Benefits and limitations of biochar amendment in agricultural soils: A review.

Current agriculture faces multiple challenges due to rapid increases in food demand and environmental concerns. Recently, biochar application in agricultural soils has attracted a good deal of attention. According to literature findings, biochar has proven to play various beneficial roles with respect to the enhancement of crop yield as a fertilizer and soil quality as a soil conditioner. It can further be used to remediate soil pollution as an adsorbent, while supporting the mitigation of greenhouse gases (GHGs) through the expansion of the soil carbon pool. The efficacy of biochar application on agricultural environments is found to be controlled by various factors such as pyrolysis temperature, feed stock, soil type, and biotic interactions. The combined effects of these factors may thus exert a decisive control on the overall outcome. Furthermore, the biochar application can also be proven to be detrimental in some scenarios. This review evaluates both the potential benefits and limitations of biochar application in agriculture soils.

Nanoparticle-supported lipid bilayers as an in situ remediation strategy for hydrophobic organic contaminants in soils.

Polycyclic aromatic hydrocarbons (PAHs) are persistent environmental organic contaminants due to their low water solubility and strong sorption onto organic/mineral surfaces. Here, nanoparticle-supported lipid bilayers (NP-SLBs) made of 100-nm SiO2 nanoparticles and the zwitterionic lipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) are investigated as constructs for removing PAHs from contaminated sites, using benzo[a]pyrene (BaP) as an example. DMPC in the form of small unilamellar vesicles (SUVs) or DMPC-NP-SLBs with excess DMPC-SUVs to support colloidal stability, when added to saturated BaP solutions, sorb BaP in ratios of up to 10/1 to 5/1 lipid/BaP, over a 2-week period at 33 °C. This rate increases with temperature. The presence of humic acid (HA), as an analog of soil organic matter, does not affect the BaP uptake rate by DMPC-NP-SLBs and DMPC-SUVs, indicating preferential BaP sorption into the hydrophobic lipids. HA increases the zeta potential of these nanosystems, but does not disrupt their morphology, and enhances their colloidal stability. Studies with the common soil bacteria Pseudomonas aeruginosa demonstrate viability and growth using DMPC-NP-SLBs and DMPC-SUVs, with and without BaP, as their sole carbon source. Thus, NP-SLBs may be an effective method for remediation of PAHs, where the lipids provide both the method of extraction and stability for transport to the contaminant site.

Differential impact of serotonin transporter activity on temperament and behavior in persons with a family history of alcoholism in the Oklahoma Family Health Patterns Project.

BACKGROUND: Central serotonergic (5-HT) function is implicated in pathways to alcohol dependence, including dysphoria manifested by symptoms of anxiety and depression. However, little is known about genetic variation in central 5-HT function and its potential impact on temperament and behavior in persons with a family history of alcoholism (FH+). METHODS: We tested 314 healthy young adults (23.5 years of age, 57% female; 193 FH- and 121 FH+) enrolled in the Oklahoma Family Health Patterns project, a study of alcoholism risk in relation to temperament and behavioral dyscontrol. Dysphoria was assessed using the Eysenck neuroticism and Beck depression scales, and Cloninger's Tridimensional Personality Questionnaire. Risk taking was assessed with the Iowa Gambling Task (IGT) and Balloon Analogue Response Task (BART). All subjects were genotyped for a functional polymorphism (5-HTTLPR) in the promoter region of the serotonin transporter gene (SLC6A4). RESULTS: FH+ subjects with the gain-of-function 5-HTTLPR genotype scored higher in neuroticism, harm avoidance, and symptoms of depression (p-values ≤ 0.03). No effect of 5-HTTLPR genotype was seen in FH-. FH+ carriers of the gain-of-function 5-HTTLPR genotype played to minimize their frequency of losses in the IGT, whereas FH- carriers played a balanced strategy (p < 0.003). No 5-HTTLPR effects were seen in the BART. Results were unaffected by sex, education, drug use, and antisocial characteristics. CONCLUSIONS: The functional 5-HTTLPR polymorphism predicted significant variation in negative moods and poorer affect regulation in FH+ persons, with possible consequences for behavior, as seen in a simulated gambling task. This pattern may contribute to a drinking pattern that is compensatory for such affective tendencies.

Net methylation of mercury in estuarine sediment microcosms amended with dissolved, nanoparticulate, and microparticulate mercuric sulfides.

The production of methylmercury (MeHg) by anaerobic microorganisms depends in part on the speciation and bioavailability of inorganic mercury to these organisms. Our previous work with pure cultures of methylating bacteria has demonstrated that the methylation potential of mercury decreased during the aging of mercuric sulfides (from dissolved to nanoparticulate and microcrystalline HgS). The objective of this study was to understand the relationship between mercury sulfide speciation and methylation potential in experiments that more closely simulate the complexity of sediment settings. The study involved sediment slurry microcosms that represented a spectrum of salinities in an estuary and were each amended with different forms of mercuric sulfides: dissolved Hg and sulfide, nanoparticulate HgS (3-4 nm in diameter), and microparticulate HgS (>500 nm). The results indicated that net MeHg production was influenced by both the activity of sulfate-reducing microorganisms (roughly represented by the rate of sulfate loss) and the bioavailability of mercury. In the presence of abundant sulfate and carbon sources (supporting relatively high microbial activity), net MeHg production in the slurries amended with dissolved Hg was greater than in slurries amended with nano-HgS, similar to previous experiments with pure bacterial cultures. In microcosms with minimal microbial activity (indicated by low rates of sulfate loss), the addition of either dissolved Hg or nano-HgS resulted in similar amounts of net MeHg production. For all slurries receiving micro-HgS, MeHg production did not exceed abiotic controls. In slurries amended with dissolved and nano-HgS, mercury was mainly partitioned to bulk-scale mineral particles and colloids, indicating that Hg bioavailability was not simply related to dissolved Hg concentration or speciation. Overall, the results suggest that models for mercury methylation potential in the environment will need to balance the relative contributions of mercury speciation and activity of methylating microorganisms.

Integrated approaches of x-ray absorption spectroscopic and electron microscopic techniques on zinc speciation and characterization in a final sewage sludge product.

Integration of complementary techniques can be powerful for the investigation of metal speciation and characterization in complex and heterogeneous environmental samples, such as sewage sludge products. In the present study, we combined analytical transmission electron microscopy (TEM)-based techniques with X-ray absorption spectroscopy (XAS) to identify and characterize nanocrystalline zinc sulfide (ZnS), considered to be the dominant Zn-containing phase in the final stage of sewage sludge material of a full-scale municipal wastewater treatment plant. We also developed sample preparation procedures to preserve the organic and sulfur-rich nature of sewage sludge matrices for microscopic and spectroscopic analyses. Analytical TEM results indicate individual ZnS nanocrystals to be in the size range of 2.5 to 7.5 nm in diameter, forming aggregates of a few hundred nanometers. Observed lattice spacings match sphalerite. The ratio of S to Zn for the ZnS nanocrystals is estimated to be 1.4, suggesting that S is present in excess. The XAS results on the Zn speciation in the bulk sludge material also support the TEM observation that approximately 80% of the total Zn has the local structure of a 3-nm ZnS nanoparticle reference material. Because sewage sludge is frequently used as a soil amendment on agricultural lands, future studies that investigate the oxidative dissolution rate of ZnS nanoparticles as a function of size and aggregation state and the change of Zn speciation during post sludge-processing and soil residency are warranted to help determine the bioavailability of sludge-born Zn in the soil environment.

Methylation of mercury by bacteria exposed to dissolved, nanoparticulate, and microparticulate mercuric sulfides.

The production of the neurotoxic methylmercury in the environment is partly controlled by the bioavailability of inorganic divalent mercury (Hg(II)) to anaerobic bacteria that methylate Hg(II). In sediment porewater, Hg(II) associates with sulfides and natural organic matter to form chemical species that include organic-coated mercury sulfide nanoparticles as reaction intermediates of heterogeneous mineral precipitation. Here, we exposed two strains of sulfate-reducing bacteria to three forms of inorganic mercury: dissolved Hg and sulfide, nanoparticulate HgS, and microparticulate HgS. The bacteria cultures exposed to HgS nanoparticles methylated mercury at a rate slower than cultures exposed to dissolved forms of mercury. However, net methylmercury production in cultures exposed to nanoparticles was 6 times greater than in cultures treated with microscale particles, even when normalized to specific surface area. Furthermore, the methylation potential of HgS nanoparticles decreased with storage time of the nanoparticles in their original stock solution. In bacteria cultures amended with nano-HgS from a 16 h-old nanoparticle stock, 6-10% of total mercury was converted to methylmercury after one day. In contrast, 2-4% was methylated in cultures amended with nano-HgS that was aged for 3 days or 1 week. The methylation of mercury derived from nanoparticles (in contrast to the larger particles) would not be predicted by equilibrium speciation of mercury in the aqueous phase (<0.2 µm) and was possibly caused by the disordered structure of nanoparticles that facilitated release of chemically labile mercury species immediately adjacent to cell surfaces. Our results add new dimensions to the mechanistic understanding of mercury methylation potential by demonstrating that bioavailability is related to the geochemical intermediates of rate-limited mercury sulfide precipitation reactions. These findings could help explain observations that the "aging" of mercury in sediments reduces its methylation potential and provide a basis for assessing and remediating methylmercury hotspots in the environment.

Characterization and environmental implications of nano- and larger TiO(2) particles in sewage sludge, and soils amended with sewage sludge.

Titanium dioxide (TiO(2)) is the most extensively used engineered nanoparticle to date, yet its fate in the soil environment has been investigated only rarely and is poorly understood. In the present study, we conducted two field-scale investigations to better describe TiO(2) nano- and larger particles in their most likely route of entry into the environment, i.e., the application of biosolids to soils. We particularly concentrated on the particles in the nano-size regime due to their novel and commercially useful properties. First, we analyzed three sewage sludge products from the US EPA TNSSS sampling inventory for the occurrence, qualitative abundance, and nature of TiO(2) nano- and larger particles by using analytical scanning electron microscopy and analytical (scanning) transmission electron microscopy. Nano- and larger particles of TiO(2) were repeatedly identified across the sewage sludge types tested, providing strong evidence of their likely concentration in sewage sludge products. The TiO(2) particles identified were as small as 40 nm, and as large as 300 nm, having faceted shapes with the rutile crystal structure, and they typically formed small, loosely packed aggregates. Second, we examined surface soils in mesocosms that had been amended with Ag nanoparticle-spiked biosolids for the occurrence of TiO(2) particles. An aggregate of TiO(2) nanoparticles with the rutile structure was again identified, but this time TiO(2) nanoparticles were found to contain Ag on their surfaces. This suggests that TiO(2) nanoparticles from biosolids can interact with toxic trace metals that would then enter the environment as a soil amendment. Therefore, the long-term behavior of TiO(2) nano- and larger particles in sewage sludge materials as well as their impacts in the soil environment need to be carefully considered.

Discovery and characterization of silver sulfide nanoparticles in final sewage sludge products.

Nanosized silver sulfide (α-Ag(2)S) particles were identified in the final stage sewage sludge materials of a full-scale municipal wastewater treatment plant using analytical high-resolution transmission electron microscopy. The Ag(2)S nanocrystals are in the size range of 5-20 nm with ellipsoidal shape, and they form very small, loosely packed aggregates. Some of the Ag(2)S nanoparticles (NPs) have excess S on the surface of the sulfide minerals under S-rich environments, resulting in a ratio of Ag to S close to 1. Considering the current extensive production of Ag NPs and their widespread use in consumer products, it is likely that they are entering wastewater streams and the treatment facilities that process this water. This study suggests that in a reduced, S-rich environment, such as the sedimentation processes during wastewater treatment, nanosized silver sulfides are being formed. This field-scale study provides for the first time nanoparticle-level information of the Ag(2)S present in sewage sludge products, and further suggests the role of wastewater treatment processes on transformation of Ag nanoparticles and ionic Ag potentially released from them.

Photocrosslinked DNA nanospheres for drug delivery.

DNA has been employed as both a genetic and a generic material. X-shaped DNA (X-DNA) in particular has four branched arms, providing multivalent functionalities that can allow for simultaneous multiple crosslinking. Here we report the synthesis of four acrylate-functionalized X-DNA monomers that can be further photocrosslinked to form monodisperse and tunable DNA nanospheres. In particular, the size and surface charge of these nanospheres were precisely controlled in a linear fashion, simply by tuning the monomer concentration in the reaction. The morphology and surface properties of the nanospheres were characterized using FT-IR, HPLC, TEM, AFM, zeta potential, and DLS analysis. In vitro studies in mammalian cells revealed that these DNA nanospheres demonstrated significant efficacy in the delivery of doxorubicin. These results highlight the potential of using DNA as material building blocks to design novel nanocarriers with properties tailored for the delivery of drugs in general and DNA/RNA in particular.

Effects, uptake, and translocation of aluminum oxide nanoparticles in lettuce: A comparison study to phytotoxic aluminum ions.

The widespread use of aluminum oxide nanoparticles (Al2O3 NPs) unavoidably causes the release of NPs into the environment, potentially having unforeseen consequences for biological processes. Due to the well-known issue of Al phytoxicity, plant interactions with Al2O3 NPs are cause for concern, but these interactions remain poorly understood. This study investigated the effects of Al2O3 NPs on lettuce (Lactuca sativa L.) to elucidate the similarities and differences in plant growth responses when compared to those of Al ions. Seed germination, root length, biomass production, and uptake of Al and nutrients were measured from hydroponically-grown lettuce with varying concentrations of Al2O3 NPs (0, 0.4, 1, and 2 mg/mL) or AlCl3 (0, 0.04, 0.4, and 1 mg/mL). The Al2O3 NPs treatments had a positive influence on root elongation, whereas AlCl3 significantly reduced emerging root lengths. While 0.4 mg/mL Al2O3 NPs promoted biomass, 1 and 2 mg/mL showed a 10.4% and 17.9% decrease in biomass, respectively, when compared to the control. Similarly, 0.4 and 1 mg/mL AlCl3 reduced biomass to 22.3% and 9.96%, respectively. Both treatments increased Al uptake by roots linearly; however, translocation of Al2O3 NPs into shoots was limited, whereas translocation of AlCl3 increased with increasing treatment concentration. Further, Al2O3 NPs adsorbed on the roots serve as adsorbents for macronutrients, promoting their absorption and uptake in plants, but not micronutrients. Calcium uptake was the most inhibited by AlCl3. A new in vivo imaging technique, with elemental analysis, confirmed that Al2O3 NPs were assimilated as particles, not ions, suggesting that the observed phytotoxicity is not due to Al ions being released from the NPs. Thus, it is concluded that Al2O3 NPs pose less phytoxicity than AlCl3, primarily due to NPs role on stimulated root growth, significant adsorption/aggregation on roots, limited lateral translocation to shoots, and increased uptake of macronutrients.

Phytotoxic effects of Cu and Zn on soybeans grown in field-aged soils: their additive and interactive actions.

A field pot experiment was conducted to investigate the interactive phytotoxicity of soil Cu and Zn on soybean plants [Glycine max (L.) Merr.]. Two soils (Arkport sandy loam [coarse-loamy, mixed, active, mesic Lamellic Hapludalf] and Hudson silty clay loam [fine, illitic, mesic Glossaquic Hapludalf]) spiked with Cu, Zn, and combinations of both to reach the final soil metal range of 0 to 400 mg kg(-1) were tested in a 2-yr bioassay after 1 yr of soil-metal equilibration in the field. The soluble and easily-extractable fraction of soil Zn (or Cu), estimated by dilute CaCl2, increased linearly in response to the total Zn (or Cu) added. This linearity was, however, strongly affected where soils were treated with both metals in combination, most notably for Zn, as approximately 50% more of soil Zn was extracted into solution when the Cu level was high. Consequently, added Zn is less likely to be stabilized by aging than added Cu when both metals are present in field soils. The predictive model relating soil metal extractability to plant Zn concentration also revealed a significant Cu-Zn interaction. By contrast, the interaction between the two metals contributed little to explain plant Cu uptake. The additive action of soil Cu and Zn was of considerable importance in explaining plant biomass reduction. This work clearly demonstrates the critical roles of the properties of the soil, the nature of the metal, and the level of other toxic metals present on the development of differential phytotoxicity due to soil Cu and Zn.

Urease activity in aged copper and zinc-spiked soils: relationship to CaCl2-extractable metals and Cu2+ activity.

In the present study, the utilization of dilute CaCl2 extraction and free metal ion activity was tested for its ability to predict urease activity in soils that was measured by a simple and rapid urease assay. Two soil series (an Arkport sandy loam and a Hudson silty clay loam) were spiked with Cu and Zn, both singly and in combination, and then field aged for over a year prior to use. For both the metal-spiked Arkport and Hudson soils, much of the inhibition in measured urease activity was explained by increased CaCl2-extractable Cu, with a lesser effect from increased Zn extractability. A positive but weak interaction between Cu and Zn suggested by regression analysis indicates the toxicity of Cu-Zn mixtures to soil urease is slightly less than additive (antagonistic). Copper extractability using CaCl2 was able to predict urease activity in only one of the tested soils. By contrast, measurements of Cu2+ activity were predictive of reduced urease activity in both soils (R2adj = 0.726, p < 0.0001), indicating that Cu2+ activity is a more useful predictor of urease inhibition in soils than CaCl2-extractable Cu. The present study also highlighted the importance that clay mineral content had on controlling the availability of added metals in soils over time since a greater aging effect on Cu toxicity was found for the fine-textured Hudson than the coarse-textured Arkport soil.

Finding the conditions for the beneficial use of ZnO nanoparticles towards plants-A review.

Zinc oxide nanoparticles (ZnO NPs) have a wide range of applications in cosmetics, electrical, and optical industries. The wide range of applications of ZnO NPs, especially in personal care products, suggest they can reach major environmental matrices causing unforeseen effects. Recent literature has shown conflicting findings regarding the beneficial or detrimental effects of ZnO NPs towards terrestrial biota. In this review we carried out a comprehensive survey about beneficial, as well as detrimental aspects, of the ZnO NPs exposure toward various terrestrial plants. A careful scrutiny of the literature indicates that at low concentrations (about 50 mg/kg), ZnO NPs have beneficial effects on plants. Conversely, at concentrations above 500 mg/kg they may have detrimental effects, unless there is a deficiency of Zn in the growing medium. This review also remarks the critical role of the biotic and abiotic factors that may elevate or ameliorate the impact of ZnO NPs in terrestrial plants.

A test of sequential extractions for determining metal speciation in sewage sludge-amended soils.

Sequential extraction procedures are widely used to estimate the quantity of trace metals bound to different solid fractions in contaminated soils. However, reliability of speciation of trace metals by these procedures remains largely unexamined. In the present study, the selectivity of each extraction step was tested by observing the effect of reversing the extraction order in the procedure. Two different sequential extraction methods and their reversed modes were used for metal fractionation in sewage sludge-amended soils. Significantly increased amounts of extractable metals (Cd, Cu, Pb and Zn) were evident in the sludge-amended soils compared to control soil by all extraction schemes; however, the amounts of metals extracted by each step were strongly dependent on the order of extraction, the type of reagents and the nature of the individual metals. Caution is advised in deducing the forms of soil metals from sequential extraction results from metal-contaminated soils.

Aggregation and Colloidal Stability of Commercially Available Al2O3 Nanoparticles in Aqueous Environments.

The aggregation and colloidal stability of three, commercially-available, gamma-aluminum oxide nanoparticles (γ-Al2O3 NPs) (nominally 5, 10, and 20-30 nm) were systematically examined as a function of pH, ionic strength, humic acid (HA) or clay minerals (e.g., montmorillonite) concentration using dynamic light scattering and transmission electron microscopy techniques. NPs possess pH-dependent surface charges, with a point of zero charge (PZC) of pH 7.5 to 8. When pH < PZC, γ-Al2O3 NPs are colloidally stable up to 100 mM NaCl and 30 mM CaCl2. However, significant aggregation of NPs is pronounced in both electrolytes at high ionic strength. In mixed systems, both HA and montmorillonite enhance NP colloidal stability through electrostatic interactions and steric hindrance when pH ≤ PZC, whereas their surface interactions are quite limited when pH > PZC. Even when pH approximates PZC, NPs became stable at a HA concentration of 1 mg·L-1. The magnitude of interactions and dominant sites of interaction (basal planes versus edge sites) are significantly dependent on pH because both NPs and montmorillonite have pH-dependent (conditional) surface charges. Thus, solution pH, ionic strength, and the presence of natural colloids greatly modify the surface conditions of commercial γ-Al2O3 NPs, affecting aggregation and colloidal stability significantly in the aqueous environment.

Antimicrobial nanotechnology: its potential for the effective management of microbial drug resistance and implications for research needs in microbial nanotoxicology.

The development of antibiotics revolutionized human health, providing a simple cure for once dreaded diseases such as tuberculosis. However, widespread production, use, and mis-use of antibiotics have contributed to the next-generation concern for global public health: the emergence of multiple drug-resistant (MDR) infectious organisms (a.k.a. "superbugs"). Recently, nanotechnology, specifically the use of nanomaterials (NMs) with antimicrobial activity, has been presented as a new defense against MDR infectious organisms. We discuss the potential for NMs to either circumvent microbial resistance or induce its development in light of our current state of knowledge, finding that this question points to a need for fundamental research targeting the molecular mechanisms causing antimicrobial activity in NMs. In the context of current microbial nanotoxicology studies, particularly reductionist laboratory studies, we offer suggestions and considerations for future research, using an illustrative example from our work with silver nanoparticles.

Low concentrations of silver nanoparticles in biosolids cause adverse ecosystem responses under realistic field scenario.

A large fraction of engineered nanomaterials in consumer and commercial products will reach natural ecosystems. To date, research on the biological impacts of environmental nanomaterial exposures has largely focused on high-concentration exposures in mechanistic lab studies with single strains of model organisms. These results are difficult to extrapolate to ecosystems, where exposures will likely be at low-concentrations and which are inhabited by a diversity of organisms. Here we show adverse responses of plants and microorganisms in a replicated long-term terrestrial mesocosm field experiment following a single low dose of silver nanoparticles (0.14 mg Ag kg(-1) soil) applied via a likely route of exposure, sewage biosolid application. While total aboveground plant biomass did not differ between treatments receiving biosolids, one plant species, Microstegium vimeneum, had 32 % less biomass in the Slurry+AgNP treatment relative to the Slurry only treatment. Microorganisms were also affected by AgNP treatment, which gave a significantly different community composition of bacteria in the Slurry+AgNPs as opposed to the Slurry treatment one day after addition as analyzed by T-RFLP analysis of 16S-rRNA genes. After eight days, N2O flux was 4.5 fold higher in the Slurry+AgNPs treatment than the Slurry treatment. After fifty days, community composition and N2O flux of the Slurry+AgNPs treatment converged with the Slurry. However, the soil microbial extracellular enzymes leucine amino peptidase and phosphatase had 52 and 27% lower activities, respectively, while microbial biomass was 35% lower than the Slurry. We also show that the magnitude of these responses was in all cases as large as or larger than the positive control, AgNO3, added at 4-fold the Ag concentration of the silver nanoparticles.

Effect of soil metal contamination on glyphosate mineralization: role of zinc in the mineralization rates of two copper-spiked mineral soils.

A systematic investigation into lowered degradation rates of glyphosate in metal-contaminated soils was performed by measuring mineralization of [(14)C]glyphosate to (14)CO(2) in two mineral soils that had been spiked with Cu and/or Zn at various loadings. Cumulative (14)CO(2) release was estimated to be approximately 6% or less of the amount of [(14)C]glyphosate originally added in both soils over an 80-d incubation. For all but the highest Cu treatments (400 mg kg(-1)) in the coarse-textured Arkport soil, mineralization began without a lag phase and declined over time. No inhibition of mineralization was observed for Zn up to 400 mg kg(-1) in either soil, suggesting differential sensitivity of glyphosate mineralization to the types of metal and soil. Interestingly, Zn appeared to alleviate high-Cu inhibition of mineralization in the Arkport soil. The protective role of Zn against Cu toxicity was also observed in the pure culture study with Pseudomonas aeruginosa, suggesting that increased mineralization rates in high Cu soil with Zn additions might have been due to alleviation of cellular toxicity by Zn rather than a mineralization specific mechanism. Extensive use of glyphosate combined with its reduced degradation in Cu-contaminated, coarse-textured soils may increase glyphosate persistence in soil and consequently facilitate Cu and glyphosate mobilization in the soil environment.

Influence of ionic strength, pH, and cation valence on aggregation kinetics of titanium dioxide nanoparticles.

The extensive use of titanium dioxide nanoparticles (nano-TiO2) in many consumer products has raised concerns about possible risks to the environment The magnitude of the threat may depend on whether nano-TiO2 remains dispersed in the environment, or forms much larger-sized aggregates or clusters. Currently, limited information is available on the issue. In this context, the purpose of the present article is to report initial measurements of the morphology and rate of formation of nano-TiO2 aggregates in aqueous suspensions as a function of ionic strength and of the nature of the electrolyte in a moderately acid to circumneutral pH range typical of soil and surface water conditions. Dynamic light scattering results show that 4-5 nm titanium dioxide particles readily form stable aggregates with an average diameter of 50-60 nm at pH approximately 4.5 in a NaCl suspension adjusted to an ionic strength of 0.0045 M. Holding the pH constant but increasing the ionic strength to 0.0165 M, leads to the formation of micron-sized aggregates within 15 min. At all other pH values tested (5.8-8.2), micron-sized aggregates form in less than 5 min (minimum detection time), even at low ionic strength (0.0084-0.0099 M with NaCl). In contrast, micron-sized aggregates form within 5 min in an aqueous suspension of CaCl2 at an ionic strength of 0.0128 M and pH of 4.8, which is significantly faster than observed for NaCI suspensions with similar ionic strength and pH. This result indicates that divalent cations may enhance aggregation of nano-TiO2 in soils and surface waters. Optical micrographs show branching aggregates of sizes ranging from the 1 microm optical limit of the microscope to tens of micrometers in diameter.

Large-volume stacking in capillary electrophoresis using a methanol run buffer.

Highly sensitive nonaqueous capillary electrophoresis of weakly acidic organic compounds has been performed using methanol as the run buffer solvent. Methanol provided appropriate suppression of the electroosmotic flow and an increase in the electrophoretic mobilities of anionic solutes compared to water. These two effects allowed large-volume stacking using the electroosmotic flow pump (LVSEP) to be achieved for larger anions using a bare fused-silica capillary under an electric field of reverse polarity, whereas only fast-moving small anions were previously known to be suitable for LVSEP in aqueous media. A field-enhanced sample injection of an additional amount of analytes during the solvent plug removal further enhanced the limits of detection to below the nanomolar range with conventional UV absorption detection. Under optimum conditions, excellent linear responses and reproducibility in the migration times together with the corrected peak areas for ten analytes were obtained in the concentration range of 10-100 nM.