Iron nanoparticles coated with amphiphilic polysiloxane graft copolymers: dispersibility and contaminant treatability

Amphiphilic polysiloxane graft copolymers (APGCs) were used as a delivery vehicle for nanoscale zerovalent iron (NZVI). The APGCs were designed to enable adsorption onto NZVI surfaces via carboxylic acid anchoring groups and polyethylene glycol (PEG) grafts were used to provide dispersibility in water. Degradation studies were conducted with trichloroethylene (TCE) as the model contaminant. TCE degradation rate with APGC-coated NZVI (CNZVI) was determined to be higher as compared to bare NZVI. The surface normalized degradation rate constants, k(SA) (Lm(2-) h(-1)), for TCE removal by CNZVI and bare NZVI ranged from 0.008 to 0.0760 to 007-0.016, respectively. Shelf life studies conducted over 12 months to access colloidal stability and 6 months to access TCE degradation indicated that colloidal stability and chemical reactivity of CNZVI remained more or less unchanged. The sedimentation characteristics of CNZVI under different ionic strength conditions (0-10 mM) did not change significantly. The steric nature of particle stabilization is expected to improve aquifer injection efficiency of the coated NZVI for groundwater remediation.     

Adsorption of humic acid onto nanoscale zerovalent iron and its effect on arsenic removal

Batch experiments were performed to investigate the feasibility of humic acid (HA) removal by synthetic nanoscale zerovalent iron (NZVI) and its interaction with As(III) and As(V), the most poisonous and abundant of groundwater pollutants. High-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) were used to characterize the particle size, surface morphology of the pristine NZVI and HA-treated NZVI (NZVI-HA), and the zero valence state of the pristine NZVI. It was determined that HA was completely removed by NZVI (0.3 g/L) within a few minutes, at a wide range of initial pH values (approximately 3.0-12.0). Fourier transform infrared (FTIR) and laser light scattering (zeta potential measurement) studies confirmed that NZVI-HA forms inner-sphere surface complexation at different initial pH conditions. The effects of competing anions showed that there was complete removal of HA in the presence of 10 mM NO(-3) and SO4(2-) whereas HA removal was observed 0%, 18% and 22% in presence of 10 mM H2PO4(2-), HCO(3-) and H4SiO4(0), respectively. However, the presence of 2 mM CA2+ and Mg2+ enhanced HA removal from 17 mg g(-1) to 76 mg g(-1) and 55 mg g(-1), respectively. Long-term time-resolved studies of XRD and field emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray (EDX) revealed the formation of various types of new iron oxides (magnetite, maghemite, and lepidocrocites) during the continuous reaction of HA in the presence of water and NZVI at 1, 30, 60, and 90 days. In addition, the surface-area-normalized rate constant (ksa) of adsorption of As(III) and As(V) onto NZVI was reduced in the presence of HA (20 mg L(-1)), from 100% to 43% and 68%, respectively. Our results show the potential use of NZVI in removing HA and its possible effects on arsenic removal during the application of NZVI in groundwater remediation.     

Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and H2 evolution

Nanoscale zero-valent iron (NZVI) is used to remediate contaminated groundwater plumes and contaminant source zones. The target contaminant concentration and groundwater solutes (NO3-, Cl-, HCO3-, SO4(2-), and HPO4(2-)) should affect the NZVI longevity and reactivity with target contaminants, but these effects are not well understood. This study evaluates the effect of trichloroethylene (TCE) concentration and common dissolved groundwater solutes on the rates of NZVI-promoted TCE dechlorination and H2 evolution in batch reactors. Both model systems and real groundwater are evaluated. The TCE reaction rate constant was unaffected by TCE concentration for [TCE] < or = 0.46 mM and decreased by less than a factor of 2 for further increases in TCE concentration up to water saturation (8.4 mM). For [TCE] > or = 0.46 mM, acetylene formation increased, and the total amount of H2 evolved at the end of the particle reactive lifetime decreased with increasing [TCE], indicating a higher Fe0 utilization efficiency for TCE dechlorination. Common groundwater anions (5mN) had a minor effect on H2 evolution but inhibited TCE reduction up to 7-fold in increasing order of Cl- < SO4(2-) < HCO3- < HPO4(2). This order is consistent with their affinity to form complexes with iron oxide. Nitrate, a NZVI-reducible groundwater solute, present at 0.2 and 1 mN did not affect the rate of TCE reduction but increased acetylene production and decreased H2 evolution. NO3- present at > 3 mM slowed TCE dechlorination due to surface passivation. NO3- present at 5 mM stopped TCE dechlorination and H2 evolution after 3 days. Dissolved solutes accounted for the observed decrease of NZVI reactivity for TCE dechlorination in natural groundwater when the total organic content was small (< 1 mg/L).     

Removal of arsenic(III) from groundwater by nanoscale zero-valent iron

Nanoscale zero-valent iron (NZVI) was synthesized and tested for the removal of As(III), which is a highly toxic, mobile, and predominant arsenic species in anoxic groundwater. We used SEM-EDX, AFM, and XRD to characterize particle size, surface morphology, and corrosion layers formed on pristine NZVI and As(III)-treated NZVI. AFM results showed that particle size ranged from 1 to 120 nm. XRD and SEM results revealed that NZVI gradually converted to magnetite/maghemite corrosion products mixed with lepidocrocite over 60 d. Arsenic(III) adsorption kinetics were rapid and occurred on a scale of minutes following a pseudo-first-order rate expression with observed reaction rate constants (K(obs)) of 0.07-1.3 min(-1) (at varied NZVI concentration). These values are about 1000x higher than K(obs) literature values for As(III) adsorption on micron size ZVI. Batch experiments were performed to determine the feasibility of NZVI as an adsorbent for As(III) treatment in groundwater as affected by initial As(III) concentration and pH (pH 3-12). The maximum As(III) adsorption capacity in batch experiments calculated by Freundlich adsorption isotherm was 3.5 mg of As(III)/g of NZVI. Laser light scattering (electrophoretic mobility measurement) confirmed NZVI-As(III) inner-sphere surface complexation. The effects of competing anions showed HCO3-, H4SiO4(0), and H2P04(2-) are potential interferences in the As(III) adsorption reaction. Our results suggest that NZVI is a suitable candidate for both in-situ and ex-situ groundwater treatment due to its high reactivity.     

Adsorption of pathogenic prion protein to quartz sand

Management responses to prion diseases of cattle, deer, and elk create a significant need for safe and effective disposal of infected carcasses and other materials. Furthermore, soil may contribute to the horizontal transmission of sheep scrapie and cervid chronic wasting disease by serving as an environmental reservoirforthe infectious agent. As an initial step toward understanding prion mobility in porous materials such as soil and landfilled waste, the influence of pH and ionic strength (l) on pathogenic prion protein (PrPsc) properties (viz. aggregation state and zeta-potential) and adsorption to quartz sand was investigated. The apparent average isoelectric point of PrPsc aggregates was 4.6. PrPsc aggregate size was largest between pH 4 and 6, and increased with increasing l at pH 7. Adsorption to quartz sand was maximal near the apparent isoelectric point of PrPsc aggregates and decreased as pH either declined or increased. PrPsc adsorption increased as suspension l increased, and reached an apparent plateau at l approximately 0.1 M. While trends with pH and l in PrPsc attachment to quartz surfaces were consistent with predictions based on Born-DLVO theory, non-DLVO forces appeared to contribute to adsorption at pH 7 and 9 (l = 10 mM). Our findings suggest that disposal strategies that elevate pH (e.g., burial in lime or fly ash), may increase PrPsc mobility. Similarly, PrPsc mobility may increase as a landfill ages, due to increases in pH and decreases in l of the leachate.     

Cation concentrations in fluid from the oviduct ampulla and isthmus of cows during the estrous cycle.

To detect variations in oviduct fluid cation concentrations, Ca++, Mg++, K+, and Na+ were determined for daily samples of blood serum and bovine oviduct fluid collected from indwelling isthmic and ampullary catheters. Isthmic oviduct fluid Ca++ concentration was significantly greater than that in ampullary fluid, particularly around estrus and ovulation. Maximum Ca++ concentrations found in isthmic oviduct fluid at estrus (2.57 +/- .22 mM) and at ovulation (2.50 +/- .29 mM) were similar to those of medium used for in vitro capacitation of bovine sperm. Concentrations of Mg++ in oviduct fluid differed significantly by estrous cycle stage, but not by oviduct region, and were consistently lower than those detected in serum. No relationships were found for K+ or Na+ with respect to region or stage, but K+ was generally higher in oviduct fluid than in serum. The concentration of K+ averaged over stage and region (4.46 +/- .13 mM) and the K+:Na+ ratio (.032 +/- .002) were similar to those reported in bovine in vitro capacitating and fertilizing media. Concentrations of Ca++ and Na+ from peritoneal fluid from nonstaged cows were similar to those of oviduct fluid or serum. The Mg++ concentration was greater, and K+ concentration was less, in peritoneal than in oviduct fluid.     

Influence of collector surface composition and water chemistry on the deposition of cerium dioxide nanoparticles: QCM-D and column experiment approaches

The deposition behavior of cerium dioxide (CeO(2)) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied in quartz crystal microbalance with dissipation (QCM-D) to examine the effect of these mineral phases on CeO(2) deposition in NaCl solution (1-200 mM). Frequency and dissipation shift followed the order: silica > iron oxide > alumina in 10 mM NaCl at pH 4.0. No significant deposition was observed at pH 6.0 and 8.5 on any of the tested sensors. However, ≥ 94.3% of CeO(2) NPs deposited onto Ottawa sand in columns in 10 mM NaCl at pH 6.0 and 8.5. The inconsistency in the different experimental approaches can be mainly attributed to NP aggregation, surface heterogeneity of Ottawa sand, and flow geometry. In QCM-D experiments, the deposition kinetics was found to be qualitatively consistent with the predictions based on the classical colloidal stability theory. The presence of low levels (1-6 mg/L) of Suwannee River humic acid, fulvic acid, alginate, citric acid, and carboxymethyl cellulose greatly enhanced the stability and mobility of CeO(2) NPs in 1 mM NaCl at pH 6.5. The poor correlation between the transport behavior and electrophoretic mobility of CeO(2) NPs implies that the electrosteric effect of OM was involved.     

Characterization of the enhancement effect of Na2CO3 on the sulfur capture capacity of limestones

It has been known for a long time that certain additives (e.g., NaCl, CaCl2, Na2CO3, Fe2O3) can increase the sulfur dioxide capture-capacity of limestones. In a recent study we demonstrated that very small amounts of Na2CO3 can be very beneficial for producing sorbents of very high sorption capacities. This paper explores what contributes to these significant increases. Mercury porosimetry measurements of calcined limestone samples reveal a change in the pore-size from 0.04-0.2 microm in untreated samples to 2-10 microm in samples treated with Na2CO3--a pore-size more favorable for penetration of sulfur into the particles. The change in pore-size facilitates reaction with lime grains throughout the whole particle without rapid plugging of pores, avoiding premature change from a fast chemical reaction to a slow solid-state diffusion controlled process, as seen for untreated samples. Calcination in a thermogravimetric reactor showed that Na2CO3 increased the rate of calcination of CaCO3 to CaO, an effect which was slightly larger at 825 degrees C than at 900 degrees C. Peak broadening analysis of powder X-ray diffraction data of the raw, calcined, and sulfated samples revealed an unaffected calcite size (approximately 125-170 nm) but a significant increase in the crystallite size for lime (approximately 60-90 nm to approximately 250-300 nm) and less for anhydrite (approximately 125-150 nm to approximately 225-250 nm). The increase in the crystallite and pore-size of the treated limestones is attributed to an increase in ionic mobility in the crystal lattice due to formation of vacancies in the crystals when Ca is partly replaced by Na.     

Aggregation kinetics and transport of single-walled carbon nanotubes at low surfactant concentrations

Little is known about how low levels of surfactants can affect the colloidal stability of single-walled carbon nanotubes (SWNTs) and how surfactant-wrapping of SWNTs can impact ecological exposures in aqueous systems. In this study, SWNTs were suspended in water with sodium dodecylsulfate (SDS) as a surface-active dispersing agent. The effect of SDS concentration on SWNT suspension stability was investigated with time-resolved dynamic light scattering (TRDLS) initial aggregation studies utilizing both monovalent (Na(+)) and divalent (Ca(2+)) cations. The critical coagulation concentration (CCC) values increased with SDS concentration for the Na(+) treatments, but the Ca(2+) treatments were less sensitive to SDS concentration changes. Longer term stability studies with SDS concentrations orders of magnitude below the SDS critical micelle concentration demonstrated that SWNTs remained suspended for over six weeks in a surface water. Transport studies in a freshwater sediment similarly showed a SDS concentration-dependent mobility of SDS-wrapped SWNTs in that SWNTs showed a relatively greater retention at lower SDS concentrations (0.001%-0.05% w/v) than at a higher SDS concentration (0.1%). It is hypothesized that the stability and mobility of SWNT suspensions is directly related to the surface coverage of SDS on the SWNT surface that simultaneously increases electrosteric repulsion and decreases surface chemical heterogeneity. Overall, these studies demonstrate that low levels of surfactant are effective in stabilizing and mobilizing SWNTs in environmental media.     

Manipulating the size and dispersibility of zerovalent iron nanoparticles by use of carboxymethyl cellulose stabilizers

Zerovalent iron (ZVI) nanoparticles of various sizes were synthesized by applying various types of carboxymethyl cellulose (CMC) as a stabilizer. At an initial Fe2+ concentration of 0.1 g/L and with 0.2% (w/w) of CMC (Mr = 90 000), nanoparticles with a hydrodynamic diameter of 18.6 nm were obtained. Smaller nanoparticles were obtained as the CMC/Fe2+ molar ratio was increased. When the initial Fe2+ concentration was increased to 1 g/L, only 1/4 of the CMC was needed to obtain similar nanoparticles. On an equal weight basis, CMC with a greater Mr or higher D.S. (degree of substitution) gave smaller nanoparticles, and lower the synthesizing temperature favored the formation of smaller nanoparticles. It is proposed that CMC stabilizes the nanoparticles through the accelerating nucleation of Fe atoms during the formation of ZVI nanoparticles and, subsequently, forms a bulky and negatively charged layer via sorption of CMC molecules on the ZVI nanoparticles, thereby preventing the nanoparticles from agglomeration through electrosteric stabilization. In agreement with the classical coagulation theory, the presence of high concentrations of cations (Na+ and Ca2+) promoted agglomeration of the nanoparticles. The strategy for manipulating the size of the ZVI nanoparticles may facilitate more effective applications of ZVI nanoparticles for in situ dechlorination in soils and groundwater.     

Colloidal stability of carbonate-coated silver nanoparticles in synthetic and natural freshwater

To gain important information on fate, mobility, and bioavailability of silver nanoparticles (AgNP) in aquatic systems, the influence of pH, ionic strength, and humic substances on the stability of carbonate-coated AgNP (average diameter 29 nm) was systematically investigated in 10 mM carbonate and 10 mM MOPS buffer, and in filtered natural freshwater. Changes in the physicochemical properties of AgNP were measured using nanoparticle tracking analysis, dynamic light scattering, and ultraviolet-visible spectroscopy. According to the pH-dependent carbonate speciation, below pH 4 the negatively charged surface of AgNP became positive and increased agglomeration was observed. Electrolyte concentrations above 2 mM Ca(2+) and 100 mM Na(+) enhanced AgNP agglomeration in the synthetic media. In the considered concentration range of humic substances, no relevant changes in the AgNP agglomeration state were measured. Agglomeration of AgNP exposed in filtered natural freshwater was observed to be primarily controlled by the electrolyte type and concentration. Moreover, agglomerated AgNP were still detected after 7 days of exposure. Consequently, slow sedimentation and high mobility of agglomerated AgNP could be expected under the considered natural conditions. A critical evaluation of the different methods used is presented as well.     

Transport of non-newtonian suspensions of highly concentrated micro- and nanoscale iron particles in porous media: a modeling approach

The use of zerovalent iron micro- and nanoparticles (MZVI and NZVI) for groundwater remediation is hindered by colloidal instability, causing aggregation (for NZVI) and sedimentation (for MZVI) of the particles. Transportability of MZVI and NZVI in porous media was previously shown to be significantly increased if viscous shear-thinning fluids (xanthan gum solutions) are used as carrier fluids. In this work, a novel modeling approach is proposed and applied for the simulation of 1D flow and transport of highly concentrated (20 g/L) non-newtonian suspensions of MZVI and NZVI, amended with xanthan gum (3 g/L). The coupled model is able to simulate the flow of a shear thinning fluid including the variable apparent viscosity arising from changes in xanthan and suspended iron particle concentrations. The transport of iron particles is modeled using a dual-site approach accounting for straining and physicochemical deposition/release phenomena. A general formulation for reversible deposition is herein proposed, that includes all commonly applied dynamics (linear attachment, blocking, ripening). Clogging of the porous medium due to deposition of iron particles is modeled by tying porosity and permeability to deposited iron particles. The numerical model proved to adequately fit the transport tests conducted using both MZVI and NZVI and can develop into a powerful tool for the design and the implementation of full scale zerovalent iron applications.     

Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. M?ssbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.     

Calcium, phosphate and citrate in human milk at initiation of lactation.

The onset of copious milk secretion (lactogenesis II) in women occurs between 1 and 3 d after birth, and during this period the composition of breast milk changes. During the first 5 d of lactation we measured the concentrations of total, diffusible and ionized Ca (Catot, Cad, Ca2+), diffusible phosphate (Pid), diffusible citrate (Citd) and lactose in the breast milk. On day 1 after birth the concentrations (mean +/- SEM) were Catot, 5.71 +/- 0.30 mM; Cad, 2.66 +/- 0.19 mM; Ca2+, 2.90 +/- 0.18 mM; Pid, 0.26 +/- 0.16 mM; Citd, 0.25 +/- 0.03 mM and lactose, 76 +/- 11 mM. Between day 1 and day 4 the concentration of Catot increased 1.7-fold to 9.56 +/- 0.39 mM, Cad increased 1.8-fold to 4.75 +/- 0.26 mM, Ca2+ decreased by 20% to 2.33 +/- 0.13 mM, Pid increased 6.6-fold to 1.69 +/- 0.11 mM, Citd increased 20-fold to 5.06 +/- 0.21 mM, and lactose increased 2.3-fold to 173 +/- 4 mM. A high correlation has been found between [Cad] and [Citd] in the milk of both ruminant and non-ruminant species, which show a wide range in concentrations of [Cad] and [Citd], and the data fit a simple physicochemical model of ion equilibria in the aqueous phase of milk. The results of the present study confirm the relationship between [Cad] and [Citd] in human milk, even during lactogenesis II when the composition of the milk is changing very rapidly.     

The Role of Chitosan in Emulsion Formation and Stabilization

This article reviews the basic principles of emulsion formation and stabilization through the electrosteric function of chitosan. Chitosan, which is a polycationic biopolymer, may act as an emulsifier and emulsion stabilizer through adsorption of the protective layer at oil-water interfaces, viscosity enhancement, and interaction with surface-active agents (e.g., surfactants, proteins, and polysaccharides). The interaction of chitosan at droplet interfaces can be associated with flocculation or electrosteric stabilization, depending on the nature and concentration of the chitosan, emulsifier characteristics, and the pH and ionic strength of solution.     

Transport of ferrihydrite nanoparticles in saturated porous media: role of ionic strength and flow rate

The use of nanoscale ferrihydrite particles, which are known to effectively enhance microbial degradation of a wide range of contaminants, represents a promising technology for in situ remediation of contaminated aquifers. Thanks to their small size, ferrihydrite nanoparticles can be dispersed in water and directly injected into the subsurface to create reactive zones where contaminant biodegradation is promoted. Field applications would require a detailed knowledge of ferrihydrite transport mechanisms in the subsurface, but such studies are lacking in the literature. The present study is intended to fill this gap, focusing in particular on the influence of flow rate and ionic strength on particle mobility. Column tests were performed under constant or transient ionic strength, including injection of ferrihydrite colloidal dispersions, followed by flushing with particle-free electrolyte solutions. Particle mobility was greatly affected by the salt concentration, and particle retention was almost irreversible under typical salt content in groundwater. Experimental results indicate that, for usual ionic strength in European aquifers (2 to 5 mM), under natural flow condition ferrihydrite nanoparticles are likely to be transported for 5 to 30 m. For higher ionic strength, corresponding to contaminated aquifers, (e.g., 10 mM) the travel distance decreases to few meters. A simple relationship is proposed for the estimation of travel distance with changing flow rate and ionic strength. For future applications to aquifer remediation, ionic strength and injection rate can be used as tuning parameters to control ferrihydrite mobility in the subsurface and therefore the radius of influence during field injections.     

Major elements in milk of the West African dwarf goats as affected by stage of lactation.

Tweove adult West African dwarf (Fouta djallon) does, about 2 years old and weighing from 25 to 28 kg were kept for lactation studies lasting two 19-week periods. During these periods the does were hand-milked twice daily and the daily samples were bulked for each animal for subsequent analysis. The results showed that the colostrum was much richer in its content (g/kg) of Na 1.44 +/- 0.17, K 3.38 +/- 0.22 and Cl 4.83 +/- 0.29 than the mature milk which contained (g/kg) Na 0.65 +/- 0.09, K 1.57 +/- 0.19 and Cl 2.46 +/- 0.58. The corresponding values obtained for Ca (0.65 +/- 0.02) and P (0.36 +/- 0.10) in the colostrum were, however, lower than 2.01 +/- 0.98 and 1.18 +/- 0.28 g/kg obtained for Ca and P respectively in the mature milk. The composition of these elements in the colostrum approached that of the normal goat's milk on the sixth d after parturition. The results showed a rise in Ca, P, Na and Cl levels with stage of lactation and a fall in K content of the milk with advancing lactation with the trends being highly significant (P less than 0.01).     

Macrominerals in guinea pig milk during 21 days of lactation

Milk samples were obtained daily from English short-hair albino guinea pigs for 21 d. Analyses included six macrominerals: Ca, P, K, chloride, Na, and Mg (in order of decreasing concentration). All minerals except K gradually increased in concentration from the beginning to the end of lactation. Calcium concentration began at 38 mM on d 1 and was 78 mM on d 21. The pattern of increase was quadratic: Y (mM) = 39 -.48X (day of lactation) + .11 X2. Phosphorus concentration was 38 mM on d 1 and highest at 51 mM on d 21. Chloride was 19 mM on d 1 and 68 mM on d 21. Sodium was 13 mM on d 1 and highest at 42 mM on d 21. Magnesium was 11 mM on d 1 and was highest on d 18 (13 mM). However, K was 31 mM on d 1, reached a high of 33 mM on d 3, and was lowest on d 19 (12 mM). These changes in concentration and previously reported volume changes suggest alterations in functional capacities of ionic transport mechanisms of secretory cell membranes in this species.     

Transport and deposition of polymer-modified Fe0 nanoparticles in 2-D heterogeneous porous media: effects of particle concentration, Fe0 content, and coatings

Concentrated suspensions of polymer-modified Fe(0) nanoparticles (NZVI) are injected into heterogeneous porous media for groundwater remediation. This study evaluated the effect of porous media heterogeneity and the dispersion properties including particle concentration, Fe(0) content, and adsorbed polymer mass and layer thickness which are expected to affect the delivery and emplacement of NZVI in heterogeneous porous media in a two-dimensional (2-D) cell. Heterogeneity in hydraulic conductivity had a significant impact on the deposition of NZVI. Polymer modified NZVI followed preferential flow paths and deposited in the regions where fluid shear is insufficient to prevent NZVI agglomeration and deposition. NZVI transported in heterogeneous porous media better at low particle concentration (0.3 g/L) than at high particle concentrations (3 and 6 g/L) due to greater particle agglomeration at high concentration. High Fe(0) content decreased transport during injection due to agglomeration promoted by magnetic attraction. NZVI with a flat adsorbed polymeric layer (thickness ～30 nm) could not be transported effectively due to pore clogging and deposition near the inlet, while NZVI with a more extended adsorbed layer thickness (i.e., ～70 nm) were mobile in porous media. This study indicates the importance of characterizing porous media heterogeneity and NZVI dispersion properties as part of the design of a robust delivery strategy for NZVI in the subsurface.     

Spermatozoa motility in the Persian sturgeon, Acipenser persicus: effects of pH, dilution rate, ions and osmolality

Sperm motility is a prerequisite factor determining semen quality and fertilizing capacity. The effects of environmental factors including pH, cations and osmolality as well as the role of dilution rate on sperm motility parameters in Acipenser persicus were studied. The best pH and dilution rate for activation of spermatozoa were pH 8.0 and dilution ratio 1:50. Ionic factors can stimulate the initiation of sperm activation. The maximum percentage of motile sperm and total duration of sperm motility were observed in solutions containing 25 mM NaCl, 0.2 mM KCl, 3 mM CaSO4, 10 mM MgSO4 and sucrose with an osmolality of 50 mosmol kg(-1). The present study provides us with some basic knowledge about sturgeon spermatozoa biosensitivity to ionic and osmolality effects. A sensitivity of A. persicus sperm was observed after induction of activation of sperm motility in solution containing cations or sucrose with high osmolality. Concentrations more than 50 mM Na+, more than 1 mM K+, more than 3 mM Ca2+ and more than 10 mM Mg2+ had negative effects on sperm motility. Also, osmolality more than 100 mosmol kg(-1) had an inhibitory effect. It is clear that ions and osmolality stimulate the motility of spermatozoa by changes in the properties of the plasma membrane including its potential and its ionic conductance. The inhibitory role of high osmolality of the swimming medium (more than 100 mosmol kg(-1)) and insufficient osmolality of the seminal plasma to inhibit semen motility suggested that osmolality is not the principal factor preventing sperm motility in seminal fluid but that K+ is a major inhibitory factor of sperm motility in seminal plasma.