苦咸水反渗透淡化中影响膜面的污染因素

由于苦咸水的化学组成和浓度分布在不同地区有着显著的差异,以及淡化工艺中普遍较高的浓缩因子(concentrate factor,CF)值(在4—10之间),苦咸水反渗透(brackish water reverse osmosis,BWRO)淡化过程中的膜污染现象、类型和程度较海水反渗透(seawater reverse osmosis,SWRO)淡化过程有明显的不同.目前,膜污染已成为BWRO大规模应用于苦咸水淡化领域的瓶颈之一,如何解决这一问题成为该领域的研究热点.本文详细综述了国内外BWRO淡化过程中影响膜面污染因素的应用研究进展,重点介绍了进水来源污染成分及污染倾向、进水水质优劣指标和进水物性对膜面污染的影响;按照分离技术的不同,分类讨论了常规预处理和膜法预处理工艺,指出后者不易受进水水质变化的影响,能够更好地降低膜面污染潜能,并针对目前的研究现状提出了建议.     

Preparation of reverse osmosis membrane with high permselectivity and anti-biofouling properties for desalination

• Nanoparticle incorporation and anti-biofouling grafting were integrated. • Flux of modified membranes was enhanced without rejection sacrificing. • Anti-biofouling property of modified membranes was improved. High performance is essential for the polyamide (PA) reverse osmosis (RO) membranes during the desalination process. Herein, RO membranes with high permselectivity and anti-biofouling properties were fabricated by nanoparticles incorporation and anti-biofouling grafting. Hydrotalcite (HT) incorporation was performed with a dual role, enhancing water flux and acting as grafting sites. The HT incorporation increased the water flux without sacrificing the salt rejection, compensating for the loss caused by the following grafting reaction. The exposed surface of HT acted as grafting sites for anti-biofouling agent dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (DMOTPAC). The combination of HT incorporation and DMOTPAC grafting endowed RO membranes with high permselectivity and anti-biofouling properties. The water flux of the modified membrane PA-HT-0.06 was 49.8 L/m²·h, which was 16.4% higher than that of the pristine membrane. The salt rejection of PA-HT-0.06 was 99.1%, which was comparable to that of the pristine membrane. As to the fouling of negatively charged lysozyme, the modified membrane’s water flux recovery was superior to that of the pristine membrane (e.g. 86.8% of PA-HT-0.06 compared to 78.2% of PA-pristine). The sterilization rates of PA-HT-0.06 for E. coli and B. subtilis were 97.3% and 98.7%, much higher than those of the pristine membrane (24.0% for E. coli and 26.7% for B. subtilis).     

Carbon nanotube- and graphene-based advanced membrane materials for desalination

The development of membrane-based desalination and water purification technologies offers new alternatives to meet the global freshwater demand. Rapid advancement in carbon nanotube-based and graphene-based nanomaterials has drawn the attention of scientific investigators on various desalination technologies. These nanomaterials indeed offer advantageous structure, size, shape, porosity and mass transport behavior for membrane separation process. This article  reviews theoretical and experimental investigations of carbon nanotube- and graphene-based composite materials for desalination. Special attention is given to the simulation of molecular transport through these materials. Further, recent advances in the application of functionalization of carbon nanotube- and graphene-based materials for salt rejection and hydraulic permeation properties are discussed.     

Sea salt bittern-driven forward osmosis for nutrient recovery from black water: A dual waste-to-resource innovation via the osmotic membrane process

• A dual “waste-to-resource” application of FO was proposed. • Performance of sea salt bittern as an economic FO draw solution was evaluated. • High quality struvite recovery from black water using FO was demonstrated. • Feed pH is a key factor to control the form of recovered phosphorous. A dual “waste-to-resource” innovation in nutrient enrichment and recovery from domestic black water using a sea salt bittern (SSB)-driven forward osmosis (FO) process is proposed and demonstrated. The performance of SSB as a “waste-to-resource” draw solution for FO was first evaluated. A synthetic SSB-driven FO provided a water flux of 25.67±3.36 L/m²⋅h, which was 1.5‒1.7 times compared with synthetic seawater, 1 M NaCl, and 1 M MgCl₂. Slightly compromised performance regarding reverse solute selectivity was observed. In compensation, the enhanced reverse diffusion of Mg²⁺ suggested superior potential in terms of recovering nutrients in the form of struvite precipitation. The nutrient enrichment was performed using both the pre-filtered influent and effluent of a domestic septic tank. Over 80% of phosphate-P recovery was achieved from both low- and high-strength black water at a feed volume reduction up to 80%‒90%. With an elevated feed pH (~9), approximately 60%‒85% enriched phosphate-P was able to be recovered in the form of precipitated stuvite. Whereas the enrichment performance of total Kjeldahl nitrogen (TKN) largely differed depending on the strength of black water. Improved concentration factor (i.e., 3-folds) and retention (>60%) of TKN was obtained in the high-nutrient-strength black water at a feed volume reduction of 80%, in comparison with a weak TKN enrichment observed in low-strength black water. The results suggested a good potential for nutrient recovery based on this dual “waste-to-resource” FO system with proper management of membrane cleaning.     

Fertilizer drawn forward osmosis as an alternative to 2nd pass seawater reverse osmosis: Estimation of boron removal and energy consumption

• The boron concentration in diluted DS can satisfy the irrigation water standard. • The boron concentration in diluted DS equaled that in two-pass RO permeate. • FDFO process SEC was slightly lower than the 2nd pass RO SEC. • FDFO has potential as an alternative to 2nd pass RO for irrigation water production. Agriculture is the largest consumer of freshwater. Desalinated seawater is an important alternative water source for sustainable irrigation. However, some issues of the current desalination technology hinder its use for agriculture irrigation, including low boron removal and high energy consumption. This study systematically explored the feasibility of employing fertilizer drawn forward osmosis (FDFO) as an alternative to 2nd pass reverse osmosis (RO) by considering the boron removal performance and specific energy consumption (SEC). Different operating conditions were investigated, such as the boron and NaCl concentrations in feed solution (FS), draw solution (DS) concentration, pH, the volume ratio of FS to DS, membrane orientation, flow rate, and operating temperature. The results indicated that a low boron concentration in FS and high pH DS (pH= 11.0) decreased the boron solute flux, and led to low final boron concentration in the DS. The other operating conditions had negligible influence on the final DS boron concentration. Also, a lower flow rate and higher specific water flux with certain permeate water volumes were conducive to reducing the SEC of the FDFO process. Overall, our study paves a new way of using FDFO in irrigation, which avoids the phytotoxicity and human health risk of boron. The results show the potential of FDFO as an alternative to 2nd pass RO for irrigation water production.     

Design of nanofibre interlayer supported forward osmosis composite membranes and its evaluation in fouling study with cleaning

• A fine fibre (40–60 nm diameter) interlayer (~1 µm thickness) was electrospun. • Fine fibre interlayer promoted formation of defect-free dense polyamide layer. • FO membrane with dual-layer substrate had less organic fouling potential. • High reverse salt flux accelerated organic fouling on FO membrane. Nanofibre-supported forward osmosis (FO) membranes have gained popularity owing to their low structural parameters and high water flux. However, the nanofibrous membranes are less stable in long-term use, and their fouling behaviours with foulants in both feed solution (FS) and draw solution (DS) is less studied. This study developed a nanofibrous thin-film composite (TFC) FO membrane by designing a tiered dual-layer nanofibrous substrate to enhance membrane stability during long-term usage and cleaning. Various characterisation methods were used to study the effect of the electrospun nanofibre interlayer and drying time, which is the interval after removing the M-phenylenediamine (MPD) solution and before reacting with trimesoyl chloride (TMC) solution, on the intrinsic separation FO performance. The separation performance of the dual-layer nanofibrous FO membranes was examined using model foulants (sodium alginate and bovine serum albumin) in both the FS and DS. The dual-layer nanofibrous substrate was superior to the single-layer nanofibrous substrate and showed a flux of 30.2 L/m²/h (LMH) when using 1.5 mol/L NaCl against deionised (DI) water in the active layer facing draw solution (AL-DS) mode. In the fouling test, the water flux was effectively improved without sacrificing the water/solute selectivity under the condition that foulants existed in both the FS and DS. In addition, the dual-layer nanofibrous TFC FO membrane was more robust during the fouling test and cleaning.     

Complete desalination of seawater using a novel polyvinylidene fluoride/zeolite membrane

Water scarcity arises rapidly with increasing human population, urbanization and industrialization. Therefore, water production from natural sources using efficient and environmental friendly technologies is gaining attention. Pervaporative desalination is a promising technology based upon membrane filtration. Here, we fabricated and tested a novel hybrid-composite membrane: polyvinylidene fluoride (PVDF)/polyvinyl pyrrolidone/(PVP)/3A zeolite. Desalination performance was evaluated in terms of flux, salt rejection, zeolite incorporation within the membrane and temperature. Results show that all membranes exhibited salt rejection higher than 99.5%. The highest flux of 2.5 kg m^?2 h^?1 and salt rejection of 99.9% were obtained using 10 wt% 3A incorporated PVDF/PVP membrane at 40 °C. The PVDF/PVP/3A zeolite membrane preserved its stability during 55-h desalination operating without performance decline.     

Surface modification of mesoporous silica nanoparticle with 4-triethoxysilylaniline to enhance seawater desalination properties of thin-film nanocomposite reverse osmosis membranes

• Mesoporous silica nanoparticle was modified with 4-triethoxysilylaniline. • AMSN-based TFN-RO membranes were prepared for seawater desalination. • Water transport capability of the AMSN was limited by polyamide. • Polyamide still plays a key role in permeability of the TFN RO membranes. Mesoporous silica nanoparticles (MSN), with higher water permeability than NaA zeolite, were used to fabricate thin-film nanocomposite (TFN) reverse osmosis (RO) membranes. However, only aminoalkyl-modified MSN and low-pressure (less than 2.1 MPa) RO membrane were investigated. In this study, aminophenyl-modified MSN (AMSN) were synthesized and used to fabricate high-pressure (5.52 MPa) RO membranes. With the increasing of AMSN dosage, the crosslinking degree of the aromatic polyamide decreased, while the hydrophilicity of the membranes increased. The membrane morphology was maintained to show a ridge-and-valley structure, with only a slight increase in membrane surface roughness. At the optimum conditions (AMSN dosage of 0.25 g/L), when compared with the pure polyamide RO membrane, the water flux of the TFN RO membrane (55.67 L/m²/h) was increased by about 21.6%, while NaCl rejection (98.97%) was slightly decreased by only 0.29%. However, the water flux of the membranes was much lower than expected. We considered that the enhancement of RO membrane permeability is attributed to the reduction of the effective thickness of the PA layer.     

Recent advances in 2D nanopores for desalination

Water shortage is a major problem facing the world today, although 70% of the earth is covered with water. With 95% of this water in seas and oceans, man has to find the most energy-efficient way of desalination for sustainable freshwater supply. Conventional desalination technologies such as reverse osmosis and thermal distillation involve large amounts of energy, especially for high salt rejection. In comparison, the discovery of two-dimensional materials such as graphene and its structural analogs boron nitride and molybdenum disulphide (MoS₂) has fostered been tremendous progress for energy-saving desalination using nanopores of these materials. This article reviews the recent developments in this technology with experimental and molecular simulation literature survey over the past few years. It explains the role of nanopores in desalination in terms of structure, energy, cost-effectiveness and process efficiency.     

Mechanism of ball milled activated carbon in improving the desalination performance of flow- and fixed-electrode in capacitive deionization desalination

● BACs were used in electrode material for both fixed and flowing electrodes. ● ASAR of FCDI and MCDI was improved by 134% and 17%, respectively. ● ENRS of FCDI and MCDI was improved by 21% and 53%. ● The mechanism of improving desalination performance was analyzed in detail. Capacitive deionization (CDI) is a novel electrochemical water-treatment technology. The electrode material is an important factor in determining the ion separation efficiency. Activated carbon (AC) is extensively used as an electrode material; however, there are still many deficiencies in commercial AC. We adopted a simple processing method, ball milling, to produce ball milled AC (BAC) to improve the physical and electrochemical properties of the original AC and desalination efficiency. The BAC was characterized in detail and used for membrane capacitive deionization (MCDI) and flow-electrode capacitive deionization (FCDI) electrode materials. After ball milling, the BAC obtained excellent pore structures and favorable surfaces for ion adsorption, which reduced electron transfer resistance and ion migration resistance in the electrodes. The optimal ball-milling time was 10 h. However, the improved effects of BAC as fixed electrodes and flow electrodes are different and the related mechanisms are discussed in detail. The average salt adsorption rates (ASAR) of FCDI and MCDI were improved by 134% and 17%, respectively, and the energy-normalized removal salt (ENRS) were enhanced by 21% and 53%, respectively. We believe that simple, low-cost, and environmentally friendly BAC has great potential for practical engineering applications of FCDI and MCDI.     

Ozonation as an efficient pretreatment method to alleviate reverse osmosis membrane fouling caused by complexes of humic acid and calcium ion

Humic acids (HA) didn’t cause obvious reverse osmosis (RO) membrane fouling in 45 h. Osmotic pressure (NaCl) affected slightly the RO membrane fouling behavior of HA. Ca²⁺ promoted aggregation of HA molecules and thus aggravated RO membrane fouling. Ozonation eliminated the effect of Ca²⁺ on the RO membrane fouling behavior of HA. The change of the structure of HA was related to its membrane fouling behavior. Humic acid has been considered as one of the most significant sources in feed water causing organic fouling of reverse osmosis (RO) membranes, but the relationship between the fouling behavior of humic acid and the change of its molecular structure has not been well developed yet. In this study, the RO membrane fouling behavior of humic acid was studied systematically with ozonation as a pretreatment method to control RO membrane fouling. Furthermore, the effect of ozone on the structure of humic acid was also explored to reveal the mechanisms. Humic acid alone (10–90 mg/L, in deionized water) was found not to cause obvious RO membrane fouling in 45-h operation. However, the presence of Ca²⁺ aggravated significantly the RO membrane fouling caused by humic acid, with significant flux reduction and denser fouling layer on RO membrane, as it was observed by scanning electron microscope (SEM) and atomic force microscope (AFM). However, after the pretreatment by ozone, the influence of Ca²⁺ was almost eliminated. Further analysis revealed that the addition of Ca²⁺ increased the particle size of humic acid solution significantly, while ozonation reduced the SUVA₂₅₄, particle size and molecular weight of the complexes of humic acid and Ca²⁺ (HA-Ca²⁺ complexes). According to these results and literature, the bridge effect of Ca²⁺ aggregating humic acid molecules and the cleavage effect of ozone breaking HA-Ca²⁺ complexes were summarized. The change of the structure of humic acid under the effect of Ca²⁺ and ozone is closely related to the change of its membrane fouling behavior.     

Biosorbents for solid-phase extraction of toxic elements in waters

Some trace metals are highly toxic for the environment. There is therefore a need for reliable methods for the determination of metals at trace levels. To this end, new sample pretreatment methods such as separation, preconcentration and speciation prior to the determination of metal ions have developed rapidly. Biosorption has become a major tool for solid-phase extraction methods. This review covers selected biosorbents such as algae, bacteria, filamentous fungi and yeasts, as new sorbents used in the solid-phase extraction of metal ions from various water sample matrices. A survey of the literature over 2004-2014 shows possible applications of selected new sorbents available for use in trace metal analysis in waters using solidphase extraction. We highlight the preconcentration of the toxic elements prior to their determination by atomic spectrometry.     

Moving policy and regulation forward for single-use plastic alternatives

Single-use plastics are often used once or cannot be reused for extended periods. They are widely consumed with the rapid development of social economy. The waste generated by single-use plastics threatens ecosystem health by entering the environment and ultimately restricts sustainable human development. The innovation of sustainable and environmentally friendly single-use plastic alternative materials and the joint participation of governments, enterprises and the public are promising technologies and management approaches that can solve the problem of single-use plastics wastes. The development of single-use plastic alternative products can be promoted fundamentally only by improving relevant legislation and standards, providing differentiated industrial policies, encouraging scientific and technological innovation and expanding public participation.     

Treatment of landfill leachates with biological pretreatments and reverse osmosis

Environmental Chemistry Letters - Landfill leachates from municipal landfills are usually heavily contaminated and thus require treatments before direct discharge into natural waters. Selecting the...     

Use of seaweeds for monitoring trace elements in coastal waters

Concentrations of a wide range of trace elements: arsenic, cadmium, cobalt, chromium, hafnium, nickel, thorium, uranium, zinc and the rare earth elements, cerium, europium, samarium, terbium and ytterbium were determined by instrumental neutron activation analysis in the brown alga,Fucus vesiculosus from Eckwarder Hörne, North Sea and from Rügen, Baltic Sea. Another brown alga,Sargassum filipendula from Sri Lanka, Indian ocean (representing an unpolluted control station) was similarly investigated. Cobalt, chromium and nickel concentrations were highest inF. vesiculosus from the North Sea while zinc was highest in samples from the Baltic Sea, reflecting high levels of these elements in coastal waters of the North and the Baltic sea. Cadmium, cobalt, nickel and zinc levels were lowest inS. filipendula from Sri Lanka, probably demonstrating lower levels of those elements in coastal waters. Concentration levels of hafnium, thorium, uranium, and the rare earth elements were highest inS. filipendula. Two years later in 1994,S. filipendula along withUlva sp. (green alga) was resampled from the same sampling site, and in addition to the above elements, six other trace elements (Ag, Ba, Br, Rb, Se and Sr) were determined.Sargassium filipendula showed a particular affinity for Ag, As, Br and Sr. For the other elements, marginal concentration differences were observed betweenS. filipendula andUlva sp., probably reflecting the regional background levels. Substantially higher concentrations of Hf, Th, U, and the rare earths were found again in the 1994Sargassum andUlva samples, reflecting the effect of a substrate rich in rare earth elements. The brown algae used in this study may be used to monitor trace elements in coastal waters.     

A modified steam distillation method for volatile acids determination in anaerobic digestors

A modified steam distillation method for the accurate determination of low levels of volatile acids found primarily in low rate anaerobic digestors has been developed. The interference of bicarbonate alkalinity is minimal with complete removal of carbon dioxide from the sample prior to distillation. This removal can be achieved by boiling the acidified sample for 30 min in an erlenmeyer flask with ground‐glass neck attached to a reflux condenser.     

Nanomaterials for water cleaning and desalination,energy production,disinfection, agriculture and green chemistry

Nanomaterials may help to solve issues such as water availability, clean energy generation, control of drug-resistant microorganisms and food safety. Here we review innovative approaches to solve these issues using nanotechnology. The major topics discussed are wastewater treatment using carbon-based, metal-based and polymeric nanoadsorbents for removing organic and metal contaminants; nanophotocatalysis for microbial control; desalination of seawater using nanomembranes; energy conversion and storage using solar cells and hydrogen-sorbents nanostructures; antimicrobial properties of nanomaterials; smart delivery systems; biocompatible nanomaterials such as nanolignocellulosis and starches-based materials, and methods to decrease the toxicity of nanomaterials. Significantly, here it is reviewed two ways to palliate nanomaterials toxicity: (a) controlling physicochemical factors affecting this toxicity in order to dispose of more safe nanomaterials, and (b) harnessing greener synthesis of them to bring down the environmental impact of toxic reagents, wastes and byproducts. All these current challenges are reviewed at the present article in an effort to evaluate environmental implications of nanomaterials technology by means of a complete, reliable and critical vision.     

水中N-亚硝胺类消毒副产物的污染现状及分析技术

N-亚硝胺是一类新兴的饮用水消毒副产物,毒性比常规的消毒副产物三卤甲烷（THMs）和卤乙酸（HAAs）更大.本文介绍了水中N-亚硝胺类消毒副产物的种类和性质,综述了水中N-亚硝胺的浓度水平及目前的分析和检测方法,指出了在N-亚硝胺的分析和检测方面有待进一步研究的方向.     

Forward osmosis coupled with lime-soda ash softening for volume minimization of reverse osmosis concentrate and CaCO3 recovery: A case study on the coal chemical industry

• Forward osmosis (FO) coupled with chemical softening for CCI ROC minimization • Effective removal of scale precursor ions by lime-soda ash softening • Enhanced water recovery from 54% to 86% by mitigation of FO membrane scaling • High-purity CaCO₃ was recovered from the softening sludge • Membrane cleaning efficiency of 88.5% was obtained by EDTA for softened ROC Reverse osmosis (RO) is frequently used for water reclamation from treated wastewater or desalination plants. The RO concentrate (ROC) produced from the coal chemical industry (CCI) generally contains refractory organic pollutants and extremely high-concentration inorganic salts with a dissolved solids content of more than 20 g/L contributed by inorganic ions, such as Na⁺, Ca²⁺, Mg²⁺, Cl⁻, and SO₄²⁻. To address this issue, in this study, we focused on coupling forward osmosis (FO) with chemical softening (FO-CS) for the volume minimization of CCI ROC and the recovery of valuable resources in the form of CaCO₃. In the case of the real raw CCI ROC, softening treatment by lime-soda ash was shown to effectively remove Ca²⁺/Ba²⁺ (>98.5%) and Mg²⁺/Sr²⁺/Si (>80%), as well as significantly mitigate membrane scaling during FO. The softened ROC and raw ROC corresponded to a maximum water recovery of 86% and 54%, respectively. During cyclic FO tests (4 × 10 h), a 27% decline in the water flux was observed for raw ROC, whereas only 4% was observed for softened ROC. The cleaning efficiency using EDTA was also found to be considerably higher for softened ROC (88.5%) than that for raw ROC (49.0%). In addition, CaCO₃ (92.2% purity) was recovered from the softening sludge with an average yield of 5.6 kg/m³ treated ROC. This study provides a proof-of-concept demonstration of the FO-CS coupling process for ROC volume minimization and valuable resources recovery, which makes the treatment of CCI ROC more efficient and more economical.     

Developments in amphibian captive breeding and reintroduction programs

Captive breeding and reintroduction remain high profile but controversial conservation interventions. It is important to understand how such programs develop and respond to strategic conservation initiatives. We analyzed the contribution to conservation made by amphibian captive breeding and reintroduction since the launch of the International Union for Conservation of Nature (IUCN) Amphibian Conservation Action Plan (ACAP) in 2007. We assembled data on amphibian captive breeding and reintroduction from a variety of sources including the Amphibian Ark database and the IUCN Red List. We also carried out systematic searches of Web of Science, JSTOR, and Google Scholar for relevant literature. Relative to data collected from 1966 to 2006, the number of species involved in captive breeding and reintroduction projects increased by 57% in the 7 years since release of the ACAP. However, there have been relatively few new reintroductions over this period; most programs have focused on securing captive‐assurance populations (i.e., species taken into captivity as a precaution against extinctions in the wild) and conservation‐related research. There has been a shift to a broader representation of frogs, salamanders, and caecilians within programs and an increasing emphasis on threatened species. There has been a relative increase of species in programs from Central and South America and the Caribbean, where amphibian biodiversity is high. About half of the programs involve zoos and aquaria with a similar proportion represented in specialist facilities run by governmental or nongovernmental agencies. Despite successful reintroduction often being regarded as the ultimate milestone for such programs, the irreversibility of many current threats to amphibians may make this an impractical goal. Instead, research on captive assurance populations may be needed to develop imaginative solutions to enable amphibians to survive alongside current, emerging, and future threats.