Facile synthesis of graphene-based hyper-cross-linked porous carbon composite with superior adsorption capability for chlorophenols.

In this work, we proposed a green and cost-effective method to prepare a graphene-based hyper-cross-linked porous carbon composite (GN/HCPC) by one-pot carbonization of hyper-cross-linked polymer (HCP) and glucose. The composite combined the advantages of graphene (GN) and hyper-cross-linked porous carbon (HCPC), leading to high specific surface area (396.93 m2/g) and large total pore volume (0.413 cm3/g). The resulting GN/HCPC composite was applied as an adsorbent to remove 2,4-dichlorophenol (2,4-DCP) from aqueous solutions. The influence of different solution conditions including pH, ionic strength, contact time, system temperature and concentration of humic acid was determined. The maximum adsorption capacity of GN/HCPC composite (calculated by the Langmuir model) could reach 348.43 mg/g, which represented increases of 43.6% and 13.6% over those of the as-prepared pure GN and HCPC, respectively. The Langmuir model and pseudo-second-order kinetic model were found to fit well with the adsorption process. Thermodynamic experiments suggested that the adsorption proceeded spontaneously and endothermically. In addition, the GN/HCPC composite showed high adsorption performance toward other organic contaminants including tetracycline, bisphenol A and phenol. Measurement of the adsorption capability of GN/HCPC in secondary effluent revealed a slight decrease over that in pure water solution. This study demonstrated that the GN/HCPC composite can be utilized as a practical and efficient adsorbent for the removal of organic contaminants in wastewater.

Simultaneous separation and determination of thallium in water samples by high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

An analytical method for separation and determination of thallium species in water using high-performance liquid chromatography with inductively coupled plasma mass spectrometry was developed. The composition and concentration of mobile phase, injection volume, and pH value were optimized respectively with an anion or cation exchange column. The results showed that Tl(I) and Tl(III) were effectively separated using anion exchange column Hamilton PRP-X100, with the mobile phase consisting of 200 mmol/L ammonium acetate and 10 mmol/L diethylenetriaminepentaacetic acid (pH = 4.2). When using a Dionex cation exchange guard column, CS12A, 15 mmol/L HNO3 , and 3 mmol/L diethylenetriaminepentaacetic acid as the mobile phase, Tl(I) and Tl(III) could be effectively separated. The detection limits of the methods were 3-6 and 9-12 ng/L, respectively. In a solution containing Fe ions and oxalic acid, a significant quantity of Tl(I) was oxidized. Fe ions and oxalic acid in the water samples did not interfere with high-performance liquid chromatography-inductively coupled plasma mass spectrometry measurement results.

[Influence of the Coagulation Mechanism on the Coagulation Performances Using New Composite Coagulants: Role of the Raw Water Characteristics].

To improve the coagulation performances, new composite coagulants were used to treat different water samples. The results indicate that Ca2+ has no significant effects on the removal efficiency for turbidity in the kaolin system. The residual aluminum decreased from 0.15 mg·L-1 to 0.10 mg·L-1 (AlCl3 was used as coagulant and the coagulant dosage was 0.10 mmol·L-1). The presence of Ca2+ led to the decrease of the amount of negative charges in the HA system and the residual aluminum decreased due to the decrease of the complexation between the HA molecules and Al-based coagulants. When the raw water contained BSA molecules and the coagulant dosage was 0.16 mmol·L-1, the flocs formed by PACl with Ca2+ were larger (~50 µm) than the flocs generated by PACl and the settleability also improved. Under alkaline conditions (pH=8.5), the DOC concentration decreased after coagulation process by~0.2-0.6 mg·L-1 and the residual aluminum decreased by~0.4-0.7 mg·L-1 using composite coagulants. Under acidic conditions (pH=5.5), the concentrations of DOC and residual aluminum did not significantly differ.

Relationship between heavy metals and dissolved organic matter released from sediment by bioturbation/bioirrigation.

Organic matter (OM) is an important component of sediment. Bioturbation/bioirrigation can remobilize OM and heavy metals that were previously buried in the sediment. The remobilization of buried organic matter, thallium (Tl), cadmium (Cd), copper (Cu) and zinc (Zn) from sediment was studied in a laboratory experiment with three organisms: tubificid, chironomid larvae and loach. Results showed that bioturbation/bioirrigation promoted the release of dissolved organic matter (DOM) and dissolved Tl, Cd, Cu and Zn, but only dissolved Zn concentrations decreased with exposure time in overlying water. The presence of organisms altered the compositions of DOM released from sediment, considerably increasing the percentage of fulvic acid-like materials (FA) and humic acid-like materials (HA). In addition, bioturbation/bioirrigation accelerated the growth and reproduction of bacteria to enhance the proportion of soluble microbial byproduct-like materials (SMP). The DOM was divided into five regions in the three-dimensional excitation emission matrix (3D-EEM), and each part had different correlation with the dissolved heavy metal concentrations. Dissolved Cu had the best correlation with each of the DOM compositions, indicating that Cu in the sediment was in the organic-bound form. Furthermore, the organism type and heavy metal characteristics both played a role in influencing the remobilization of heavy metal.

Effect of single-wall carbon nanotubes on bioconcentration and toxicity of perfluorooctane sulfonate in zebrafish (Danio rerio).

The wide application of nanoparticles will lead its release into the aquatic environment, which may alter the bioavailability and toxicity of other contaminants to aquatic organisms. This work aimed to study the effects of perfluorooctane sulfonate (PFOS), single-wall carbon nanotubes (SWCNT), and their mixture on PFOS accumulation, antioxidant defenses and acetylcholinesterase (AChE) activity in zebrafish. The fish was dissected after being exposed (24, 48, 72 and 96h) separately to PFOS, SWCNT and PFOS+SWCNT co-exposure. The bioaccumulation of PFOS in fish tissues (liver, intestines, gills and brain) decreased with increasing dosage of SWCNT, however, the opposite trend was observed in fish skin, which indicated that the bioavailability of PFOS changed by adsorption on SWCNT. Meanwhile, co-exposure induced more reactive oxygen species (ROS) than PFOS alone and enhanced the effect of PFOS on the superoxide dismutase (SOD), and catalase (CAT) and AChE activities. Furthermore, the integrated biomarker response (IBR) showed that co-exposure was the most stressful circumstance.

Investigation of heavy metals release from sediment with bioturbation/bioirrigation.

Bioturbation/bioirrigation can affect the remobilization of metals from sediments. In this study, experiments were performed to examine the effect of bioturbation/bioirrigation by different organisms on cadmium (Cd), copper (Cu), zinc (Zn) and lead (Pb) releasing from the spiked sediment. The diffusive gradient in thin films technique (DGT) revealed that at the end of exposure time, the labile heavy metals concentrations in the pore water for all metal and organisms combinations except Cu and chironomid larvae were much lower than that in the control group. However, the concentrations of heavy metals detected by the DGT were virtually indistinguishable among the treatments with tubificid, chironomid larvae and loach. The correlation analysis of heavy metals with iron (Fe) and manganese (Mn) suggested that Cd, Zn and Pb were most likely bound as Fe-Mn oxidation form in the pore water, but Cu was in other forms. After 28 d of exposure, bioturbation/bioirrigation produced a significant release of particulate heavy metals into the overlying water, especially in the treatment with loach. The bioturbation/bioirrigation impact on the Pb remobilization was less than the other three heavy metals. The effects of bioturbaiton/bioirrigation on the heavy metals remobilization in the sediment were complex that with studying the heavy metals remobilization in the sediment and water interface, the biological indicators should be recommended.

On-line batch production of ferrate with an chemical method and its potential application for greywater recycling with Al(III) salt.

Ferrate(VI) salt is an oxidant and coagulant for water and wastewater treatment. It is considered as a possible alternative method in greywater treatment. However, challenges have existed in putting ferrate(VI) technology into full-scale practice in water and wastewater treatment due to the instability of ferrate solution and high production cost of solid ferrate products. This study demonstrated a new approach of greywater treatment with on-line batch production of Fe(VI) to which Fe(III) salt was oxidized at a weak acidity solution. A series of experiments were conducted to investigate the effect of Fe(VI) on light greywater (total organic carbon (TOC)=19.5mg/L) and dark greywater (TOC=55mg/L) treatment under different conditions with varying pH and Fe(VI) doses. In addition, the combination use of Fe(VI) and Al(III) salts was proved to be more efficient than using the Fe(VI) salts alone at greywater recycling. The optimum dosage of Fe(VI)/Al(III) salts was 25/25mg/L for light greywater, 90/60mg/L for dark greywater, respectively. The TOC values of both light greywater and dark greywater were reduced to less than 3mg/L with the dosages. The cost for treating greywater was 0.06-0.2$/ton at ferrate(VI) dosage of 25-90mg/L and 0.008-0.024$/ton at AlCl3 dosage of 25-60mg/L. The full operating cost needs further assessment before the Fe(VI)/Al(III) technology could be implemented in greywater treatment.

[Effects of Algal Morphology and Al Species Distribution on the Coagulation-Ultrafiltration Process].

In order to ensure drinking water quality, three different Al-based coagulants [Al2(SO4)3(AS), Al13, Al30] were used to treat water laden with different algae [Microcystis aeruginosa(cyanobacteria), Chlorella(green algae), Cyclotella (diatoms)]. Floc size, strength factor, and recovery factor under different conditions were measured to investigate the mechanisms in the coagulation-ultrafiltration process. The results indicated that the main mechanism in the coagulation process using Al13 or Al30 as coagulants was electrostatic patching and the main mechanism using AS was charge neutralization. In the Microcystis aeruginosa and Chlorella systems, when Al13 and Al30 were used as coagulants at low dosage, the coagulants that were adsorbed on the side (which existed on the surfaces of Microcystis aeruginosa and Chlorella cells) would lose their ability to aggregate the algal cells. When AS was used as coagulant, the electric double layer was effectively compressed. The repulsive force between algal particles decreased, and the flocs formed easily. In the Cyclotella system, Al13 and Al30coagulants effectively formed the flocs through electrostatic patch effects. There was a significant correlation between membrane flux and floc size, and the larger flocs formed a looser cake layer on the membrane surface.

Bioturbation effects on heavy metals fluxes from sediment treated with activated carbon.

Adding activated carbon (AC) to sediment has been proposed as an in situ sediment remediation technique. To date, it is not clear whether this technique is effective in the treatment of heavy metal-contaminated sediment in the presence of bioturbators. In the present study, we compare the ability of granular-activated carbon (GAC) and powder-activated carbon (PAC) to reduce Cu, Zn, and Pb pore water concentrations at environmentally relevant concentrations in the absence and presence of Chironomid larvae. Compared to untreated sediment, PAC and GAC addition in the absence of Chironomid larvae resulted in reductions of free Cu concentrations of 78 and 66 % just below the sediment-water interface after 28 days, respectively. While for Pb and Zn these concentration reductions were only 40 and 38, 19 and 25 %, respectively. The presence of Chironomid larvae in untreated, and GAC sediment generally increased the free heavy metals concentrations in pore water, especially in the deeper layers. In comparison with untreated sediment, the coexistence of AC enhanced the accumulation of heavy metals, especially for PAC. This increased bioaccumulation may decrease the survival of Chironomid larvae. The result indicated that ACs may not be suitable for the remediation of heavy metal-contaminated sediments.

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review.

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals (OH) from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH. Hence, it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology. Due to the complex reaction system, the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating, and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies. Iron-based materials usually possess high catalytic activity, low cost, negligible toxicity and easy recovery, and are a superior type of heterogeneous Fenton catalysts. Therefore, this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials. OH, hydroperoxyl radicals/superoxide anions (HO2/O2(-)) and high-valent iron are the three main types of reactive oxygen species (ROS), with different oxidation reactivity and selectivity. Based on the mechanisms of ROS generation, the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron, the heterogeneous catalysis mechanism, and the heterogeneous reaction-induced homogeneous mechanism. Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed. Finally, related future research directions are also suggested.

Application of nitrate to enhance biodegradation of gasoline components in soil by indigenous microorganisms under anoxic condition.

Anaerobic/anoxic biodegradation of hydrocarbons offers an attractive approach to the removal of these compounds from polluted environments such as aquifers, aquatic sediments, submerged soils and subsurface soils. The application of nitrate was investigated to accelerate the degradation of gasoline components such as mono-aromatic hydrocarbons and total petroleum hydrocarbons (TPH) in soil by indigenous microorganisms under anoxic condition. The addition of nitrate had little effect on the degradation of mono-aromatic hydrocarbons m- & p-xylene, o-xylene, sec-butylbenzene and 1,2,4-trimethylbenzene, but facilitated the degradation of TPH (C6-C12) and mono-aromatic hydrocarbons toluene and ethylbenzene markedly. Furthermore, the more nitrate added, the higher the percentage of toluene, ethylbenzene and TPH (C6-C12) degraded after 180 days of anoxic incubation. Microorganisms capable of degrading toluene, ethylbenzene and TPH (C6-C12) with nitrate as the electron acceptor under anaerobic/anoxic condition are composed predominantly of Alpha-, Beta-, Gamma- or Delta-proteobacteria. Beta- and Gamma-proteobacteria were the main components of indigenous microorganisms, and accounted for 83-100% of the total amount of indigenous microorganisms in soil used in this study. Furthermore, the total amount of indigenous microorganisms increased with nitrate added. The addition of nitrate stimulated the growth of indigenous microorganisms, and therefore facilitated the degradation of toluene, ethylbenzene and TPH (C6-C12).

Bioturbation/bioirrigation effect on thallium released from reservoir sediment by different organism types.

Bioturbation can remobilize heavy metal in the sediments and may pose a risk for aquatic biota. The effects of bioturbation/bioirrigation by three different riverine organism types (Tubificid, Chironomid larvae, and Loach) on thallium release from contaminated sediment (10.0 ± 1.1 mg Tl/kg sediment, dry wt.) were evaluated in this study. The bioturbation by the epibenthos clearly caused an increased turbidity in the overlying water, and the effect was in the order of Loach > Chironomid larvae > Tubificid. A significant release of Tl into the water column via the resuspended sediment particles was observed, especially for Loach. During the first few days, the leaching of dissolved Tl from sediment into water was fast, and the dissolved Tl under bioturbation/bioirrigation was much higher than the control group. However, after 14 days, the bioturbation/bioirrigation process seemed to suppress the release of Tl from the sediment particles to water, especially for sediment with Loach. This may partly be due to the sorption or coprecipitation of Tl simultaneous with the formation of iron and manganese hydrous oxides with increased pH values as a consequence of phytoplankton growth. Linear regression analysis confirmed that both the total and particulate Tl concentrations had good correlations with particulate Fe and Mn concentrations as well as turbidity in the overlying water. Additionally, planktonic bacteria may oxidize the Tl(I) to Tl(III), resulting in a reduced solubility of Tl by which Tl(OH)3 becomes the predominant form of Tl.

Distributions of polychlorinated biphenyls in the Daliao River estuary of Liaodong Bay, Bohai Sea (China).

The distributions of 41 polychlorinated biphenyls (PCBs) were determined in the aqueous phase, suspended particulate matter (SPM), and sediment of the Daliao River estuary in Liaodong Bay, Bohai Sea (China). The total PCB concentrations ranged from 5.51 to 40.28 ng L(-1) in the surface water, from 6.78 to 66.55 ng L(-1) dry weight in the SPM, and from 0.83 to 7.29 ng g(-1) dry weight in the sediment. The PCB concentrations in water, SPM, and sediment were moderate relative to those reported for other estuary and marine systems around the world. Sedimentary PCB concentrations decreased offshore due to the active deposition of laterally transported river-borne particles. The predominance of the highly chlorinated congeners for the water, SPM, and sediment samples are an indication of either a lack of degradation or the presence of nearby or recent releases into the environment.

Chemical forms and ecological risk of arsenic in the sediment of the Daliao River System in China.

The chemical forms and ecological risk of As were characterized in the sediment of the Daliao River System (DRS), which has been affected by long-term intensive industrial, urban, and agricultural activities. Twenty-seven samples of surface sediment were collected and analyzed for total As content and that of its chemical forms. The results indicated that the average total As content in the sediment was 9.83 mg kg(- 1) but that the levels ranged from 1.57 to 83.09 mg kg(- 1). At the sites near cities, mining sites, and the estuary of the DRS, it is likely that adverse effects on aquatic organisms occur, due to As levels in the sediment that are often higher than the threshold effect level and occasionally higher than the probable effect level. A selectively sequential extraction indicated that the majority of As in the sediment was bound to Fe oxides (62.1%), with moderate proportions of residual As (19.8%), specifically adsorbed As (17.9%), and a low proportion of non-specifically adsorbed As (1.1%). In addition, the content of Fe in the sediment was positively and significantly correlated with the contents of amorphous and crystalline Fe oxide-bound As, confirming the crucial role of Fe oxides in immobilizing high amounts of As in superficial environments. The average molar ratio of As to Fe was 1.18 × 10(- 4) in the surface sediment of the DRS, similar to that of natural Fe oxides, but much lower than that of synthesized Schwertmannite. Therefore, the release of As under reduced and low pH conditions can cause serious problems for water resources and for living organisms.

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection.

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF(3)/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5%h(-1)). However, the addition of dissolved Fe(III) species at 2.0 µM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.

Distribution patterns of nitroaromatic compounds in the water, suspended particle and sediment of the river in a long-term industrial zone (China).

Nitroaromatic compounds are known to be hazardous to ecological and human health. To assess the status of nitroaromatic compounds contamination in the main rivers in the important industrial bases of the northeastern China, we collected water, suspended particulate matter (SPM) and sediment samples from 28 sites in the Daliao River watershed and analysed them for eight nitroaromatic compounds by gas chromatography. The total concentrations of eight nitrobenzenes in the water column including aqueous and SPM phases ranged from 740 to 15,828 ng L( - 1), with a mean concentration of 3,460 ng L( - 1). The total concentrations of eight nitrobenzenes in the sediment were 7.47 to 8,185.76 ng g( - 1), with a mean concentration of 921.98 ng g( - 1), and several times higher than those found from the Yellow River in China. 4-Nitrotoluene was the predominant contaminant in the water and sediment of the three rivers of the Daliao River watershed. 2,6-Dichloro-4-nitroaniline was generally dominant in the SPM. The levels of nitroaromatic compounds were different among different sites in the Daliao River watershed, mainly caused by the distribution of pollution sources. No obvious correlation was found between the total concentrations of eight nitrobenzenes concentrations and TOC or the slit-clay content of the sediments.

Distributions of polycyclic aromatic hydrocarbons in the Daliao River Estuary of Liaodong Bay, Bohai Sea (China).

The distributions of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the aqueous phase, suspended particulate matter (SPM), sediment, and pore water of the Daliao River Estuary in Liaodong Bay, Bohai Sea (China). Total PAH concentrations ranged from 139.16 to 1717.87ngL(-1) in surface water, from 226.57 to 1404.85ngL(-1) dry weight in SPM, from 276.26 to 1606.89ngg(-1) dry weight in sediments, and from 10.20 to 47.27microgL(-1) in pore water. PAH concentrations were at relatively moderate levels in water, SPM, sediment and pore water in comparison with those reported for other estuary and marine systems around the world. Sedimentary PAH concentrations decreased offshore owing to active deposition of laterally-transported river-borne particles. PCA analysis of the possible PAH source suggested petrogenic and pyrolytic PAH inputs in the studied region.