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The impact of the Coronavirus Disease 2019 (COVID-19) pandemic on microplastic (MP) occurrence in aquatic environments deserves an in-depth study. In this study, the occurrence of MPs and environmental flux of plastics before (2019) and during (2020 and 2021) the pandemic were comparatively investigated in various aquatic compartments in the Taihu Lake Basin in China. The field-based investigations from 2019 to 2021 for Taihu Lake have shown that, at the onset of the outbreak, the MP abundance declined at a rate of 62.3 %, but gradually recovered to the pre-pandemic level. However, the amount of plastics being released into aquatic environments showed a declining trend in 2020 and 2021 compared to those in 2019, with decrease rates of 13.7 % and 15.8 %, respectively. Characterization analysis of MP particles and source apportionment framework implied that while the contributions of tire abrasion and domestic waste to MP occurrence were depleted owing to the reduction in human activity during the pandemic, weathering and fragmentation of retained plastics contributed to the recovery of stored MPs. This study provides insights into the anthropogenic influences on MP occurrence, and supports policymakers in managing and controlling plastic contamination in large freshwater systems in the "new normal" phase., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Microplastics (MPs) have attracted increasing attention due to their ubiquitous occurrence in freshwater sediments and the detrimental effects on benthic invertebrates. However, a clear understanding of their downstream impacts on ecosystem services is still lacking. This study examines the effects of bio-based polylactic acid (PLA), fuel-based polyethylene terephthalate (PET), and biofilm-covered PET (BPET) MPs on the bioturbator chironomid larvae (Tanypus chinensis), and the influence on phosphorus (P) profiles in microcosms. The changes in biochemical responses and metabolic pathways indicated that MPs disrupted energy synthesis by causing intestinal blockage and oxidative stress in T. chinensis, leading to energy depletion and impaired bioturbation activity. The impairment further resulted in enhanced sedimentary P immobilization. For larval treatments, the internal-P loadings were respectively 11.4%, 8.6%, and 9.0% higher in the PLA, PET, and BPET groups compared to the non-MP control. Furthermore, the influence of bioturbation on P profiles was MP-type dependent. Both BPET and PLA treatments displayed more obvious impacts on P profiles compared to PET due to the changes in MP bioavailability or sediment microenvironment. This study connects individual physiological responses to broader ecosystem services, showing that MPs alter P biogeochemical processes by disrupting the bioturbation activities of chironomid larvae., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Clean soil is a potential capping material for controlling internal nutrient loading and helping the recovery of macrophytes in eutrophic lakes, but the long-term effects and underlying mechanisms of clean soil capping under in-situ conditions remain poorly understood. In this study, a three-year field capping enclosure experiment combining intact sediment core incubation, in-situ porewater sampling, isotherm adsorption experiments and analysis of sediment nitrogen (N) and phosphorus (P) fractions was conducted to assess the long-term performance of clean soil capping on internal loading in Lake Taihu. Our results indicate that clean soil has excellent P adsorption and retention capacity as an ecologically safe capping material and can effectively mitigate NH 4 + -N and SRP (soluble reactive P) fluxes at the sediment-water interface (SWI) and porewater SRP concentration for one year after capping. The mean NH 4 + -N and SRP fluxes of capping sediment were 34.86 mg m -2 h -1 and -1.58 mg m -2 h -1 , compared 82.99 mg m -2 h -1 and 6.29 mg m -2 h -1 for control sediment. Clean soil controls internal NH 4 + -N release through cation (mainly Al 3+ ) exchange mechanisms, while for SRP, clean soil can not only react with SRP due to its high Al and Fe content, but also stimulate the migration of active Ca 2+ to the capping layer, thus precipitating as Ca-bound P (Ca-P). Clean soil capping also contributed to the restoration of macrophytes during the growing season. However, the effect of controlling internal nutrient loading only lasted for one year under in-situ conditions, after which the sediment properties returned to pre-capping conditions. Our results highlight that clean Ca-poor soil is a promising capping material and further research is needed to extend the longevity of this geoengineering technology., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Sediment hypoxia is a growing problem and has negative ecological impacts on the aquatic ecosystem. Hypoxia can disturb the biodiversity and biogeochemical cycles of both phosphorus (P) and nitrogen (N) in water columns and sediments. Anthropogenic eutrophication and internal nutrient release from lakebed sediment accelerate hypoxia to form a dead zone. Thus, sediment hypoxia mitigation is necessary for ecological restoration and sustainable development. Conventional aeration practices to control sediment hypoxia, are not effective due to high cost, sediment disturbance and less sustainability. Owing to high solubility and stability, micro-nanobubbles (MNBs) offer several advantages over conventional water and wastewater treatment practices. Clay loaded oxygen micro-nanobubbles (OMNBs) can be delivered into deep water sediment by gravity and settling. Nanobubble technology provides a promising route for cost-effective oxygen delivery in large natural water systems. OMNBs also have the immense potential to manipulate biochemical pathways and microbial processes for remediating sediment pollution in natural waters. This review article aims to analyze recent trends employing OMNBs loaded materials to mitigate sediment hypoxia and subsequent pollution. The first part of the review highlights various minerals/materials used for the delivery of OMNBs into benthic sediments of freshwater bodies. Release of OMNBs at hypoxic sediment water interphase (SWI) can provide significant dissolved oxygen (DO) to remediate hypoxia induced sediment pollution Second part of the manuscript unveils the impacts of OMNBs on sediment pollutants (e.g., methylmercury, arsenic, and greenhouse gases) remediation and microbial processes for improved biogeochemical cycles. The review article will facilitate environmental engineers and ecologists to control sediment pollution along with ecological restoration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The 2013 "Qingdao oil pipeline explosion" contaminated about 2.5 km of shoreline in the Jiaozhou Bay area and aroused widespread concern because of the serious casualties even though it was not the most severe oil-spill contamination in China. To evaluate the long-term impact, we collected thirty-three surface sediment samples after 3 years of the accident, with sixteen polycyclic aromatic hydrocarbons (PAHs) detected. Spatial-temporal variation in PAHs revealed that a minimal impact might still be present after 3 years. Source analysis combined with a one-way ANOVA showed that pyrolytic sources were consistently predominant. The environmental impact was already minimal 3 years later and negligible thereafter. Although the cancer risk has decreased over the years, there has always been a potential hazard to human for specific occupation, with all of the risk values exceeded 10 -6 . This study offers a reference for assessing the long-term impact of oil spills in similar bay areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Reutilization of the waste by-products from industrial and agricultural activities is crucially important towards attainment of environmental sustainability and the 'circular economy'. In this study, we have developed and evaluated a sustainably-sourced adsorbent from coal fly ash, which was modified by a small amount of lanthanum (La-FA), for the recapture of phosphorous (P) from both synthetic and real natural waters. The prepared La-FA adsorbent possessed typical characteristic diffraction peaks similar to zeolite type Na-P1, and the BET surface area of La-FA was measured to be 10.9 times higher than that of the original FA. Investigation of P adsorption capability indicated that the maximum adsorption (10.8 mg P g -1 ) was 6.14 times higher than that (1.8 mg P g -1 ) of the original fly ash material. The ζ potentials measurement and P K-edge X-ray Absorption Near Edge Structure (XANES) spectra demonstrated that P was bonded on La-FA surfaces via an adsorption mechanism. After applying the proposed adsorbent to real lake water with La/P molar ratios in the range from 0.5:1 to 3:1, the La-FA adsorbent showed the highest phosphate removal ability with a La/P molar ratio 1:1, and the P adsorption was similar to that performance with the synthetic solution. Moreover, the La-FA absorbent produced a negligible effect on the concentrations of total dissolved nitrogen (TDN), NH 4 + -N and NO 3 - -N in water. This study thus provides a potential material for effective P recapture and details of its operation., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The arsenic (As)-bearing eutrophic waters may suffer from the dual conditions of harmful algal blooms and release of As, driven by algal-induced hypoxia/anoxia. Here, we investigate the use of interfacial oxygen (O 2 ) nanobubble technology to combat the hypoxia and control As exposure in simulated mesocosm experiments. It was observed that remediation of algal-induced hypoxia at the sediment-water interfaces (SWI) by application of O 2 nanobubbles reduced the level of dissolved As from 23.2 μg L -1 to <10 μg L -1 and stimulated the conversion of As(III) to the less toxic As(V) (65-75%) and methylated As (10-15%) species. More than half of the oxidation and all the methylation of As(III) resulted from the manipulation by O 2 nanobubbles of microbes responsible for As(III) oxidation and methylation. Hydroxyl radicals were generated during the oxidation of reductive substances at the SWI in darkness, and should be dominant contributors to As(III) abiotic oxidation. X-ray absorption near-edge structure (XANES) spectroscopic analysis demonstrated that surface sediments changed from being sources to acting as sinks of As, due to the formation of Fe-(hydr)oxide. Overall, this study suggests that interfacial O 2 nanobubble technology could be a potential method for remediation of sediment As pollution through the manipulation of O 2 -related microbial and geochemical reactions., (Copyright © 2021. Published by Elsevier Ltd.)

Eutrophication in freshwater environments may be enhanced by the elevation of sulfate in waters, through the release of internal phosphorus (P) from anoxic sediments. However, the influence of increasing but modest sulfate concentrations (less than 3000 μM) on P release under oxic conditions across the sediment-water interface (SWI) in eutrophic freshwater is poorly understood. In this study, the profiles of P, iron (Fe), sulfur (S) and physicochemical parameters were measured in a simulated lacustrine system with varying concentrations of sulfate (970-2600 μM) in overlying water. The results indicated that elevated concentrations of sulfate increased the soluble reactive P in overlying waters under oxic conditions across the SWI. A 100 μM increase of sulfate was found to induce a 0.128 mgm -2 d -1 increase of P flux from surface sediments into overlying waters under oxic conditions. Higher sulfate concentrations in the overlying waters increased the concentrations of labile S(-II) in the deep sediments, due to sulfate penetration and subsequent reduction to S(-II). We also found the fluxes of labile Fe (10.34 to 18.33 mgm -2 d -1 ) and P (2.70 to 1.33 mgm -2 d -1 ) from deep to surface sediment were both positive and greater than the corresponding fluxes (Fe, 2.2 to 3.51 and P, 2.6 to 0.39 mgm -2 d -1 , respectively) from surface sediment to the overlying water, suggesting that reduction of P-bearing Fe(III)(oxyhydr)oxides in deep anoxic sediment acted as a major source of internal P release. In addition, the upward flux of Fe(II) was significantly lower under higher sulfate conditions, indicating that the Fe(II) flux could be mitigated by formation of Fe(II) sulfides in the deep sediment. Under these conditions, less Fe(II) from deep sediments could be re-oxidized and combine with P in the surface, oxic sediment, thereby reducing the retention capacity for P and leading to higher release of internal P to the water column., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Phenol contamination is a common occurrence in aquatic environments in different parts of the world and strategies that utilize cheap and eco-friendly phytoremediation technologies are required to overcome associated environmental problems. In the present study, the submersed macrophyte Hydrilla verticillata (L.F.) Royle was exposed to different concentrations of phenol (0-200 mg L -1 ) to assess its potential in phenol treatment. H. verticillata efficiently degraded phenol in solutions with initial concentrations lower than 200 mg L -1 . The adverse effects of phenol on physiological parameters of H. verticillata were also investigated after 7 d of phenol stress. In order to explore the effect of phenol on the metabolism of H. verticillata during phytoremediation, gas chromatography-mass spectrometry (GC-MS) was used to analyze endogenous soluble organic compounds. The results revealed the presence of greater than 60 soluble organic compounds in H. verticillata. In the process of phenol degradation, fatty acid composition and carbon number distribution were affected in the plants while unsaturated fatty acid content was significantly lower, and several compounds including aliphatic dicarboxylic acids and aromatic ketones were degraded while new compounds were synthesized by the plant. In summary, H. verticillata is a promising candidate for the phytoremediation of the phenol-contaminated aquatic system., Competing Interests: Declaration of Competing Interest None., (Copyright © 2019. Published by Elsevier B.V.)

In mercury (Hg)-polluted eutrophic waters, algal blooms are likely to aggravate methylmercury (MeHg) production by causing intensified hypoxia and enriching organic matter at the sediment-water interface. The technology of interfacial oxygen (O 2 ) nanobubbles is proven to alleviate hypoxia and may have potential to mitigate the risks of MeHg formation. In this study, incubation column experiments were performed using sediment and overlying water samples collected from the Baihua Reservoir (China), which is currently suffering from co-contamination of Hg and eutrophication. The results indicated that after the application of O 2 nanobubbles, the %MeHg (ratio of MeHg to total Hg) in the overlying water and surface sediment decreased by up to 76% and 56% respectively. In addition, the MeHg concentrations decreased from 0.54 ± 0.15 to 0.17 ± 0.01 ng L -1 in the overlying water and from 56.61 ± 9.23 to 25.48 ± 4.08 ng g -1 in the surface sediment. The decline could be attributed to the alleviation of anoxia and the decrease of labile organic matter and bioavailable Hg. In addition, hgcA gene abundances in the overlying water and surface sediment decreased by up to 69% and 44% after the addition of O 2 nanobubbles, as is consistent with MeHg occurrence in such areas. Accordingly, this work proposed a promising strategy of using interfacial oxygen nanobubbles to alleviate the potentially enhanced MeHg production during algal bloom outbreaks in Hg-polluted eutrophic waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Eutrophication can induce hypoxia/anoxia and rich organic matter at the sediment-water interface in surface waters. When eutrophic waters are impacted with mercury (Hg) pollution, methylmercury (MeHg) production ability (MPA) of surface sediment would increase and more MeHg might be produced. To tackle this risk, this study firstly collected samples of surface sediment and overlying water from a typical eutrophic lake-Taihu Lake. Then from a sediment-water simulation system, we demonstrated that eutrophic waters were able to methylate Hg spontaneously, and that sediment is the major Hg sink in the system. After the addition of HgCl 2 solution (approximately 1 mg L -1 in the slurry), MeHg concentrations in the sediment increased by 11.7 times after 48 h. The subsequent column experiments proved that O 2 nanobubbles could significantly decrease the MPA of surface sediment, by up to 48%. Furthermore, we found that O 2 nanobubbles could remediate anoxia mainly by increasing dissolved oxygen (from 0 to 2.1 mg L -1 ), oxidation-reduction potentials (by 37% on average), and sulfate (by 31% on average) in the overlying water. In addition, O 2 nanobubbles could also help decrease organic matter concentration, as was revealed by the decline of dissolved organic carbon in the overlying water (by up to 57%) and total organic carbon in surface sediment (by up to 37%). The remediation of anoxia and reduction of organic matter could contribute to the decrease of hgcA gene abundance (by up to 86%), and thus result in the reduction of MPA after the addition of O 2 nanobubbles. This study revealed the risk of MeHg production in case Hg pollution occurs in eutrophic waters and proposed a feasible solution for MeHg remediation., (Crown Copyright © 2019. Published by Elsevier Inc. All rights reserved.)

Methylmercury (MeHg) in sediment is difficult to be determined due to its low concentration and binding compounds like sulfide and organic matter. Moreover, wet sediment samples have been suggested to behave differently from certified reference materials in MeHg analysis. Optimal pretreatment procedure for MeHg determination in sediments has not been ascertained and whether the procedure could apply to sediment samples with complex matrix merits further research. This work firstly compared recovery results of five pretreatment procedures for MeHg determination using ERM-CC580. Using the optimal pretreatment procedure, recovery results were analyzed in different sediment samples after manipulation of moisture content, organic matter, and acid volatile sulfide. The procedure using CuSO 4 /HNO 3 as leaching solutions and mechanical shaking as extraction method was proved to produce the most satisfactory recovery results (100.67 ± 6.75%, mean ± standard deviation). And when moisture content varied from 20 to 80%, average recovery results in sediment samples ranged from 100 to 125%. Furthermore, before and after the manipulation of organic matter or acid volatile sulfide, spiking recovery results varied little and were all within acceptable limit (85~105%). Therefore, the procedure of CuSO 4 /HNO 3 -mechanical is proposed as a universal pretreatment method for MeHg determination in sediment samples with various characteristics.

Many arsenic-bearing freshwaters are facing with eutrophication and consequent algae-induced anoxia/hypoxia events. However, arsenic cycling in eutrophic waters and its impact on public health are poorly understood. Laboratory simulation experiments are performed in this study to investigate the effect of algal blooms on the cycling of arsenic in a sediment-water-air system. We found that the anoxia induced by the degradation of algal biomass promoted an acute arsenic (mostly As(III)) release within two days from sediment to both the water and atmosphere, and the release effluxes were proportional to the algae dosage. The reduction and methylation of arsenic were enhanced at the sediment-water interface, owing to the significant increase in arsenate reductase genes (arrA and arsC), and arsenite methyltransferase genes (arsM) caused by increased anoxia. The analysis of synchrotron-based X-ray absorption spectroscopy indicated that the concomitantly released natural organic matter (NOM) and sulfur (S) at the sediment-water interface reduced the As(III) release to a certain extent in the later reducing period of incubation, by forming As 2 S 3 (43-51%) and As(III)-Fe-NOM (28-35%). Our results highlight the needs for the in-situ assessment of volatile arsenic in eutrophic freshwaters with its risk to human and animal health., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Combating hypoxia/anoxia is an increasingly common need for restoring natural waters suffering from eutrophication. Oxygen nanobubble modified natural particles were investigated for mitigating hypoxia/anoxia at the sediment-water interface (SWI) in a simulated column experiment. By adding oxygen nanobubble modified zeolites (ONMZ) and local soils (ONMS), the oxygen nanobubble concentrations (10 5 -10 7  particles/mL) were several orders of magnitude higher in the water than the original water solution (10 4  particles/mL) within 24 h. In the column experiment, an oxygen-locking surface sediment layer was formed after capping with ONMZ and ONMS particles. The synergy of diffusion of oxygen nanobubbles and retention of oxygen in this layer contributes to both the increase of DO and reversal of hypoxic conditions. The overlying water had significantly higher dissolved oxygen (DO) values (4-7.5 mg/L) over the experimental period of 127 days in ONMZ and ONMS compared with the control systems (around 1 mg/L). Moreover, the oxidation-reduction potential (ORP) was reversed from -200 mV to 180-210 mV and maintained positive values for 89 days in ONMZ systems. In the control systems, ORP was consistently negative and decreased from -200 mV to -350 mV. The total phosphorus (TP) flux from sediment to water across the SWI was negative in the ONMZ and ONMS treated systems, but positive in the control system, indicating the sediment could be switched from TP source to sink. The oxygen-locking capping layer was crucial in preventing oxygen consumption caused by the reduced substances released from the anoxic sediment. The study outlines a potentially promising technology for mitigating sediment anoxia and controlling nutrient release from sediments, which could contribute significantly to addressing eutrophication and ecological restoration., (Copyright © 2018. Published by Elsevier B.V.)

Heavy metal ions coexisting with salts in the contaminant water are difficult to remove due to the interference of salts. Herein, biochars were pyrolyzed by corn straw at different temperatures, aiming to remove Cr(VI) in the presence of salts. Results show that biochars had surprisingly selective adsorption of Cr(VI). X-ray photoelectron and X-ray absorption near edge spectra revealed that Cr(VI) was reduced to Cr(III). All the adsorption was conducted at pH ∼ 7, which differed from the previous studies that Cr(VI) could only be reduced at pH 2-4. Environmental persistent free radicals (EPFRs) on biochars were found to play the role in reducing Cr(VI) in neutral solutions, which was confirmed by electron spin resonance and free radical quenching. The biochar with EPFRs reveals a highly selective removal of Cr(VI), which has implications for the remediation of contaminated water. This work provides a new insight into biochar's properties and potential environmental applications., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Modified soils (MSs) are being increasingly used as geo-engineering materials for the sedimentation removal of cyanobacterial blooms. Cationic starch (CS) has been tested as an effective soil modifier, but little is known about its potential impacts on the treated water. This study investigated dissolved organic matters in the bloom water after algal removal using cationic starch modified soils (CS-MSs). Results showed that the dissolved organic carbon (DOC) could be decreased by CS-MS flocculation and the use of higher charge density CS yielded a greater DOC reduction. When CS with the charge density of 0.052, 0.102 and 0.293meq/g were used, DOC was decreased from 3.4 to 3.0, 2.3 and 1.7mg/L, respectively. The excitation-emission matrix fluorescence spectroscopy and UV254 analysis indicated that CS-MS exhibits an ability to remove some soluble organics, which contributed to the DOC reduction. However, the use of low charge density CS posed a potential risk of DOC increase due to the high CS loading for effective algal removal. When CS with the charge density of 0.044meq/g was used, DOC was increased from 3.4 to 3.9mg/L. This study suggested, when CS-MS is used for cyanobacterial bloom removal, the content of dissolved organic matters in the treated water can be controlled by optimizing the charge density of CS. For the settled organic matters, other measures (e.g., capping treatments using oxygen loaded materials) should be jointly applied after algal flocculation., (Copyright © 2016. Published by Elsevier B.V.)

Perfluorooctanoic acid (PFOA) is recalcitrant to degrade and mineralize. Here, the effect of temperature on the photolytic decomposition of PFOA was investigated. The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85°C under UV light (201-600 nm). The limited degree of decomposition at 25°C was due to low quantum yield, which was increased by a factor of 12 at 85°C. Under the imposed conditions, the defluorination ratio increased from 8% at 25°C to 50% at 85°C in 60 min. Production of perfluorinated carboxylic acids (PFCAs, C7-C5), PFCAs (C4-C3) and TFA (trifluoroacetic acid, C2) accelerated and attained a maximum within 30 to 90 min at 85°C. However, these reactions did not occur at 25°C despite extended irradiation to 180 min. PFOA was decomposed in a step-wise process by surrendering one CF2 unit. In each cyclical process, increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals. The energy consumption for removing each μmol of PFOA was reduced from 82.5 kJ at 25°C to 10.9 kJ at 85°C using photolysis. Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination., (Copyright © 2015. Published by Elsevier B.V.)

The distribution in water and sediment, the sources/sinks and the risk of perfluorinated compounds (PFCs) in Lake Taihu, China were investigated. The total PFCs concentration was 164 to 299 ng L(-1) in water and 5.8 to 35 ng g(-1) (dw) in sediment. The highest concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) in water were 29.2 ng L(-1) and 136ngL(-1). PFOS was largely associated with sediment, whereas short chain PFCs predominated in water. The partition coefficient (Kd) was positively correlated with the organic carbon fraction (ƒoc) for PFOS but not for the other PFCs. The organic carbon normalized partition coefficient (Koc) increased by 0.51 log units for each additional CF2 moiety from perfluoro-butanesulfonate (PFBS) to PFOS. For the same chain length but different functional groups, the log Koc of PFOS was 1.35 units higher than PFOA. PFOS exhibited the highest affinity for sediment through the partition mechanism, and ƒoc affected the sediment as a sink of PFOS. Although there was no immediate health impact by the intake of the water alone, the consumption of aquatic products may cause potential health risks for animals/humans on the time scale of months to years. The relationship between the concentration, water-sediment distribution, bioaccumulation and toxicity should be considered in determining the water standards of PFCs., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A natural red soil and a lanthanum-modified soil (LMS) were tested to compare their phosphorus (P) adsorption capacities and their effectiveness in removing P from the water column and reducing P release from sediment. The equilibrium of P adsorption demonstrated that the maximum P adsorption for the soil was 1.29 and 2.22 mg g(-1) at pH 8.5 and 5.5, respectively, and for the LMS these were increased by 45.6 and 77.6% at pH 8.5 and 5.5, respectively, indicating that the soil was effective in P adsorption and the doping of lanthanum could substantially increase P adsorption. The sediment-water column incubation showed that, due to the P adsorption of the soil and LMS, the total P in the water column decreased by 58.5, 60.6, 68.2 and 77.2% for 180 g m(-2) soil, 900 g m(-2) soil, 180 g m(-2) LMS and 900 g m(-2) LMS treated systems, respectively, in a short time (6 h), and the capping layer substantially reduced the P release from sediment during column incubation, indicating that the soils were effective in reducing internal P load. However, considering the cost of LMS, the natural soil was suggested to be a cost-effective material to control internal P load.

Phosphorus (P) in water and sediment in the Yellow River was measured for 21 stations from the source to the Bohai Sea in 2006-2007. The average total particulate matter (TPM) increased from 40 mg/L (upper reaches) to 520 mg/L (middle reaches) and 950 mg/L in the lower reaches of the river. The average dissolved PO4 concentration (0.43 μmol/L) was significantly higher than that in 1980's but lower than the world average level despite high nutrient input to the system. Much of the P input was removed by adsorption, which was due to the high TPM rather than the surface activity of the particles since they had low labile Fe and low affinity for P. The sediment was a sink for P in the middle to lower reaches but not in the upper to middle reaches. TPM has been reduced by more than an order of magnitude due to artificial dams operating over recent decades. Modeling revealed that TPM of 0.2-1 g/L was a critical threshold for the Yellow River, below which most of the phosphate input cannot be removed by the particles and may cause eutrophication. These findings are important for river management and land-ocean modeling of global biogeochemical P cycling.

The surface-associated structures and growth modes of perfluorooctane sulfonate (PFOS) at water-rutile TiO2 interfaces were defined by molecular dynamics (MD) simulations. The results showed that a compact PFOS layer was generated at the rutile surfaces, and the assembling structures and dynamic profiles were crystal-face-dependent. PFOS molecules were attached to the (110) and (001) surfaces mainly by the sulfonate headgroups. A well-defined monolayer was formed on the (110) surface with the perfluorinated alkyl chains nearly perpendicular to the substrate, whereas the C-F chains were inclined at an angle (30-75°) and formed a hemicylinder-like configuration on the (001) surface. On the other hand, the perfluorinated amphiphiles interacted with the (100) plane through both the sulfonate headgroups (relatively strong electrostatic attraction) and the C-F tailgroups (weak van der Waals forces) and yielded an irregular assembling pattern. Water molecules were mostly concentrated more than 17.0 Å away from the solid surfaces and formed a continuous solvent layer, suggesting the super hydrophobicity of perfluorinated alkyl chains. A counterion-bridging mechanism suggested in surfactant adsorption was observed at the molecular scale, where the sulfonate headgroups were linked together by the potassium ions at the surfaces and caused the formation of surface aggregates., (Copyright © 2013 Elsevier Inc. All rights reserved.)

The hexadecyltrimethylammonium bromide (HDTMAB) immobilized hollow mesoporous silica spheres were prepared for the efficient removal of perfluorooctane sulfonate (PFOS) from aqueous solution. Besides the traditional sorption behavior including sorption kinetics as well as effect of solution pH and temperature, the effect of increasing volume which simulated the natural river where the rate of solute and solvent was relatively constant and solution volume was always changing was investigated. The result indicated that the residual PFOS concentrations in aqueous phase decreased with increasing solution pH and ionic strength, whereas they increased with increasing temperature. The HDTMAB immobilized material still maintained high efficiency after increasing volume, that is, the removal kept more than 99% after the treatment when the initial PFOS concentration was 1 mg L(-1). The uptake behavior and morphology of spheres which was characterized by transmission electron microscopy (TEM) revealed that the additional HDTMAB and mesoporous shell were responsible for the enhanced sorption of PFOS. It was concluded that electrostatic interaction and Ca-bridge role played an important role in the sorption of PFOS on the mesoporous SiO(2) hollow spheres, whereas, hydrophobic interaction contributed to the nice sorption performance of PFOS on the HDTMAB immobilized sorbent., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

It has been shown that starch can effectively stabilize nanoscale magnetite particles, and starch-stabilized magnetite nanoparticles (SMNP) are promising for in situ remediation of arsenic-contaminated soils. However, a molecular level understanding has been lacking. Here, we carried out XAFS studies to bridge this knowledge gap. Fe K-edge XAFS spectra indicated that the Fe-O and Fe-Fe coordination numbers of SMNP were lower than those for bare magnetite particles, and these coordination numbers decreased with increasing starch concentration. The decrease in the average coordination number at elevated stabilizer concentration was attributed to the increase in the surface-to-volume ratio. Arsenic K-edge XAFS spectra indicated that adsorbed arsenate on SMNP consisted primarily of binuclear bidentate (BB) complexes and monodentate mononuclear (MM) complexes. More BB complexes (energetically more favorable) were observed at higher starch concentrations, indicating that SMNP not only offered greater adsorption surface area, but also stronger adsorption affinity toward arsenate., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Analysis of Perfluorooctane sulfonate (PFOS) distribution in water and sediment in Yangtze River Estuary showed that the estuary was a sink for PFOS. Salinity was an important parameter in controlling the sediment-water interactions and the fate or transport of PFOS in the aquatic environment. As the salinity (S per thousand) increased from 0.18 to 3.31, the distribution coefficient (K(d)) between sediment and water linearly increased from 0.76 to 4.70 L g(-1). The study suggests that PFOS may be carried with the river water and transported for long distances before it reaches to the sea and largely scavenged to the sediment in the estuaries due to the dramatic change in salinity., (Copyright 2010 Elsevier Ltd. All rights reserved.)

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl(2) concentration increased from 0.005 to 0.5 mol L(-1) at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl(2). Maximum irreversibility was found in the sorption systems with CaCl(2) in the concentration of 0.5 mol L(-1). The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS., (Copyright 2010 Elsevier Ltd. All rights reserved.)

Composite nano-scale Fe3O4 particles were prepared in sodium carboxymethyl cellulose (CMC) solution by the oxidation deposition method. The adsorptions of phosphorus by micro-scale Fe3O4 and composite nano-scale Fe3O4 were investigated in water and soil, and the role of cellulase in the adsorption of composite nano-scale Fe3O4 was studied. Kinetic tests indicated that the equilibrium adsorption capacity of phosphorous on the composite nano-scale Fe3O4 (2.1 mg/g) was less than that of micro-scale Fe3O4 (3.2 mg/g). When cellulase was added to the solution of composite nano-scale Fe3O4 to degrade CMC, the removal rate of P by the nanoparticles (86%) was enhanced to the same level as the microparticles (90%). In the column tests, when the composite nano-scale Fe3O4 suspension was introduced in the downflow mode through the soil column, 72% of Fe3O4 penetrated through the soil bed under gravity. In contrast, the micro-scale Fe3O4 failed to pass through the soil column. The retention rate of P was 45% in the soil column when treated by the CMC-stabilized nanoparticles, in comparison with only 30% for the untreated soil column, however it could be improved to 74% in the soil column when treated by both the CMC-stabilized nanoparticles and cellulase, which degraded CMC after the nanoparticles were delivered into the soil.

Sorption behavior of phosphorus on sediment samples taken from Inner Mongolia reach of the Yellow River in 6 different geographical sites was determined in laboratory, and the correlation between chemical-physical properties of the sediments and their phosphorus sorption characteristics was analyzed. The maximum sorption capacities were 43.64-85.46 mg/kg. The zero equilibrium P concentration (EPC0) of the sediments ranged from 0.0003 to 0.0198 mg/L, which was positively correlated to the contents of native adsorbed P (NAP). The sediments played a dual role of sink and source of P at different geographical sites. Sediments from Shizuishan, Wulateqianqi and Qingshuihe along the Yellow River were sources of phosphorus, while sediments from Wuhai, Linhe and Baotou cross sections were sinks of phosphorus, at the typical P concentrations of the river water. However, both the sorption and desorption capacities were low at the conditions tested here. The Langmuir sorption constant (k) was positively correlated to the cation exchange capacity (CEC), organic matter and clay mineral content, but negatively correlated to the particle size of the sediments. The maximum sorption capacity of phosphorus was remarkably correlated to the active Fe content. Active Fe played a key role in holding phosphorus on the sediments.

The equilibrium phosphate concentration (EPC0) of the Yellow River bed sediments has been measured, which was used to predict whether bed sediments are acting as a source or sink of soluble reactive phosphate (SRP). The modified Langmuir isotherm equation was used to describe phosphate (P) sorption on the Yellow River sediments. The maximum P sorption capacity (PAC) and P-binding energy constant (k) were obtained by the modified Langmuir isotherm model. Native adsorbed exchangeable phosphorus (NAP), the EPC0, and partitioning coefficients (Kp) were subsequently calculated by the corresponding formulae. The influence of pH values and ion strength were evaluated. All the EPC0 s are higher than the P concentration in the overlying water, indicating a potential source of phosphate from the sediments. PAC is linearly related to the contents of TOC of the sediment. The sorption capacity of P increased rapidly with pH below 6.0, and then reached a plateau between pH 6.0 to 9.7, and finally maintained at a slightly higher level from pH 9.7 to 12.0.The adsorption of P by the sediment decreased with the increase in Ca2+ ionic strength.

Perchlorate has emerged as a widespread contaminant in groundwater and surface water. Because of the unique chemistry of perchlorate, it has been challenging to destroy perchlorate. This study tested the feasibility of using a new class of stabilized zero-valent iron (ZVI) nanoparticles for complete transformation of perchlorate in water or ion-exchange brine. Batch kinetic tests showed that at an iron dosage of 1.8 g L(-1) and at moderately elevated temperatures (90-95 degrees C), approximately 90% of perchlorate in both fresh water and a simulated ion-exchange brine (NaCl=6% (w/w)) was destroyed within 7h. An activation energy (Ea) of 52.59+/-8.41 kJ mol(-1) was determined for the reaction. Kinetic tests suggested that Cl(VII) in perchlorate was rapidly reduced to chloride without accumulation of any intermediate products. Based on the surface-area-normalized rate constant k(SA), starch- and CMC-stabilized ZVI nanoparticles degraded perchlorate 1.8 and 3.3 times, respectively, faster than non-stabilized ZVI particles. Addition of a metal catalyst (Al, Cu, Co, Ni, Pd, or Re) did not show any reaction improvement. This technology provides an effective method for complete destruction of perchlorate in both contaminated water and brine.

A method for the measurement of the relative toxicity of Cu2+ in aquatic environments is proposed. It is based on the quantitative measurement on the shape change of the supercoiled DNA after it is contacted with different levels of Cu2+ for various time intervals. In the absence of any redox reagents, all supercoiled DNA degraded into other forms of DNA after 24h incubation in the presence of 5.13 x 10(-3), 5.08 x 10(-4) and 5.35 x 10(-5)mol/L Cu2+. At a lower Cu2+ concentration (10(-6)mol/L), 44% of supercoiled DNA retained its original supercoiled form after 24 h, and 29% after 48 h. The concentration of RC50, i.e. concentration of pollutants at which 50% of the supercoiled DNA was relaxed compared to control samples, can be obtained from the does-response curves at different exposure time, which may provide a rapid and convenient approach to assess the relative toxicity of environmental pollutants.

Adsorption/desorption in a new Zn(II)-TiO2 adsorption system was investigated at different particle concentrations (Cp). TEM, SEM and XRD analyses revealed that the TiO2 particles were an aggregation of nano-sized (approximately 10 nm) pure anatase-type TiO2. Adsorption experiments were carried out with particle concentrations of 100, 400 and 1000 mg/L, and their adsorption isotherms were found to decline successively, showing an obvious Cp effect. Desorption experiments indicated that adsorption in this system was irreversible, and the irreversibility increased with increasing Cp. These phenomena could be explained by the MEA (metastable equilibrium adsorption) theory and the Cp effect could be modeled well with an MEA-Freundlich-type Cp effect isotherm equation. This study may help understand environmental behavior of contaminants on ultrafine natural particles.

The effective concentrations of copper on the inhibition of the growth of Scenedesmus obliquus, Chlorella pyrenoidosa and Closterium lunula at 96 h (96 h EC50) were determined to be 50, 68 and 200 microg/l, respectively. The low initial bioaccumulation of Cu by C. lunula was found to be responsible for its tolerance to Cu. The amount of Cu accumulated by all three microalgae reached the maximum value and decreased quickly after the peak followed by a slow decrease over the next 6 d. Bioaccumulation of Cu by C. lunula was directly proportional to the initial Cu concentration. After reaching the first peak after 1 d, the bioconcentration factor of Cu by microalgae declined to its minimum value during the exponential growth phase but increased in the stationary growth phase again. This indicates that desorption of Cu from microalgae was higher during the exponential growth phase but lower in the stationary growth phase. Smaller microalgae with low 96 h EC50 values are more efficient in removing Cu from wastewater.