Controlling organic carbon increase in oxygenated marine sediment by using decarburization slag.

The chemical oxygen demand (COD) in the Seto Inland Sea, Japan has increased in the recent decades due to the increase of bottom dissolved oxygen (DO) concentration which stimulated several autotrophic microorganisms, specially sulfur oxidizing bacteria (SOB). This increased SOB activity due to the oxygenation of the bottom sediment synthesized new organic matter (OM) which contributed dissolved organic carbon to the overlying seawater. This phenomenon further led to hypoxia in some subareas in the Seto Inland Sea. Higher pH or alkaline environment has been found to be an unfavorable condition for SOB. In this research, we used decarburization slag to elevate the pH of sediment to control the SOB activity and consequently reduce OM production in the sediment. Ignition loss of the surface sediment increased from 5.14% 6.38% after 21 days of incubation with aeration; whereas the sediment showed the less ignition loss of 5.71% after 21 days when the slag was incubated in the same experimental setup. Microbial community analysis showed less SOB activity in the slag added aerated sediment which accounts for the controlled increase of OM in the sediment. An additional experiment was conducted with magnesium oxide to confirm whether elevated pH can control the OM increase in sediment due to rising DO. All these results showed that decarburization slag can elevate the pH of the sediment to a certain level which can control the SOB activity followed by controlled increase of OM in the sediment. The findings may be beneficial to control accumulation of sedimentary OM which can act as a source of organic carbon in the overlying seawater.

Deterioration Mechanism of a Tertiary Polyamide Reverse Osmosis Membrane by Hypochlorite.

A tertiary polyamide membrane was synthesized using N,N'-dimethyl-m-phenylenediamine. The durability of this membrane to chlorination by hypochlorite treatment followed by sodium hydroxide treatment was examined, and then deterioration mechanisms were proposed. The tertiary polyamide membrane demonstrated better durability to free chlorine than a conventional secondary polyamide one; however, the former was deteriorated by hypochlorite for 24 h at 2000 ppm of free chlorine below pH 7.5. The salt rejection and permeation performance of the membrane were almost unchanged, and the least chlorination of the active layer occurred during hypochlorite treatment at pH 10. These results indicated that hypochlorous acid rather than hypochlorite ion was the free chlorine species that induced membrane deterioration. The deterioration became severe as chlorination progressed, resulting in collapse of the active layer below pH 7.5. Chlorination and hydrolysis of the model tertiary amide N-methylbenzanilide and Fourier transfer infrared spectroscopy of a deteriorated membrane showed that chlorination of the tertiary polyamide occurred via direct chlorination of the benzene bound to the amidic nitrogen. Silver ion probing of the deteriorated membrane revealed that amide bond scission occurred in the active layer, which might be related to the electron deficiency of the amidic nitrogen caused by chlorination of its benzene ring.

Functional Hydrogels Promote Vegetable Growth in Cadmium-Contaminated Soil.

Over the years, the concentration of cadmium in soil has increased due to industrialization. Cadmium in the soil enters the human body through plant accumulation, seriously endangering human health. In the current study, two types of hydrogels were successfully synthesized using a free radical polymerization method: an ion-type hydrogel referred to as DMAPAA (N-(3-(Dimethyl amino) propyl) acrylamide)/DMAPAAQ (N,N-Dimethyl amino propyl acrylamide, methyl chloride quaternary) and a non-ion-type hydrogel known as DMAA (N,N-Dimethylacrylamide). In the experiment carried out in this study, the ion-type hydrogel DMAPAA/DMAPAAQ was introduced to cadmium-contaminated soil for vegetable cultivation. The study found that at cadmium levels of 0 and 2 mg/kg in soil, when exposed to a pH 2 solution, cadmium wasn't detected in the filtrate using ICP. As the amount of cadmium increased to 500 mg/kg, hydrogel addition gradually reduced the filtrate cadmium concentration. Notably, the use of the 4% hydrogel resulted in 0 mg/L of cadmium. For the 0% hydrogel, vegetable cadmium absorption was determined to be 0.07 mg/g, contrasting with 0.03 mg/g for the 4% hydrogel. The DMAPAA/DMAPAAQ hydrogel significantly boosts vegetable growth by efficiently absorbing nitrate ions through ion exchange, releasing them for plant uptake. In contrast, the DMAA hydrogel, used as a control, does not enhance plant growth despite its water absorption properties. In summary, the composite hydrogel shows great potential for enhancing vegetable yield and immobilizing heavy metals in soil.

A Novel Composite Hydrogel Material for Sodium Removal and Potassium Provision.

Sodium ions are commonly found in natural water sources, and their high concentrations can potentially lead to adverse effects on both the water sources and soil quality. In this study, we successfully synthesized potassium polyacrylate (KMAA) hydrogel through free radical polymerization and evaluated its capability to remove sodium ions from and supply potassium ions to aqueous solutions. To assess its performance, inductively coupled plasma emission spectroscopy (ICP) was employed to analyze the sodium ion removal capacity and potassium ion exchange capability of the KMAA hydrogel at various initial sodium ion concentrations and pH values. The results demonstrated that the KMAA hydrogel exhibited remarkable efficiency in removing sodium ions and providing potassium ions. At pH 7, the maximum adsorption capacity for sodium ions was measured at 70.7 mg·g-1. The Langmuir model, with a correlation coefficient of 0.98, was found to be more suitable for describing the adsorption process of sodium ions. Moreover, at pH 4, the maximum exchange capacity for potassium ions reached 243.7 mg·g-1. The Freundlich model, with a correlation coefficient of 0.99, was deemed more appropriate for characterizing the ion exchange behavior of potassium ions. In conclusion, the successfully synthesized KMAA hydrogel demonstrates superior performance in removing sodium ions and supplying potassium ions, providing valuable insights for addressing high sodium ion concentrations in water sources and facilitating potassium fertilizer supply.

Dual Benefits of Hydrogel Remediation of Cadmium-Contaminated Water or Soil and Promotion of Vegetable Growth under Cadmium Stress.

This study aims to solve the problem of cadmium heavy metal ion pollution caused by the abuse of chemical fertilizers and activities such as mining, which pose a serious threat to the plant growth environment. We successfully synthesized DMAPAA (N-(3-(Dimethyl amino) propyl) acrylamide)/DMAPAAQ (N, N-Dimethyl amino propyl acrylamide, methyl chloride quaternary) hydrogels via free radical polymerization. Subsequently, we conducted experiments on this hydrogel for growing vegetables under cadmium stress conditions in aqueous solutions and soil. The cadmium capture capacity of DMAPAA/DMAPAAQ hydrogels under different cadmium ion concentrations and pH values was evaluated by using inductively coupled plasma optical emission spectrometry (ICP). The research results show that under the condition of pH = 7.3, the cadmium capture capacity of DMAPAA/DMAPAAQ hydrogels is the greatest. We used the Langmuir model to fit the adsorption data, and the correlation coefficient was as high as 0.96, indicating that the model fits well. The application of the hydrogels promoted the growth of vegetables in soil under cadmium stress conditions. The results showed that when the added amount of hydrogel was 4%, the dry weight of the vegetables was the largest. In addition, when the added amount of cadmium was 500 mg/kg and the added amount of hydrogel was 4%, the absorption of cadmium by the vegetables decreased to an undetectable level. In summary, the hydrogel successfully synthesized in this study can be effectively used to immobilize cadmium ions in soil while positively promoting the growth and yield of vegetables. This achievement has practical significance for solving the problem of heavy metal ion pollution.

Removal of Acetic Acid from Bacterial Culture Media by Adsorption onto a Two-Component Composite Polymer Gel.

Organic acids, including acetic acid, are the metabolic products of many microorganisms. Acetic acid is a target product useful in the fermentation process. However, acetic acid has an inhibitory effect on microorganisms and limits fermentation. Thus, it would be beneficial to recover the acid from the culture medium. However, conventional recovery processes are expensive and environmentally unfriendly. Here, we report the use of a two-component hydrogel to adsorb dissociated and undissociated acetic acid from the culture medium. The Langmuir model revealed the maximum adsorption amount to be 44.8 mg acetic acid/g of dry gel at neutral pH value. The adsorption capacity was similar to that of an ion-exchange resin. In addition, the hydrogel maintained its adsorption capability in a culture medium comprising complex components, whereas the ion-exchange did not adsorb in this medium. The adsorbed acetic acid was readily desorbed using a solution containing a high salt concentration. Thus, the recovered acetic acid can be utilized for subsequent processes, and the gel-treated fermentation broth can be reused for the next round of fermentation. Use of this hydrogel may prove to be a more sustainable downstream process to recover biosynthesized acetic acid.

The Removal of Hydrophobic Matter from Thermosensitive Poly[oligo(ethylene glycol) Monomethyl Ether Acrylate] Gel Adsorbent in Alcohol-Water Mixtures.

A thermosensitive gel that exhibits lower critical solution temperature (LCST) becomes hydrophilic at low temperatures and hydrophobic at high temperatures in water. A system for absorbing hydrophobic organic matters that exploits this property has been reported. While washing the gel at a low temperature with a good solvent is a possible method for removing the adsorbed matter, a process that then shrinks the gel is also required. Herein, we focused on poly[oligo(ethylene glycol) mono(m)ethyl ether acrylate] (POEGA) gels as thermosensitive gels suitable for use in this system. POEGAs are known to contain poly(ethylene glycol) (PEG) units in their side chains and exhibit upper critical solution temperature (UCST) behavior in aliphatic alcohols. By exploiting this property, we developed a method for removing hydrophobic matters that accumulate in these gels; we also evaluated the LCST and UCST behavior of POEGA gels in alcohol-water mixtures, and measured the LCSTs of these gels in water and their UCSTs in some alcohols.

Simultaneous Removal of Arsenic and Manganese from Synthetic Aqueous Solutions Using Polymer Gel Composites.

The groundwater in approximately 50% of the Bangladesh landmass contains Mn concentrations greater than the limit prescribed by the WHO drinking water guidelines. Although studies have suggested that γ-FeOOH can effectively remove Mn from water, its practicability has not been investigated, considering that the additional processes required to separate the adsorbents and precipitates are not environment-friendly. To improve the efficiency of adsorptive Mn-removal under natural conditions, we employed a cationic polymer gel composite, N,N'-Dimethylaminopropyl acrylamide, methyl chloride quaternary (DMAPAAQ) loaded with iron hydroxide (DMAPAAQ + FeOOH), and a non-ionic polymer gel composite, N,N'-Dimethylacrylamide (DMAA) loaded with iron hydroxide (DMAA + FeOOH). DMAPAAQ + FeOOH exhibited a higher As removal efficiency under natural conditions while being environment-friendly. Our results suggest that the higher efficiency of the cationic gel composite is owed to the higher γ-FeOOH content in its gel structure. The maximum adsorption of Mn by DMAPAAQ + FeOOH was 39.02 mg/g. Furthermore, the presence of As did not influence the adsorption of Mn on the DMAPAAQ + FeOOH gel composite and vice versa. DMAPAAQ adsorbed As and the γ-FeOOH particles simultaneously adsorbed Mn. Our findings can serve as a basis for the simultaneous removal of contaminants such as As, Mn, Cr, and Cd.

Synthesis of Oxidant Functionalised Cationic Polymer Hydrogel for Enhanced Removal of Arsenic (III).

A cationic polymer gel (N-[3-(dimethylamino)propyl]acrylamide, methyl chloride quaternary)(DMAPAA-Q gel)-supported oxidising agent (KMnO4 or K2Cr2O7) was proposed to remove As from water. The gel could adsorb arsenite, As(III), and arsenate, As(V), through the ion exchange method, where the oxidising agent oxidised As(III) to As(V). theoretically speaking, the amount of oxidant in the gels can reach 73.7 Mol%. The maximal adsorption capacity of the D-Mn gel (DMAPAA-Q gel carrying MnO4-) and D-Cr gel (DMAPAA-Q gel carrying Cr2O72-) for As(III) could reach 200 mg g-1 and 263 mg g-1, respectively; moreover, the As(III) removal rate of the gels could still be maintained above 85% in a neutral or weak acid aquatic solution. Studies on the kinetic and adsorption isotherms indicated that the As adsorption by the D-Mn and D-Cr gels was dominated by chemisorption. The thermodynamic parameters of adsorption confirmed that the adsorption was an endothermic process. The removal of As is influenced by the co-existing high-valence anions. Based on these results, the gels were found to be efficient for the As(III) adsorption and could be employed for the As(III) removal from the industrial wastewater.

Novel Thermosensitive-co-Zwitterionic Sulfobetaine Gels for Metal Ion Removal: Synthesis and Characterization.

Zwitterionic betaine polymers are promising adsorbents for the removal of heavy metal ions from industrial effluents. Although the presence of both negative and positively charged groups imparts them the ability to simultaneously remove cations and anions, intra- and/or inter-chain interactions can significantly reduce their adsorption efficiencies. Therefore, in this study, novel gels based on crosslinked co-polymers of thermosensitive N-isopropylacrylamide (NIPAAM) and zwitterionic sulfobetaine N,N-dimethylacrylamido propyl ammonium propane sulfonate (DMAAPS) were synthesized, characterized, and evaluated for ion removal. Fourier-transform infrared (FTIR) and proton nuclear magnetic resonance (1H NMR) analyses confirmed the success of the co-polymerization of NIPAAM and DMAAPS to form poly(NIPAAM-co-DMAAPS). The phase transition temperature of the co-polymer increased with increasing DMAAPS content in the co-polymer, indicating temperature-dependent amphiphilic behavior, as evidenced by contact angle measurements. The ion adsorption analyses of the poly(NIPAAM-co-DMAAPS) gels indicated that co-polymerization increased the molecular distance and weakened the interaction between the DMAAPS-charged groups (SO3- and N+), thereby increasing the ion adsorption. The results confirmed that, with a low concentration of DMAAPS in the co-polymer gels (~10%), the maximum amount of Cr3+ ions adsorbed onto the gel was ~58.49% of the sulfonate content in the gel.

Increase in sedimentary organic carbon with a change from hypoxic to oxic conditions.

In the Seto Inland Sea, Japan, chemical oxygen demand has increased over recent decades, while average dissolved oxygen concentrations in the bottom water have increased. In this study, we investigated responses of organic carbon (OC) in hypoxic sediment to changes of redox conditions using experimental columns containing sediment and overlying water. Surface sediment showed an increase in OC along with the change to an aerobic condition. Microbial community analysis showed a predominance of sulfur-oxidizing bacteria (SOB) such as Sulfurovum sp. in the sediment. This dominance could account for the increased OC. Additionally, the dissolved organic carbon (DOC) concentration in the overlying water increased. Further experiments using sandy sediment showed that biodegradation of Sulfurimonas denitrificans was associated with DOC release. These results show that a change in the sedimentary environment (increase in dissolved oxygen) increased the sedimentary OC and DOC of overlying water by stimulating certain autotrophic bacteria, especially the SOB.

Application of Aurantiochytrium sp. L3W for food-processing wastewater treatment in combination with polyunsaturated fatty acids production for fish aquaculture.

Thraustochytrids such as Aurantiochytrium are heterotrophic microorganisms that are known to produce valuable polyunsaturated fatty acids (PUFAs) such as docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA). In this study, Aurantiochytrium sp. strain L3W was used to remove dissolved organic carbon (DOC) and dissolved nitrogen (DN) from bean-boiling (BB) and miso-processing (MP) wastewater and to simultaneously produce PUFAs. Strain L3W removed 52% of the DOC and 37% of the DN from sterilized BB wastewater and produced biomass that contained 137 mg/g of fatty acids (FAs), including 96.2 mg/g of DHA. Growth of strain L3W in sterilized MP wastewater resulted in the production of biomass containing 147.6 mg/g of FAs, including 97.8 mg/g of DHA, and removal of 47% of the DOC and 55% of the DN from the wastewater. The biomass of strain L3W was digestible by the enzymes extracted from the stomachs of rainbow trout. These results confirmed the potential for use of strain L3W to remove DOC and DN from food processing wastewater and to produce PUFAs. This study also provided the first evidence that the raw biomass of Aurantiochytrium sp. can be used as a fish feed additive.

Synthesis, Phase-Transition Behaviour, and Oil Adsorption Performance of Porous Poly(oligo(ethylene glycol) Alkyl Ether Acrylate) Gels.

To probe the effects of pendant side-chain structures on the properties of porous thermoresponsive polymer gels, oligo(ethylene glycol) alkyl ether acrylates were polymerised in an aqueous medium under radical-mediated phase-separation conditions. The monomer structures varied according to the lengths and termini of their ethylene glycol side chains. The porous poly(oligo(ethylene glycol) alkyl ether acrylate) (POEGA) gels exhibited variable lower critical solution temperatures (LCSTs) but similar and rapid swelling-deswelling behaviours. Although the LCST of the poly(tri(ethylene glycol) monomethyl ether acrylate) (PTEGA) gel decreased with increasing aqueous NaCl or CaCl2 concentration, PTEGA showed excellent thermosensitivity in highly concentrated salt solutions, recommending its application in saline environments. Examination of PTEGA adsorption performance in an oil-water emulsion showed that n-tridecane adsorption increased with temperature. Although n-tridecane was effectively adsorbed at 70 °C, its release from the fully adsorbed PTEGA gel was difficult despite a temperature reduction from 70 to 20 °C.

Development and regeneration of composite of cationic gel and iron hydroxide for adsorbing arsenic from ground water.

Globally, arsenic contaminated groundwater is a serious concern for human health. Previous studies have developed various methods to remove arsenic. But, most of them fail to selectively adsorb arsenic and regenerate. In this study, we developed an adsorbent, a cationic polymer gel loaded with iron hydroxide, which can adsorb arsenic from groundwater more effectively than the other adsorbents. The cationic polymer gel is N,N-dimethylamino propylacrylamide, methyl chloride quaternary (DMAPAAQ). The preparation of the gel is different from the other polymer gels used for adsorption of arsenic and other metals, and it ensures that the gel contains 53.7% FeOOH particles. It should also provide good selectivity, be simple to use and be cost-effective in terms of reusability. The study showed that the gel selectively adsorbed arsenic effectively at neutral pH levels. The results demonstrate that the maximum amount of As(V) adsorption was 123.4 mg/g, which is higher than the other adsorbents. In addition, the gel adsorbed As(V) selectively in the presence of Sulphate. Also, regeneration of the gel was performed for eight consecutive days with 87.6% effectiveness. Additionally, the adsorption mechanism of this gel composite and time required for reaching the equilibrium adsorption is discussed in this paper.

Influence of Hydrophobicity of Backbone Polymer in Thermo-responsive Hydrogel with Immobilized Amine on Cycle Capacity for Absorption and Recovery of CO2.

The chemisorption process with amines is the major separation and recovery method of CO2 because of its high processing capacity and simplicity. However, large energy consumption for the desorption of CO2 is also associated with the process. To develop a separation and recovery process that is capable of desorbing CO2 at low temperatures and with minimal energy consumption, polymer hydrogels with a lower critical solution temperature (LCST) polymer network and amine groups immobilized in the polymer network of the hydrogels were exploited. Thermo-responsive amine gels with a series of hydrophobicity of polymer networks were systematically synthesized, and the influence of the hydrophobicity of the gels on the CO2 desorption temperature and cycle capacity (CO2 amount that can be separated and recovered by 1 cycle of temperature swing operation) was investigated using slurries with the series of gels. A significant decrease in the CO2 desorption temperature and increase in the cycle capacity occurred simultaneously by lowering the LCST of the gels via hydrophobisation of the polymer network. Based on an equilibrium adsorption model representing the CO2 separation and a recovery system with the gel slurries, an analysis of the system dynamics was performed in order to understand the recovery mechanism in the process.

Removal of Arsenic Using a Cationic Polymer Gel Impregnated with Iron Hydroxide.

In this work, we prepared an adsorbent composed of a cationic polymer gel containing iron hydroxide in its structure designed to adsorb arsenic from groundwater. The gel we selected was the N,N-dimethylamino propylacrylamide methyl chloride quaternary (DMAPAAQ) gel. The objective of our preparation method was to ensure the maximum content of iron hydroxide in the structure of the gel. This design approach enabled simultaneous adsorption by both the polymer structure of the gel and the iron hydroxide component, thus, enhancing the adsorption capacity of the material. To examine the performance of the gel, we measured reaction kinetics, carried out pH sensitivity and selectivity analyses, monitored arsenic adsorption performance, and conducted regeneration experiments. We determined that the gel undergoes a chemisorption process and reaches equilibrium at 10 h. Moreover, the gel adsorbed arsenic effectively at neutral pH levels and selectively in complex ion environments, achieving a maximum adsorption volume of 1.63 mM/g. The gel could be regenerated with 87.6% efficiency and NaCl could be used for desorption instead of harmful NaOH. Taken together, the presented gel-based design method is an effective approach for constructing high-performance arsenic adsorbents.

The effect of γ-FeOOH on enhancing arsenic adsorption from groundwater with DMAPAAQ + FeOOH gel composite.

Arsenic contamination of groundwater is a serious concern worldwide. The research gaps in removing arsenic are selectivity, regeneration and effective removal rate at neutral pH levels. In this study, we discussed the reasons of the high arsenic adsorption from groundwater of our previously developed adsorbent, a cationic polymer gel, N,N-dimethylamino propylacrylamide, methyl chloride quaternary (DMAPAAQ), loaded with iron hydroxide. We used a transmission electron microscope (TEM) and thermogravimetric analyser (TGA) to detect the iron contents in the gel and ensure its maximum impregnation. We found that the gel contains 62.05% FeOOH components. In addition, we used the Mössbauer spectroscopy to examine the type of impregnated iron in the gel composite and found that it was γ-FeOOH. Finally, we used Fourier transform infrared spectroscopy (FTIR) to examine the surface functional groups present in the gel and the differences in those groups before and after iron impregnation. Similarly, we also investigated the differences of the surface functional groups in the gel, before and after the adsorption of both forms of arsenic. To summarize, this study described the characteristics of the gel composite, which is selective in adsorption and cost effective, however further applications should be investigated.