Search

Abstract: Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe–Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1×cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the presence of SDS at sub-cmc increased TCE degraded by ∼10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5×cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe–Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses. [Copyright &y& Elsevier]

Abstract: This study pilot-tested carboxymethyl cellulose (CMC) stabilized zero-valent iron (ZVI) nanoparticles (with a trace amount of Pd catalyst) for in situ destruction of chlorinated ethenes such as perchloroethylene (PCE) and trichloroethylene (TCE) and polychlorinated biphenyls (PCBs) that had been in groundwater for decades. The test site was located in a well-characterized secondary source zone of PCBs and chlorinated ethenes. Four test wells were installed along the groundwater flow direction (spaced 5 ft apart), including one injection well (IW), one up-gradient monitoring well (MW-3) and two down-gradient monitoring wells (MW-1 and MW-2). Stabilized nanoparticle suspension was prepared on-site and injected into the 50-ft deep, unconfined aquifer. Approximately 150 gallons of 0.2 g/L Fe–Pd (CMC = 0.1 wt%, Pd/Fe = 0.1 wt%) was gravity-fed through IW-1 over a 4-h period (Injection #1). One month later, another 150 gallons of 1.0 g/L Fe–Pd (CMC = 0.6 wt%, Pd/Fe = 0.1 wt%) was injected into IW-1 at an injection pressure <5 psi (Injection #2). When benchmarked against the tracer, approximately 37.4% and 70.0% of the injected Fe was detected in MW-1 during injection #1 and #2, respectively, confirming the soil mobility of the nanoparticles through the aquifer, and higher mobility of the particles was observed when the injection was performed under higher pressure. Rapid degradation of PCE and TCE was observed in both MW-1 and MW-2 following each injection, with the maximum degradation being observed during the first week of the injections. The chlorinated ethenes concentrations gradually returned to their pre-injection levels after ∼2 weeks, indicating exhaustion of the ZVI''s reducing power. However, the injection of CMC-stabilized nanoparticle and the abiotic reductive dechlorination process appeared to have boosted a long-term in situ biological dechlorination thereafter, which was evidenced by the fact that PCE and TCE concentrations showed further reduction after two weeks. After 596 days from the first injection, the total chlorinated ethenes concentration decreased by about 40% and 61% in MW-1 and MW-2, respectively. No significant long-term reduction of PCB 1242 was observed in MW-1, but a reduction of 87% was evident in MW-2. During the 596 days of testing, the total concentrations of cis-DCE (dichloroethylene) and VC (vinyl chloride) decreased by 20% and 38% in MW-1 and MW-2, respectively. However, the combined fraction of cis-DCE and VC in the total chlorinated ethenes (PCE, TCE, cis-DCE and VC) increased from 73% to 98% and from 62% to 98%, respectively, which supports the notion that biological dechlorination of PCE and TCE was active. It is proposed that CMC-stabilized ZVI-Pd nanoparticles facilitated the early stage rapid abiotic degradation. Over the long run, the existing biological degradation process was boosted with CMC as the carbon source and hydrogen from the abiotic/biotic processes as the electron donor, resulting in the sustained enhanced destruction of the chlorinated organic chlorinated ethenes in the subsurface. [Copyright &y& Elsevier]

Abstract: Mercury (Hg) immobilization using stabilized iron sulfide (FeS) nanoparticles was investigated through a series of batch and column experiments. The nanoparticles were prepared using a low-cost, food-grade cellulose (sodium carboxymethyl cellulose, CMC) as the stabilizer. The hydrodynamic diameter of fresh FeS–CMC nanoparticles was measured to be 38.5±5.4nm. Batch tests showed that the nanoparticles can effectively immobilize Hg in a clay loam sediment. The Hg distribution coefficient for the nanoparticles was determined to be 8930±1480L/g, which is >4 orders of magnitude greater than for the sediment. When the Hg-laden sediment was treated at an FeS-to-Hg molar ratio of 26.5, the Hg concentration leached into water was reduced by 97% and the TCLP (toxicity characteristic leaching procedure) leachability of Hg was reduced by 99%. Column tests showed that water-leachable mercury from the sediment containing 3120mg/L Hg was reduced by 67% and the TCLP leachability by >77% when the sediment was treated with 67 pore volumes (PVs) of a 0.5g/L FeS nanoparticle suspension. Column tests proved that the stabilized nanoparticles were highly mobile in the sediment and full breakthrough of the nanoparticles occurred at ∼18 PVs. [Copyright &y& Elsevier]

• LISST can well applied to monitor the mean cell size and colony size of cyanoHABs. • Cell density of algae can be estimated reliably based on total and mean cell biovolume. • The protocol for in-situ tracking migration of cyanoHABs was validated in the tank. • The 3D section views of cyanoHABs in Dianchi lake were well obtained by LISST-HAB. Cyanobacterial harmful algal blooms (cyanoHABs) are becoming increasingly common in aquatic ecosystems worldwide. However, their heterogeneous distributions make it difficult to accurately estimate the total algae biomass and forecast the occurrence of surface cyanoHABs by using traditional monitoring methods. Although various optical instruments and remote sensing methods have been employed to monitor the dynamics of cyanoHABs at the water surface (i.e., bloom area, chlorophyll a), there is no effective in-situ methodology to monitor the dynamic change of cell density and integrated biovolume of algae throughout the water column. In this study, we propose a quantitative protocol for simultaneously measurements of multiple indicators (i.e., biovolume concentration, size distribution, cell density, and column-integrated biovolume) of cyanoHABs in water bodies by using the laser in-situ scattering and transmissometry (LISST) instrument. The accuracy of measurements of the biovolume and colony size of algae was evaluated and exceeded 95% when the water bloom was dominated by cyanobacteria. Furthermore, the cell density of cyanobacteria was well estimated based on total biovolume and mean cell volume measured by the instrument. Therefore, this methodology has the potential to be used for broader applications, not only to monitor the spatial and temporal distribution of algal biovolume concentration but also monitor the vertical distribution of cell density, biomass and their relationship with size distribution patterns. This provides new technical means for the monitoring and analysis of algae migration and early warning of the formation of cyanoHABs in lakes and reservoirs. [Display omitted] [ABSTRACT FROM AUTHOR]

• Iron oxides on MNZVI surface were conducive to the sulfidation reaction. • H• generated on MNZVI surface reduced S0 and promoted the formation of FeS x. • H 2 partial pressure in water affected the sulfidation efficiency of S-MNZVI. • Sulfur loading on S-MNZVI changed the degradation mechanism of TCE. Sulfidated zero valent iron (ZVI) is a popular material for the reductive degradation of halogenated organic pollutants. Simple and economic synthesis of this material is highly demanded. In this study, sulfidated micro/nanostructured ZVI (MNZVI) particles were prepared by simply heating MNZVI particles and sulfur elements (S0) in pure water (50℃). The iron oxides on the surface of MNZVI particles were conducive to sulfidation reaction, indicating the formation of iron-sulphide minerals (FeS x) on the surface of MNZVI particles might not be from the direct reaction of Fe0 with S0 (Fe0 and S0 acted as reductant and oxidant, respectively). As an important reductant, hydrogen atom (H•) can be generated from the reduction of H+ by MNZVI particles and participate in the formation of FeS x. Quenching experiment and cyclic voltammetry analysis proved the existence of H• on the surface of MNZVI particles. DFT calculation found that the potential barrier of H•/S0 and Fe0/S0 were 1.91 and 7.24 eV, respectively, indicating that S0 would preferentially react with H• instead of Fe0. The formed H• can quickly react with S0 to generate hydrogen sulfide (H 2 S), which can further react with iron oxides such as α-Fe 2 O 3 on the surface of MNZVI particles to form FeS x. In addition, the H 2 partial pressure in water significantly affected the amount of H• generated, thereby affecting the sulfidation efficiency. For TCE degradation, as the sulfur loading of sulfidated MNZVI particles increased, the contribution of H• significantly decreased while the contribution of direct electron transfer increased. This study provided new insights into the synthesis mechanism of sulfidated ZVI in water. [Display omitted] [ABSTRACT FROM AUTHOR]

Groundwater pH is one of the most important geochemical parameters in controlling the interfacial reactions of zero-valent iron (ZVI) with water and contaminants. Ball milled, microscale ZVI (mZVIbm) efficiently dechlorinated TCE at initial stage (<24 h) at pH 6–7 but got passivated at later stage due to pH rise caused by iron corrosion. At pH > 9, mZVIbm almost completely lost its reactivity. In contrast, ball milled, sulfidated microscale ZVI (S-mZVIbm) didn't experience any reactivity loss during the whole reaction stage across pH 6–10 and could efficiently dechlorinate TCE at pH 10 with a reaction rate of 0.03 h−1. Increasing pH from 6 to 9 also enhanced electron utilization efficiency from 0.95% to 5.3%, and from 3.2% to 22%, for mZVIbm and S-mZVIbm, respectively. SEM images of the reacted particles showed that the corrosion product layer on S-mZVIbm had a puffy/porous structure while that on mZVIbm was dense, which may account for the mitigated passivation of S-mZVIbm under alkaline pHs. Density functional theory calculations show that covered S atoms on the Fe(100) surface weaken the interactions of H 2 O molecules with Fe surfaces, which renders the sulfidated Fe surface inefficient for H 2 O dissociation and resistant to surface passivation. The observation from this study provides important implication that natural sulfidation of ZVI may largely contribute to the long-term (>10 years) efficiency of TCE decontamination by permeable reactive barriers with pore water pH above 9. Image 1 • Sulfidated ZVI effectively dechlorinated TCE at alkaline pHs but ZVI couldn't. • Increasing pH enhanced electron efficiency of both particles. • Sulfidation produced a puffy structure of corrosion products to mitigate passivation. • S atoms weaken the interaction of H 2 O with Fe surface to cause the puffy structure. [ABSTRACT FROM AUTHOR]

• Cations (Mg2+, Ca2+, K+, Na+, Fe2+) can accelerate the sulfidation of mZVI by S0. • Mg2+ was most efficient in promoting sulfidation of mZVI by S0. • Mg2+ inhibited the formation of cis-DCE during TCE dechlorination by S-mZVI. • mZVI and S0 can react quickly in actual groundwater. The solid-solid reaction of microscale zero-valent iron (mZVI) with elemental sulfur (S0) in water can form sulfidated mZVI (S-mZVI) with high reactivity and selectivity. However, the inherent passivation layer of mZVI hinders the sulfidation. In this study, we demonstrate that ionic solutions of Me-chloride (Me: Mg2+, Ca2+, K+, Na+ and Fe2+) can accelerate the sulfidation of mZVI by S0. The S0 with S/Fe molar ratio of 0.1 was fully reacted with mZVI in all solutions to form unevenly distributed FeS species on S-mZVIs as confirmed by SEM-EDX and XANES characterization. The cations depassivated the mZVI surface by driving the proton release from the surface site (FeOH) and resulting in localized acidification. The probe reaction test (tetrachloride dechlorination) and open circuit potential (E OCP) measurement demonstrated that Mg2+ was most efficient in depassivating the mZVI and therefore promoting sulfidation. The decrease of surface proton for hydrogenolysis on the S-mZVI synthesized in MgCl 2 solution also inhibited the formation of cis-1,2-dichloroethylene by 14–79% compared to other S-mZVIs during trichloroethylene dechlorination. In addition, the synthesized S-mZVIs exhibited the highest reduction capacity reported so far. These findings provide a theoretical basis for the facile on-site sulfidation of mZVI by S0 with cation-rich natural waters for sustainable remediation of contaminated sites. [Display omitted] [ABSTRACT FROM AUTHOR]

Characteristics of extracellular polymeric substances (EPS) in activated sludge strongly depend on wastewater substrates. Proteinaceous substrates (ProS) present in heterogeneous polymeric form are intrinsic and important parts of wastewater substrates for microorganisms in activated sludge systems. However, correlations between ProS and characteristics of EPS are scarce. This study systematically explored the impacts of monomeric (Mono-), low polymeric (LoP-) and high polymeric (HiP-) ProS on compositions and functional groups of EPS in activated sludge. The results showed that the change of polymerization degree of ProS significantly altered the composition of EPS. Compared to EPS Mono-ProS , the proportion of proteins in EPS LoP-ProS and EPS HiP-ProS increased by 12.8% and 27.7%, respectively, while that of polysaccharides decreased by 22.9% and 63.6%, respectively. Moreover, the proportion of humic compounds in EPS LoP-ProS and EPS HiP-ProS were ∼6 and ∼16–fold higher than that in EPS Mono-ProS , respectively. The accumulation of humic compounds in EPS increased the unsaturation degree of EPS molecules, and thereby reduced the energy requirement for electrons transition of amide bonds and aromatic groups. Size exclusion chromatography (SEC) analyses detected more molecular clusters in EPS HiP-ProS , indicating more complex composition of EPS in HiP-ProS fed activated sludge. Spectroscopic characterization revealed the dominance of hydrocarbon, protein, polysaccharide and aromatic associated bonds in all three EPS. Nevertheless, with the increase of polymerization degree of ProS, the protein associated bonds (such as CO NH , C O, N C, N H) increased, while the polysaccharide associated bonds (such as C O C, C O H, O C OH) decreased. This paper paves a path to understand the role of ProS in affecting the production and characteristics of EPS in biological wastewater treatment systems. [ABSTRACT FROM AUTHOR]

Mn(III) is a strong oxidant for one electron transfer, which may be important in the transformation of organic contaminants during water/wastewater treatment and biogeochemical redox processes. This study explored the reaction mechanisms of dissolved Mn(III) with organics. The role of dissolved Mn(III) either as a catalyst or an oxidant in reactions with organics was recognized. Aquo and/or hydroxo (or free) Mn(III), generated from the bisulfite activated permanganate process, facilitated efficient N-dealkylation of atrazine via a β-elimination mechanism, resulting no net redox reaction. In contrast, free Mn(III) degraded 4-chlorophenol via intramolecular redox processes, the same as hydroxyl radical ( OH), resulting in dechlorination, OH substitution, ring-opening and mineralization. Mn(III)-pyrophosphate compounds did not react with atrazine because complexation by pyrophosphate rendered Mn(III) unable to bond with atrazine, thus the electron and proton transfers between the reactants couldn't occur. However, it degraded 4-chlorophenol at a slower rate compared to free Mn(III), due to its reduced oxidation potential. These results showed two distinct mechanisms on the degradation of organic contaminants and the insights may be applied in natural manganese-rich environments and water treatment processes with manganese compounds. [ABSTRACT FROM AUTHOR]

Abstract: An exploratory study on the management of undesirable cyanobacteria blooms with respect to off-flavor problems using an integrated vertical-flow constructed wetland (CW) was performed at a small commercial-scale channel catfish farm from 2004 to 2007. The results of the three-year experiment indicated that water treatment by the CW could reduce the possibility of dominance by undesirable cyanobacteria species that often cause off-flavor problems. A detailed investigation in 2007, showed that the concentrations of geosmin, MIB (2-methylisoborneol), and β-cyclocitral in the water of the recirculating pond (4.3ngL−1, U.D. (undetected) and 0.2ngL−1, respectively) treated by the CW were significantly lower than those in the control pond (152.6ngL−1, 63.3ngL−1 and 254.8ngL−1, respectively). In addition, the relationships among the cyanobacteria species, the off-flavor compounds and ten environmental variables were explored by canonical correspondence analysis (CCA). The results showed that Oscillatoria sp., Oscillatoria kawamurae and Microcystis aeruginosa were the main sources of off-flavor compounds in the catfish ponds. The successful manipulation of undesirable cyanobacteria species potentially resulted in lower concentrations of odorous compounds in the water of the recirculating pond. An investigation of the concentrations of geosmin and MIB in catfish fillets showed that the levels of odorous compounds were below the OTC (odor threshold concentration) values in the recirculating pond but were above the OTC values from July to October in the control pond. Water recycling by the CW could potentially be one of the best management practices to control off-flavor occurrences in aquaculture. [Copyright &y& Elsevier]

• As(III) can be effectively removed by ball milled, sulfidated ZVI (S-mZVIbm). • As(III) was removed primarily through As 4 S 4 formation under anoxic conditions. • As(III) was removed through adsorption onto corrosion product under oxic conditions. • S-mZVIbm/sand column rapidly reduces As(III) in a groundwater from 300 to 10 µg/L. • S-mZVIbm in sand column treats >750 BV groundwater with a capacity of 12.2 mg/g. The interaction of As(III) with micron-sized, mechanochemically sulfidated zero-valent iron (S-mZVIbm) has been studied under both anoxic and oxic conditions. The As(III) removal capacity varied with the increase of S/Fe molar ratio under anoxic conditions, while it continuously decreased under oxic conditions. A series of sequential extractions, X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) spectroscopy analyses were used to investigate As(III) removal mechanisms. In the absence of oxygen, As(III) was removed from solution primarily through the formation of As 4 S 4 with less than half of the removal resulting from the adsorption of As(III)/As(V) and FeAsS precipitation. Under oxic conditions, adsorption onto iron (oxyhydr)oxides was the dominant mechanism of As(III) removal. Increasing sulfidation decreased particle Fe(0) content, which resulted in less production of iron (oxyhydr)oxides and therefore lower As(III) removal capacities. Column experiments showed that less than 2 wt% of S-mZVIbm in sand was able to rapidly reduce the As(III) concentration in a real groundwater from 300 to 10 µg/L, the Chinese drinking water standard, for up to 750 BV with an EBCT of 2.54 min. This study demonstrates that S-mZVIbm is an efficient and cost-effective material in treating As-contaminated water to ensure water safety. [Display omitted] [ABSTRACT FROM AUTHOR]

• The long-term effects of environmental factors on submerged plants were studied. • Submerged plants distribution exhibited much closer correlation to water nutrients. • Increasing trend of each characteristic parameter of sedimentation has been observed. • Large distribution of V. natans is dependent on its physiology and growth form. • Well-reestablished food webs need to be considered for ecological restoration. Submerged macrophyte restoration is the key stage in the reestablishment of an aquatic ecosystem. Previous studies have paid considerable attention to the effect of multiple environmental factors on submerged macrophytes. Meanwhile, few studies have been conducted regarding the spatial and seasonal characteristics of water and sediment properties and their long-term relationship with submerged macrophytes after the implementation of the submerged macrophytes restoration project. On a monthly basis, we monitored the spatial and seasonal variation in water parameters, sediment properties, and the submerged macrophyte characteristics of West Lake in Hangzhou from August 2013 to July 2019. From these measurements, we characterized the relationship between environmental factors and submerged macrophytes. Water nutrient concentrations continuously decreased with time, and the accumulation of sediment nutrients was accelerated as the submerged macrophyte communities developed on a long-term scale. The results indicated that the difference in water parameters was due to seasonal changes and land-use types in the watershed. The differences in the sediment properties were mainly attributed to seasonal changes and changes in the flow field. Redundancy analysis showed that the influence of water nutrients on the submerged macrophyte distribution was greater than that of sediment nutrients. The result also suggested that the developed root system, high stoichiometric homeostasis coefficients of P, and compensation ability of substantial leaf tissue may lead to a large distribution of Vallisneria natans in West Lake in Hangzhou. The correlation of water parameters and sediment properties with submerged macrophytes for a long time was very important as the restoration was achieved. To ensure the stability of the aquatic ecosystem after performing the submerged macrophyte restoration, a greater emphasis must be placed on reestablishing the entire ecosystem, including the restoration of aquatic animals and fish stocks. We expect these findings to serve as a reference for researchers and government agencies in the field of aquatic ecosystem restoration. Image, graphical abstract [ABSTRACT FROM AUTHOR]