Behaviour of environmental aquatic nanocolloids when separated by split-flow thin-cell fractionation (SPLITT)

A split-flow thin-cell (SPLITT) system in different operating modes was used to size fractionate colloids and particles in a lake water. The unperturbed lake water sample and eluent fractions (nominally a<1 microm; b>1 microm) were analysed with atomic force microscopy (AFM) to assess the quality of the separation, in particular to quantify the contamination of the b (>1 microm) fraction with nanocolloids (defined here as material <100 nm in size). Particle size distribution (PSD) results from AFM indicated that there was substantial contamination with nanocolloids. This contamination was, most likely, from diffusive transport across flow regimes within the SPLITT and this is supported by the fact that vertical distances between laminar flow regimes within the SPLITT channel are similar in magnitude, but slightly larger than the mean distances travelled by diffusion during the residence time of particles within the channel. Nevertheless, AFM surface density data showed that the concentration of nanoparticles in the a fraction was 6-9 times higher than in the b fraction, depending on the SPLITT mode, indicating that contamination of the b fraction was limited. Fluorescence data using monodisperse, low molar mass standards confirm the AFM results, with substantial contamination of the b fraction by the fluorescent molecular probes. The increased contamination of the b fraction of the standard molecular probes compared to natural nanocolloids is likely because they are smaller and more diffusive than the average of the natural material. Due to this contamination and the likelihood that these small colloids bind a large fraction of metals, SPLITT can only be used for metal fractionation and speciation in combination with other methods capable of performing further metal speciation analysis.     

The effects of sediment size fraction and associated algal biofilms on the kinetics of phosphorus release

Experiments using flumes containing sediment of three different size fractions, from two sites on the River Tame, investigated the influences of sediment particle size, and an associated biofilm, on sediment-water exchanges in heterogeneous sediment deposits. This is the first study undertaken to understand the kinetics of the release of soluble reactive phosphorus from sediments of natural systems to identify which of the size compartments affected those fluxes most. Samples of fine material (<2 mm), gravel (2-20 mm), and stones (>20 mm) were collected over a period of several weeks and brought to a fluvarium where they were placed in artificial, controlled flow, and flume channels. Synthetic solutions of similar ionic strength to the river were prepared using calcium chloride. Temperature, pH, and dissolved oxygen of the solution overlying the sediment were monitored automatically whilst filtered samples were obtained at 2 h intervals over 48 h. The biomass, expressed as mg m(-2) chlorophyll a, of the algal component of the biofilm from the surface of the sediment was estimated using methanol extraction. Differences in the responses were observed between the sediment size fractions and the two sites, where contaminant concentrations varied. The equilibrium phosphate concentration and a phosphorus transfer index were used to establish that there was a net uptake of phosphorus by all three sediment size fractions, from both sites, at the time of sampling. The kinetic results showed very fast initial reactions of phosphorus release from the larger size fractions with a well-developed filamentous algal growth present implying a different mechanism than diffusion being involved. The stones and associated biofilms also released more phosphorus than the fine fraction, e.g. final release concentrations for the most contaminated site were: fines approximately 2.5 microM, gravel approximately 6.5 microM, and stones approximately 65.0 microM (expressed as soluble reactive phosphorus). Phosphorus fluxes, calculated assuming the concentration of phosphorus in the sediment was less than the equilibrium concentration, were a maximum at the most contaminated site, e.g. fines 6.4 nmol m(-2) s(-1), gravel 27 nmol m(-2) s(-1), and stones 109 nmol m(-2) s(-1) (normalised with respect to the river bed area). These results confirm that sediment having a biofilm and associated particulate material results in a greater flux than fine sediment, which does not support a filamentous biomass. Removal of the fine particulates trapped in the algal growth reduced soluble phosphorus release. These factors demonstrate that both gravel and stone substrates have an important control over the release of soluble reactive phosphorus.     

纳米SiO2的分散表征及其强化混凝低温低浊水研究

采用原子力显微镜、激光粒度仪对超声分散纳米SiO2的粒径分布、微观形状等进行了表征，并使用该纳米分散液对低温、低浊水进行了强化混凝研究。结果表明：纳米SiO2可均匀、稳定地分散在水溶液中，平均粒径为30nm，形状呈球形，在pH值为3～12时其表面带负电；将其用于强化混凝处理低温、低浊水时可以显著降低出水浊度，提高所形成矾花的密实程度，同时改善矾花的沉降性能。     

Characterization of isolated fractions of dissolved organic matter from natural waters and a wastewater effluent

Dissolved organic matter (DOM) was concentrated from natural waters and the effluent of a wastewater treatment plant using a portable reverse osmosis (RO) system. The humic acid (HA), fulvic acid (FA) and hydrophilic (HyI) fractions were isolated and purified by the XAD-8 resin combined with the cation exchange resin method. The FA fractions predominated in natural waters and accounted for 54-68% of the total amount of dissolved organic carbon (DOC), whereas the HA and HyI fractions constituted, respectively, 13-29 and 9-30% of the total DOC. The effluent of wastewater was almost devoid of HA and the HyI fraction exceeded FA. The elemental compositions of HA and FA were in the ranges typical for natural humic materials, but the HyI fractions did not exhibit humic character. 1H NMR spectra revealed that the HyI fractions were almost devoid of aromatic protons and the aliphatic region featured more sharp signals than HA and FA fractions, indicating that HyI fractions were consisted of more simple compounds and less complex mixtures. The aliphatic functional groups in these fractions of DOM samples followed the order HA < FA HyI. The rate of Cu complexation with the HyI fraction was faster than the rate with the HA or FA fraction of the Suwannee River DOM, implying that copper reacted with relatively weak ligands faster than with strong ligands.     

Characterization of natural organic matter fractions separated by ultrafiltration using flow field-flow fractionation

Natural organic matter (NOM) from two sites in South Australia were separated by Amicon YM and YC ultrafiltration (UF) membranes into five nominal fractions (<0.5, 0.5-3, 3-10, 10-30 and >30 kDa). These nominal fractions were then characterized for size and molecular weight (MW) distributions using flow field-flow fractionation. The results show that separation by UF did not produce fractions with the expected MW and size. Electrophoretic mobility measurements of the NOM fractions adsorbed to colloidal goethite showed no significant difference between the fractions. However solid-state (13)C NMR of the NOM fractions showed that the separation was influenced by molecular structure as well as molecular size. The results suggest that great caution needs to be exercised when interpreting molecular size and speciation results for humic substances obtained by membrane UF.     

Mercury content and speciation in the plankton and benthos of Lake Superior

As part of a study is to assess the importance of watersheds in controlling sources, transport, fate, and bioavailability of monomethyl mercury (MeHg) in Lake Superior, biotic samples were collected and analyzed to determine total mercury (HgT) and MeHg content, and to examine size, species, trophic and geographic trends. Plankton was collected in two ways: vertical tows of non-metallic, 153 microm mesh net (bulk zooplankton), and by passively filtering near-surface water through stacked Nitex sieves, generating size-fractionated seston (<35, 35-63, 63-112, and >112 microm). Benthos was sampled using a Ponar grab to collect sediment, and a non-metallic sieve to separate biota from substrate. Samples were processed to quantify dry weights, HgT and MeHg. Results for bulk zooplankton sampled offshore showed a range of approximately from 35 to 50 ng MeHg/gram dry weight (gdw) and from 80 to 130 ng HgT/gdw during April, and from 15 to 25 ng MeHg/gdw and from 20 to 70 ng HgT/gdw during August. Results from sieved, near-surface water from offshore sites in April showed a dominance by the <35 microm size fraction both in total mass and mass of MeHg compared to other size fractions. On a dry weight basis, however, we found little difference between the size fractions in April (MeHg ranges from 2 to 10 ng/gdw). During the summer cruise, we found similar concentrations in the <35 microm fraction, but higher in the 112-243 microm size fraction (MeHg 14-16 ng/gdw). The MeHg concentration in Mysis relicta ranged from 33 to 54 ng/gdw throughout the lake. Chironomid larvae were 8 ng MeHg/gdw and amphipods were 32 ng MeHg/gdw.     

Exploration of CeO₂ nanoparticles as a chemi-sensor and photo-catalyst for environmental applications

CeO₂ nanoparticles were synthesized hydrothermally and utilized as redox mediator for the fabrication of efficient ethanol chemi-sensor. The developed chemi-sensor showed an excellent performance for electrocatalytic oxidization of ethanol by exhibiting higher sensitivity (0.92 μA?cm^− 2?mM^− 1) and lower limit of detection (0.124 ± 0.010 mM) with the linear dynamic range of 0.17 mM-0.17 M. CeO₂ nanoparticles have been characterized by field emission scanning electron microscopy (FESEM), Energy dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), Raman spectrum, Fourier transform infrared spectroscopy (FTIR), and UV-visible absorption spectrum which revealed that the synthesized CeO₂ is an aggregated form of optically active spherical nanoparticles with the range of 15-36 nm (average size of ~ 25 ±10 nm) and possessing well crystalline cubic phase. Additionally, CeO₂ performed well as a photo-catalyst by degrading amido black and acridine orange.     

Size effect in reactivity of copper nanoparticles to carbon tetrachloride degradation

Surface area-normalized rate constants (k(SA)) of reaction between metallic nanoparticles and reducible contaminants, such as chlorinated hydrocarbons, heavy metals, and nitrate, have been reported to be dramatically increased as compared to that of commercial metallic powder. However, k(SA) for individual pollutants in previously published data vary by as much as 1-2 orders of magnitude and much of this variability is due to the effect of various sizes. The size dependence of the reactivity of nanoparticles is not yet fully understood; however, yielding nanoparticles with uniform size and without agglomeration during the period of reaction would demonstrate the effect of varying particle size. In this study, resin-supported zerovalent copper with average particle size of 7, 10, 18, 26, and 29, respectively, were successfully synthesized and evidenced no agglomeration during the reaction period of 10h. The k(SA) of copper nanoparticles (k(n,SA)) was 110-120 times higher than that of powdered copper particles (k(p,SA)) when the copper particle size was about 10nm. However, for diameters of 18-29 nm, the ratio of k(n,SA)/k(p,SA) was around 10-20, indicating that the reactivity of small copper nanoparticles (approximately 10nm) varies discontinuously. Thus, most variability in previous k(SA) is attributed to the presence of small nanoparticles.     

Reactivity of natural organic matter fractions with chlorine dioxide and ozone

The effects of ozone and chlorine dioxide on the aquatic natural organic matter (NOM) were studied. The natural as well as oxidised organic matter in aerated and sand filtered water were fractionated using XAD, anion-exchange, and cation-exchange resins procedure into humic acid, hydrophobic acids and neutrals, and hydrophilic acids, bases and neutrals. The main NOM components were hydrophobic, while oxidation with both ozone and chlorine dioxide increased the proportion of hydrophilic fractions. High-pressure size exclusion chromatography with UV-254 nm and UV-220 nm detection was used to determine the differences between molecular weight distribution of natural and oxidised organic matter fractions. The main purpose of this paper was to compare the reactivity of individual NOM fractions with oxidants in order to compare the productivity of biodegradable by-products after oxidation with chlorine dioxide and ozone. The quantity as well as the quality of by-products were analysed by means of ion and gas chromatography.     

In vitro evaluation of the cytotoxicity of iron oxide nanoparticles with different coatings and different sizes in A3 human T lymphocytes

The ever expanding use of engineered nanoscaled materials has brought about a commensurate growth in concern about their potential risks to human and environmental health. Toxicity of nanoparticles could vary with their physicochemical parameters. The dependence of cytotoxicity on particle size and surface coating of iron oxide nanoparticles was investigated in this in vitro study using the A3 human T lymphocyte as a model. Two different sizes (10 nm and 50 nm) and two different surface coatings (amine and carboxyl groups) of iron oxide (IO) nanoparticles were tested with fluorescein diacetate (FDA) assay and WST-1 assay. In the 1-h FDA assay with PBS, IO nanoparticles did not show size-dependent toxicity to A3 cells in terms of mass concentration; however, in terms of the number of particles per well and the total surface area, they did exhibit size-dependent toxicity. Fifty nanometer IO nanoparticles are more toxic than the 10 nm counterparts. The results of both the 24-h FDA and WST-1 assays in a complete growth medium indicate size- and surface coating-dependent toxicity to A3 cells in terms of mass concentration. IO nanoparticles of the smaller size are more toxic than those of the larger size. IO nanoparticles with the carboxyl group have a higher toxicity than those with the amine group. However, in the 24-h FDA assay, in terms of the number of particles per well and the resultant total surface area per well, the 50 nm IO nanoparticles are more toxic than those of size 10 nm. In terms of mass concentration, the number of particles per well and the total surface area, both of the 24-h assays showed the consistent results that IO nanoparticles with the carboxyl group have a higher toxicity than those with the amine group.     

The effect of natural water conditions on the anti-bacterial performance and stability of silver nanoparticles capped with different polymers

This study evaluated the effect of natural water composition onto the bactericidal and physicochemical properties of silver nanoparticles (AgNPs) stabilized with three different polymeric compounds.All the nanoparticles behaved similarly in the water conditions tested. Compared to solutions with low organic matter content and monovalent ions, lower disinfection performances of AgNPs suspensions were obtained in the following order seawater ≤ high organic matter content water ≤ high divalent cations content synthetic water. Suspension of AgNPs in seawater and water with divalent cations (Ca²⁺ and Mg²⁺) formed larger AgNPs aggregates (less than 1400 nm) compared to other solutions tested (up to approximately 38 nm). The critical coagulation concentration (CCC) of AgNPs was determined to quantitatively evaluate the stability of the nanoparticle suspension in different water conditions. When the concentration of dissolved organic matter was increased from 0 mg/L to 5 mg/L, the CCC increased by a factor in the range of 2.19 ± 0.25 for all AgNPs in divalent solutions, but a smaller increase occurred, in the range of 1.54 ± 0.21 fold, when monovalent solutions were used.The concentration of ionic silver released indicated that the dissolved Ag⁺ (3.6-48.2 ppb) was less than 0.5% of the total mass of Ag⁰ added. At all the conditions tested, the concentration of silver ions in solution had a negligible contribution to the overall anti-bacterial performance of AgNPs.This study demonstrated that the anti-bacterial performance of AgNPs at selected natural water conditions decreases in the presence of dissolved natural organic matter or divalent ions, such as humic acid and calcium carbonate. These results may be helpful in understanding the toxicity of AgNP in various natural water conditions and in explaining the risk associated with discharging AgNP in natural aquatic systems.     

Electrocatalytic characterization and dye degradation of Nano-TiO2 electrode films fabricated by CVD

A 20-40 nm anatase-titania film on a titanium electrode was fabricated using chemical vapor deposition (CVD). The film was characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and atomic force microscopy (AFM). The CVD deposition time and number of deposition coatings were evaluated to establish the appropriate film fabrication parameters. Results indicate that two coatings at a deposition time of 6 h each produced the best nano-TiO₂ electrode films (NTEFs) with an even distribution of ca. 20 nm diameter nanoparticles in the anatase lattice. The NTEF was tested as an electrocatalytic anode to investigate the degradation efficiency in treating methyl orange dye wastewater. A high removal efficiency of methyl orange dye and total organic carbon (TOC) of 97 and 56%, respectively; was achieved using a current density of 20 mA cm^− 2 for 160 min. Cyclic voltammetry showed that the electrochemical degradation reaction rate at the NTEF surface was predominately driven by molecular diffusion. The electrocatalytic decomposition rate of organic pollutants at the NTEF is controlled by mass transport, which was associated with the nanostructure of the electrocatalytic electrode.     

Application of fluorescence spectroscopy in the studies of natural organic matter fractions reactivity with chlorine dioxide and ozone

The composition of natural organic matter (NOM) fractions before and after the reaction with chlorine dioxide as well as ozone was studied by means of total luminescence spectroscopy (TLS) and synchronous scanning fluorescence measurements. The excitation-emission matrices spectra (EEMs) of natural as well as oxidised NOM fractions revealed two well-resolved bands with maxima at Ex/Em of 250-265/422-452 nm and at Ex/Em 300-336/414-446 nm ascribed to humic and fulvic material. The study of emission and synchronous spectra also confirmed the presence of protein-like constituents in all examined NOM fractions. The study of EEMs proved, that oxidation of all NOM fractions with ClO(2) caused mainly the break-up of molecules into smaller fragments and a decrease of the aromaticity. Changes in EEMs after the oxidation of individual NOM fractions with O(3) confirmed the formation of a significant amount of ozonation by-products, i.e. carboxylic acids, aldehydes and ketones during the oxidation process. In addition, the fluorescence studies confirmed relatively high reactivity of all NOM fractions with ClO(2) as well as with ozone.     

Study of pH effects on the evolution of properties of brown-water natural organic matter as revealed by size-exclusion chromatography during photocatalytic degradation

This study shows the effect of pH on the photocatalytic degradation of natural organic matter (NOM). The experiments were carried out in batch reactor (a solar UV-light simulator) with Degussa P-25 titanium dioxide (TiO₂). The NOM degradation was followed by size-exclusion chromatography for dissolved organic carbon (DOC), ultraviolet absorption and fluorescence-detection (SEC-DOC, SEC-UV₂₅₄ and SEC-Fl_254/450). Changes in pH values affected the adsorption of NOM onto TiO₂, but did not affect the photodegradation sequence of NOM. For high or low pH values, the degradation of the NOM preferentially removed the larger molecular size fraction in comparison to the middle and small molecular size fractions, resulting in the relative increase of these smaller fractions. This sequence of NOM degradation leads to the evolution of the formation potential for disinfection by-products (DBPs). Specifically, the trihalomethanes and halogenated organic compounds formation potential (THMF and AOXFP) decreased steadily.     

Characterization of natural organic matter adsorption in granular activated carbon adsorbers

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.     

Experimental investigation on heat transfer enhancement in a minichannel using CuO-water nanofluid

In this work, CuO-water nanofluid with an average size of nanoparticles (24?nm) and volume concentrations of 0.1% and 0.5% is used. For the computer microprocessor cooling, an aluminium minichannel of dimension (40?×?1?×?3) mm³ is fabricated instead of an aluminium heat sink and a cooling fan. It is shown that the dispersion of nanoparticles into the distilled water has produced a considerable enhancement of the cooling of the minichannel. Experiments were conducted for Reynolds number ranging from 25 to 800 under a laminar regime. From the experiments, it is found that better heat transfer is achieved when CuO-water nanofluid is used as the working fluid.     

Variations of nanoparticle concentrations at the Fresno Supersite

Particle size distributions from 3 nm to 2 mum were measured at the Fresno, CA, Supersite from August 25, 2002 through July 31, 2003. Nanoparticle (3-10 nm) concentrations and the ratio of nanoparticle to total particle concentration were inversely related to particle surface areas from 50 to 1000 mum(2) cm(-3). Elevated nanoparticle concentrations were associated with motor vehicle emissions and with photochemical particle production. In contrast with Atlanta, GA, where concentrations of photochemically derived nanoparticles exceeded 10(5) cm(-3), 5-min average nanoparticle concentrations in Fresno never exceeded 24,400 cm(-3). While photochemical particle production occurs in Fresno, evidence of new particle production (i.e., an increase in number concentration with decreasing size below 10 nm) was not observed. This suggests that photochemical particle production may have occurred at a higher altitude followed by mixing to the surface, or that the fresh particle production rate was smaller with respect to the loss rate by coagulation than it was in Atlanta. Lower production rates in Fresno are more consistent with lower concentrations of sulfur precurors and low relative humidity in Fresno than they are in Atlanta.     

Genotoxicity of silver nanoparticles in Allium cepa

Potential health and environmental effects of nanoparticles need to be thoroughly assessed before their widespread commercialization. Though there are few studies on cytotoxicity of nanoparticles on mammalian and human cell lines, there are hardly any reports on genotoxic and cytotoxic behavior of nanoparticles in plant cells. This study aims to investigate cytotoxic and genotoxic impacts of silver nanoparticles using root tip cells of Allium cepa as an indicator organism. A.cepa root tip cells were treated with four different concentrations (25, 20, 75, and 100 ppm) of engineered silver nanoparticles (below 100 nm size) dispersion, to study endpoints like mitotic index, distribution of cells in mitotic phases, different types of chromosomal aberrations, disturbed metaphase, sticky chromosome, cell wall disintegration, and breaks. For each concentration five sets of microscopic observations were carried out. No chromosomal aberration was observed in the control (untreated onion root tips) and the mitotic index (MI) value was 60.3%. With increasing concentration of the nanoparticles decrease in the mitotic index was noticed (60.30% to 27.62%). The different cytological effects including the chromosomal aberrations were studied in detail for the treated cells as well as control. We infer from this study that silver nanoparticles could penetrate plant system and may impair stages of cell division causing chromatin bridge, stickiness, disturbed metaphase, multiple chromosomal breaks and cell disintegration. The findings also suggest that plants as an important component of the ecosystems need to be included when evaluating the overall toxicological impact of the nanoparticles in the environment.     

Applicability of light absorbance and fluorescence as measures of concentration and molecular size of dissolved organic carbon in humic Lake Tjeukemeer

Ultrafiltration results of humic Lake Tjeukemeer water demonstrated that light absorbance at 250 nm (E250), fluorescence (λ_ex = 365 nm; λ_em = 470 nm) (F), and concentration of dissolved organic carbon (DOC) vary with the molecular size (5–200 nm) of the dissolved organic matter. The ratio of the ultrafiltered organic fractions increased with decreasing molecular size of the DOC. However, under field conditions this ratio failed to predict molecular size distribution.These results limit the applicability of E250 and F as measures of molecular size and concentration of DOC. However, E250 measurements can be made rapidly and easily, and so are useful in estimating (30%) concentrations of DOC in humic waters.     

Molecular size fractions of treated aquatic humus

The effects of ozone, chlorine, hydrogen peroxide, and permanganate on the aquatic humic matter with different molecular size fractions and the organic acid formation in drinking water treatment were studied. Aquatic humus in lake water (LW), artificially recharged groundwater (AW), and purified artificially recharged groundwater (PW) were fractionated by high-pressure size-exclusion chromatography (HP-SEC) with UV-254nm detection before and after oxidation, a technique which resulted generally in seven peaks. The sum of the molecular size fractions (SMSF) of the LW was reduced by 47% during the bank filtration process, and the SMSF of the AW was reduced by 55% during the process in the water treatment plant. The oxidation of the AW resulted in reductions in the range of 18-35% of the SMSF; the respective range of the PW was 15-69%. However, the content of the total organic carbon (TOC) reduced only slightly, and a high correlation between the TOC and the SMSF (0.911) was observed in the whole material. The greatest decreases appeared in the highest-molecular-weight fractions while the low-molecular-weight fractions remained nearly unchanged. The total content of the six organic small-molecular-weight acids (sum of the organic acids, SOA) (formate, acetate, propionate, pyruvate, oxalate, and citrate) varied between 0.1-5.1% and 0.1-9.7% of the reduced TOC in the AW and the PW, respectively. The formation of the SOA, especially of oxalate, was the greatest after hydrogen peroxide combined with ozonation (as much as 1,100 microg/L), while chlorination resulted in the SOA of < 50 microg/L.