technology is an emerging novel and sustainable technique for soil stabilization and remediation. MICP, a microorganism-mediated biomineralization process, has attracted interest for its potential to enhance soil characteristics. The inclusion of biochar, a carbon-rich substance formed by biomass pyrolysis, adds another degree of intricacy to this process. The study highlights the impact of the combination of biochar and MICP together, using a bacterium, Sporosarcina ureae, on soil improvement. This blend of MICP and biochar improved the soil in terms of its geotechnical properties and also enabled the sequestering of carbon safely. It was observed that addition of 4% biochar significantly increased the soil's shear strength parameters (c and φ) as well as its stiffness after 21 treatment cycles. This improvement was because the calcium carbonate precipitate, which acts as a crucial binding agent, increased significantly due to microbial action in the soil-biochar mixture compared to the pure soil sample. The excess carbonate precipitation on account of biochar addition was verified through SEM-EDAX analysis where the images showed noteworthy carbonate precipitation on the surface of particles and increment in the calcium mass at the same treatment cycles when compared with untreated sand. The collaboration between MICP and biochar effectively increased the carbon sequestration within the sand sample. It was observed that at 21 cycles of treatment, the carbon storage within the sand sample increased by almost 3 times at 4% biochar compared to sand without any biochar. The statistical analysis further affirmed that strength depends on both biochar and the number of treatment cycles, whereas carbon sequestration potential is primarily influenced by the biochar content alone. This strategy, as a sustainable and environmentally friendly approach, has the potential to reform soil improvement practices and contribute to both soil strength enhancement and climate change mitigation, supporting the maintenance of ecological balance.

Ecofriendly solidification of sand using microbially induced calcium phosphate precipitation.

This study introduces microbiologically induced calcium phosphate precipitation (MICPP) as a novel and environmentally sustainable method of soil stabilization. Using Limosilactobacillus sp., especially NBRC 14511 and fish bone solution (FBS) extracted from Tuna fish bones, the study was aimed at testing the feasibility of calcium phosphate compounds (CPCs) deposition and sand stabilization. Dynamic changes in pH and calcium ion (Ca2+) concentration during the precipitation experiments affected the precipitation and sequential conversion of dicalcium phosphate dihydrate (DCPD) to hydroxyapatite (HAp), which was confirmed by XRD and SEM analysis. Sand solidification experiments demonstrated improvements in unconfined compressive strength (UCS), especially at higher Urea/Ca2+ ratios. The UCS values obtained were 10.35 MPa at a ratio of 2.0, 3.34 MPa at a ratio of 1.0, and 0.43 MPa at a ratio of 0.5, highlighting the advantages of MICPP over traditional methods. Microstructural analysis further clarified the mineral composition, demonstrating the potential of MICPP in environmentally friendly soil engineering. The study highlights the promise of MICPP for sustainable soil stabilization, offering improved mechanical properties and reducing environmental impact, paving the way for novel geotechnical practices.

Influence of clay minerals on pH and major cation concentrations in acid-leached sands: Column experiments and reactive-transport modeling.

A series of laboratory experiments are conducted to simulate the acidification and subsequent recovery of a sand aquifer exploited by in situ recovery (ISR) mining. A sulfuric acid solution (pH 2) is first injected into a column packed with sand from the Zoovch Ovoo uranium roll front deposit (Mongolia). Solutions representative of local groundwater or enriched in cations (Na+, Mg2+) are then circulated through the column to simulate the inflow of aquifer water. pH and major ion concentrations (Na+, Cl-, SO42-, Ca2+, Mg2+, K+) measured at the column outlet reproduce the overall evolution of porewater chemistry observed in the field. The presence of minor quantities of swelling clay minerals (≈6 wt% smectite) is shown to exert an important influence on the behavior of inorganic cations, particularly H+, via ion-exchange reactions. Numerical models that consider ion-exchange on smectite as the sole solid-solution interaction are able to reproduce variations in pH and cation concentrations in the column experiments. This highlights the importance of clay minerals in controlling H+ mobility and demonstrates that sand from the studied aquifer can be described to a first order as an ion-exchanger. The present study confirms the key role of clay minerals in controlling water chemistry in acidic environments through ion-exchange processes. In a context of managing the long-term environmental footprint of industrial and mining activities (ISR, acid mine drainage…), this work will bring insights for modeling choices and identification of key parameters to help operators to define their production and/or remediation strategies.

Experimental study on the effect of different cement content on the improvement of dynamic characteristics of seismic-prone poor soil.

The improvement of sandy soils with poor seismic properties to modify their dynamic characteristics is of great importance in seismic design for engineering sites. In this study, a series of dynamic tests on sandy soils sandy soils with poor seismic conditions were conducted using the GCTS resonant column system to investigate the improvements effects of different cement contents on dynamic characteristic parameters. The research findings are as follows: The cement content has certain influences on the dynamic shear modulus, dynamic shear modulus ratio, the maximum dynamic shear modulus, and the damping ratio of sandy soils with poor seismic properties. Among them, the influence on dynamic shear modulus is limited, while the damping ratio is significantly affected. The addition of cement to seismic-poor sandy soils significantly enhances their dynamic characteristics. The most noticeable improvement is observed when the cement content is 8%. Through curve fitting analysis, a relationship equation is established between the maximum dynamic shear modulus and the cement content, and the relevant parameters are provided. A comparative test between the improved soils and the remolded soils reveals that the addition of cement significantly improves the seismic performance of the poor soils. The recommended values for the range of variation of the dynamic shear modulus ratio and damping ratio are provided, considering the effect of improvement. These research findings provide reference guidelines for seismic design and engineering sites.

Transport and retention of positively charged zinc oxide nanoparticles in saturated porous media: Effects of metal oxides and clays.

The effects of metal oxides and clays on the transport of zinc oxide nanoparticles (ZnO-NPs) in saturated porous media were investigated under different ionic strength (IS) conditions. We studied the transport and retention behavior of ZnO-NPs for different types of porous media (untreated, acid treated, and acid-salt treated sand). The selected untreated sand was used as a representative sand, coated with both metal oxide and clay. The acid treated and acid-salt-treated sands were used and compared to investigate the effects of clays on the surface of the sand. In addition, the effects of clay particles in bulk solutions on the mobility and retention of ZnO-NPs were observed using bentonite as a representative clay particle. We found that the increased mobility of positively charged ZnO-NPs can be attributed to increasing charge heterogeneity of silica sand with metal oxides (mainly, iron oxide) and clays in untreated sand. No breakthrough of ZnO-NP was observed for acid-treated (presence of clays and absence of metal oxides) and acid-salt-treated sand (absence of both metal oxide and clays). Most of the injected ZnO-NPs were deposited on the surface of the sand near the column inlet. The transport of bentonite-facilitated ZnO-NPs was improved at the lowest IS (0.1 mM) (∼20%), whereas there was no difference in the mobility of ZnO-NPs at high IS solutions (1 mM and 10 mM). In particular, the breakthrough amount improved with increasing bentonite concentration. Classical Derjaguin-Landau-Verwey-Overbeek interactions help explain observed interactions between ZnO-NPs and sand as well as bentonite and sand.

Architecture dependent transport behavior of iron (0) entrapped biodegradable polymeric particles for groundwater remediation.

Polylactic acid based spherical particles with three architectural variations (Isotropic (P1), Semi porous (P2), and Janus (P3)) were employed to encapsulate zero valent iron nanoparticles (ZVINPs), and their performance was extensively evaluated in our previous studies. However, little was known about their transportability through saturated porous media of varying grain size kept under varying ionic strength. In this particular study, we aimed to investigate the architectural effect of polymeric particles (P1-P3) on their mobility through the sand column of varying grain size in presence of mono, di, and tri-valent ions of varying concentrations (25-200 mM (millimoles)). As per column breakthrough experiments (BTCs) using various types of sands, amphiphilic Janus type (P3) particles exhibited the maximum transportability among all the tested particles, irrespective of the nature of the sand. Owing to the narrower travel path, sands with lower porosity (31%) delayed the plateau by shifting it to a higher pore volume with a minimum retention of iron (C/Co: 0.94 for P3) in the column. The impact of mono (Na+, K+), di (Ca2+, Mg2+), and trivalent (Al3+) ions on their transportability was progressively increased from P3 to P1, especially at higher ionic concentrations (200 mM), with P3 being the most mobile particles (C/Co:0.54 for Al3+). Among all the ions, Al3+ exhibited maximum hindrance to their mobility through the sand column. This could be due to their strong charge screening effect coupled with cation bridging complex formation with moving particles. Experimental results obtained from BTCs were found to be well-fitted with a theoretical model based on advection-dispersion equation, showing minimum retention for P3 particles. Overall, it can be inferred that encapsulation of ZVINPs inside Janus particles (P3) with a right balance of amphiphilicity and highly negative surface charge would be required to achieve considerable transportability through sand aquifers to target contaminants in polluted groundwater existing under harsh conditions (high ionic concentrations).

Low adsorption affinity of athabasca oil sands naphthenic acid fraction compounds to a peat-mineral mixture.

Much of the toxicity in oil sands process-affected water in Athabasca oil sands tailings has been attributed to naphthenic acids (NAs) and associated naphthenic acid fraction compounds (NAFCs). Previous work has characterized the environmental behaviour and fate of these compounds, particularly in the context of constructed treatment wetlands. There is evidence that wetlands can attenuate NAFCs in natural and engineered contexts, but relative contributions of chemical, biotic, and physical adsorption with sequestration require deconvolution. In this work, the objective was to evaluate the extent to which prospective wetland substrate material may adsorb NAFCs using a peat-mineral mix (PMM) sourced from the Athabasca Oil Sands Region (AOSR). The PMM and NAFCs were first mixed and then equilibrated across a range of NAFC concentrations (5-500 mg/L) with moderate ionic strength and hardness (∼200 ppm combined Ca2+ and Mg2+) that approximate wetland water chemistry. Under these experimental conditions, low sorption of NAFCs to PMM was observed, where sorbed concentrations of NAFCs were approximately zero mg/kg at equilibrium. When NAFCs and PMM were mixed and equilibrated together at environmentally relevant concentrations, formula diversity increased more than could be explained by combining constituent spectra. The TOC present in this PMM was largely cellulose-derived, with low levels of thermally recalcitrant carbon (e.g., lignin, black carbon). The apparent enhancement of the concentration and diversity of components in PMM/NAFCs mixtures are likely related to aqueous solubility of some PMM-derived organic materials, as post-hoc combination of dissolved components from PMM and NAFCs cannot replicate enhanced complexity observed when the two components are agitated and equilibrated together.

Adsorption-desorption of 241Am(â ¢) on montmorillonite colloids and quartz sand: Effects of pH, ionic strength, colloid concentration and grain size.

Clay colloids in the subsurface environment have a strong adsorption capacity for radionuclides, and the mobile colloids will carry the nuclides for migration, which would promote the movability of radionuclides in the groundwater environment and pose a threat to the ecosphere. The investigations of the adsorption/desorption behaviors of radionuclides in colloids and porous media are significant for the evaluation of the geological disposal of radioactive wastes. To illustrate the adsorption/desorption behaviors of 241Am(Ⅲ) in Na-montmorillonite colloid and/or quartz sand systems at different pH (5, 7 and 9), ionic strengths (0, 0.1 and 5 mM), colloid concentrations (300 and 900 mg/L), nuclide concentrations (500, 800, 1100 and 1400 Bq/mL) and grain sizes (40 and 60 mesh), a series of batch sorption-desorption experiments were conducted. Combining the analysis of the physical and chemical properties of Na-montmorillonite with the Freundlich model, the influencing mechanism of different controlling factors is discussed. The experimental results show that the adsorption/desorption behaviors of 241Am(Ⅲ) in Na-montmorillonite colloid and/or quartz sand strongly are influenced by the pH value and ionic strength of a solution, the colloid concentration as well as quartz sand grain size. The adsorption and desorption isotherms within all the experimental conditions could be well-fitted by the Freundlich model and the correlation coefficients (R2) are bigger than 0.9. With the increase in pH, the adsorption partition coefficient (Kd) at 241Am(Ⅲ)-Na-montmorillonite colloid two-phase system and 241Am(Ⅲ)-Na-montmorillonite colloid-quartz sand three-phase system presents a trend which increases firstly followed by decreasing, due to the changes in the morphology of Am with pH. The Kd of 241Am(Ⅲ) adsorption on montmorillonite colloid and quartz sand decreases with increasing in ionic strength, which is mainly attributed to the competitive adsorption, surface complexation and the reduction of surface zeta potential. Additionally, the Kd increases with increasing colloid concentrations because of the increase in adsorption sites. When the mean grain diameter changes from 0.45 to 0.3 mm, the adsorption variation trends of 241Am(Ⅲ) remain basically unchanged. The research results obtained in this work are meaningful and helpful in understanding the migration behaviors of radionuclides in the underground environment.

Nutrient supplementation-induced metabolic profile changes and early appearance of free N-glycans in nutrient deficient tomato plants revealed by mass spectrometry.

Inorganic fertilizers are routinely used in large scale crop production for the supplementation of nitrogen, phosphorus, and potassium in nutrient poor soil. To explore metabolic changes in tomato plants grown on humic sand under different nutritional conditions, matrix-assisted laser desorption ionization (MALDI) mass spectrometry was utilized for the analysis of xylem sap. Variations in the abundances of metabolites and oligosaccharides, including free N-glycans (FNGs), were determined. Statistical analysis of the sample-related peaks revealed significant differences in the abundance ratios of multiple metabolites, including oligosaccharides, between the control plants, grown with no fertilizers, and plants raised under "ideal" and "nitrogen deficient" nutritional conditions, i.e., under the three treatment types. Among the 36 spectral features tentatively identified as oligosaccharides, the potential molecular structures for 18 species were predicted based on their accurate masses and isotope distribution patterns. To find the spectral features that account for most of the differences between the spectra corresponding to the three different treatments, multivariate statistical analysis was carried out by orthogonal partial least squares-discriminant analysis (OPLS-DA). They included both FNGs and non-FNG compounds that can be considered as early indicators of nutrient deficiency. Our results reveal that the potential nutrient deficiency indicators can be expanded to other metabolites beyond FNGs. The m/z values for 20 spectral features with the highest variable influence on projection (VIP) scores were ranked in the order of their influence on the statistical model.

Analysing the role of Fe (II) on flocculation of sand-clay mixtures under estuarine mixing.

Estuaries are fragile environment that are most affected by climate change. One of the major consequences of climate change on estuarine processes is the enhancement in salt intrusion leading to higher salinity values. This has several implications on the estuarine sediment dynamics. Of the various factors that affect the flocculation of cohesive sediments, salinity and turbulence have been recognized as to have great significance. Many of the estuaries are contaminated with heavy metals, of which, the concentration of Iron (Fe (II)) are generally on the higher range. However, the influence of Fe (II) on the flocculation of cohesive sediments at various estuarine mixing conditions is not well known. The present study investigated the influence of Fe (II) on the flocculation of kaolin at various concentration of Fe (II), salinity and turbulence shear. The results indicated that Fe (II) and salinity have a positive influence on kaolin flocculation. The increase in turbulence shear caused an initial increase and then a decrease in floc size. In case of sand-clay mixtures, that are observed in mixed sediment estuarine environments, a reduction in the floc size was observed, which is attributed to the breakage of flocs induced by the shear of sand. Breakage coefficient, which is a measure of break-up of flocs, is generally adopted as 0.5 assuming binary breakage. The present study revealed that the breakage coefficient can take values from 0 to 1 and is a direct function of Fe (II) and salinity and an inverse function of turbulence and sand concentration. Thus, a new model for breakage coefficient with the influencing parameters has been proposed, which is an improvement of existing model that is expressed in terms of turbulence alone. Sensitivity analysis showed that the proposed model can very well predict the breakage coefficient of Fe (II) - kaolin flocs. Thus, the model can quantify the breakage coefficient of flocs in estuaries contaminated with Fe (II) that is a vital parameter for population balance models.

Validation and Simultaneous Monitoring of 311 Pesticide Residues in Loamy Sand Agricultural Soils by LC-MS/MS and GC-MS/MS, Combined with QuEChERS-Based Extraction.

Soil can be contaminated by pesticide residues through agricultural practices, by direct application or through spray-drift in cultivations. The dissipation of those chemicals in the soil may pose risks to the environment and human health. A simple and sensitive multi-residue analytical method was optimized and validated for the simultaneous determination of 311 active substances of pesticides in agricultural soils. The method involves sample preparation with QuEChERS-based extraction, and determination of the analytes with a combination of GC-MS/MS and LC-MS/MS techniques. Calibration plots were linear for both detectors over the range of five concentration levels, using matrix-matched calibration standards. The obtained recoveries from fortified-soil samples ranged from 70 to 119% and from 72.6 to 119% for GC-MS/MS and LC-MS/MS, respectively, while precision values were <20% in all cases. As regards the matrix effect (ME), signal suppression was observed in the liquid chromatography (LC)-amenable compounds, which was further estimated to be negligible. The gas chromatography (GC)-amenable compounds showed enhancement in the chromatographic response estimated as medium or strong ME. The calibrated limit of quantification (LOQ) value was 0.01 µg g-1 dry weight for most of the analytes, while the corresponding calculated limit of determination (LOD) value was 0.003 µg g-1 d.w. The proposed method was subsequently applied to agricultural soils from Greece, and positive determinations were obtained, among which were non-authorized compounds. The results indicate that the developed multi-residue method is fit for the purpose of analyzing low levels of pesticides in soil, according to EU requirements.