A new strategy for utilization of gasification ash: Manganese oxides-modified activated carbon for efficient copper citrate removal.

To address the challenges posed by solid waste generated from coal gasification ash, a pyrolysis self-activation method was employed to prepare activated carbon by gasification ash, followed by the modification with manganese oxide to enhance its adsorption performance. Subsequently, the removal efficiency and mechanism for copper citrate were investigated. The results demonstrated the successful preparation of manganese oxides modified gasification ash-derived activated carbon (GAC-MnOx), exhibiting a specific surface area of 158.3 m2/g and a pore volume of 0.1948 cm³/g. The kinetic process could be described by the pseudo-second-order kinetic model (R2 = 0.958). High removal efficiency and low concentration of dissolved Mn were observed within the pH range of 3-10, where the adsorption capacity of GAC-MnOx for copper citrate exhibited an inverse relationship with pH. Notably, the fitting results of the Langmuir model demonstrated that the maximum adsorption capacity of GAC-MnOx for copper citrate is determined to be 7.196 mg/g at pH 3. The adsorption capacity of GAC-MnOx was found to be significantly reduced to 0.26 mg/g as the pH decreased below 2, potentially attributed to the dissolution of Mn. The findings of the Dual-Mode model demonstrated that the copper citrate removal mechanism by GAC-MnOx involved both surface adsorption and precipitation processes as follows: the porous structure of activated carbon enables physical adsorption of copper citrate, the MnOx or oxygen-containing functional groups establish chemical bonds with copper citrate and subsequently precipitate onto the surface of the adsorbent. The physical adsorption remains predominant in the removal of copper citrate, despite a gradual decrease in its proportion with increasing pH and equilibrium concentrations. Moreover, the X-ray photoelectron spectroscopy results indicated that copper citrate might be oxidized by MnOx to release copper ions and be retained on the surface of the adsorbent, meaning the adsorption efficiency of Cu(II)-Cit by GAC was enhanced through MnOx oxidation. This study could provide a new strategy for the high-value resource utilization of gasification ash.

Assessment and prediction of the effect of ageing on the adsorption of nonylphenol in black carbon-sediment systems.

Black carbon (BC) is a promising sediment amendment, as proven by its considerable adsorption capacity for hydrophobic organic pollutants and accessibility, but its reliability when used for the removal of pollutants in natural sediments still needs to be evaluated. For example, the ageing process, resulting in changing of surface physicochemical properties of BC, will decrease the adsorption capacity and performance of BC when applied to sediment pollution control. In this study, how the ageing process and BC proportion affect the adsorption capacity of BC-sediment systems was modelled and quantitatively investigated to predict their adsorption capacity under different ageing times and BC additions. The results showed that the ageing process decreased the adsorption capacity of both BC-sediment systems, due to the blockage of the non-linear adsorption sites of BC. The adsorption capacity of rice straw black carbon (RC)-sediment systems was higher than that of fly ash black carbon (FC)-sediment systems, indicating that RC is more efficient than FC for nonylphenol (NP) pollution control in sediment. The newly established model for the prediction of adsorption capacity fits the experimental data appropriately and yields acceptable predictions, especially when based on parameters from the Freundlich model. However, to fully reflect the influence of the ageing process on BC-sediment systems and make more precise predictions, it is recommended that future work considering more factors and conditions, such as modelling of the correlation between the adsorption capacity and the pore volume or specific surface area of BC, be applied to build an accurate and sound model.

The effect of the ageing process on the desorption of nonylphenol in black carbon-sediment systems: a kineto-mechanistic and modeling investigation.

Black carbon (BC) exhibits promising potential as a sediment amendment owing to its commendable adsorption capacity for hydrophobic organic contaminants (HOCs), thereby resulting in HOC-laden sediments. Desorption kinetic studies play a crucial role in comprehending the release potential of HOCs from BC-sediment systems. Although the adsorption capacity of BC for HOCs has been found to decrease with aging, there is limited research on its impact on HOC desorption kinetics. In this study, BCs derived from agricultural waste (rice straw carbon, RC) and industrial waste (fly ash carbon, FC), respectively, were used to investigate the desorption kinetics of nonylphenol (NP). Additionally, a predictive model was established using the fitting parameters obtained from the modified two-domain model. The results showed that desorption of NP was divided into three fractions: rapid fraction (Frap), slow fraction (Fslow) and resistant fraction (Fr). BCs significantly decreased, while ageing increased the desorption amount and rate of NP. The performance of RC in controlling NP release was superior to that of FC. The predicted values calculated by the established model exhibit significant positive correlations with the measured values (p < 0.01). Additionally, the correlation analysis between sorption sites and desorption fractions revealed that the concentration of NP in the desorbing fraction was nearly equivalent to that of NP in partition sites within aged sediment/FC-sediment systems. However, the aged RC-sediment systems do not conform well to this rule. In other words, the estimation of NP release risk from sediments with a strong adsorbent would be overestimated, if Frap + Fsolw is considered equivalent to the desorbing fraction.

Development of a novel solid-phase extraction element for the detection of nonylphenol in the surface water of Hangzhou.

Nonylphenol (NP) is a representative environmental endocrine-disrupting chemical and persistent toxic pollutant. Previous studies have shown that the average concentration of NP in environmental waters was approximately tens to hundreds of ng L(-1) and it could even reach up to tens of µg L(-1). A simple, fast and accurate method employing a novel solid-phase extraction element named "Magic Chemisorber" (MC) followed by high-performance liquid chromatography (HPLC) using a fluorescence detector (FLD) was used for detecting NP. The most important parameters that affect the extraction process, including extraction time, desorption time, desorption solvent and repeatability, were optimized. The MC-HPLC method showed good linearity with concentrations of NP from 10 to 200 µg L(-1), a correlation coefficient of 0.9995 and the limit of detection (LOD) and limit of quantification (LOQ) of this method was 0.44 and 1.47 µg L(-1), respectively. Compared to commercial polydimethylsiloxane (PDMS) glass fiber, MC had both higher capacity and recovery and it could be used repeatedly. Using the MC-HPLC method we found that the concentration of NP in river water from Hangzhou city ranged from 8.54 ± 1.23 µg L(-1) (Qiantang River) to 65.77 ± 3.69 µg L(-1) (Tiesha River), which was similar to that of international regions heavily polluted with NP and higher than that of Bohai Bay, the Yellow River and the Pearl River Delta in China. This level of NP pollution is possibly related to the rapid development of the textile, printing and paper industries of Zhejiang province.

Aqueous Hg(II) immobilization by chitosan stabilized magnetic iron sulfide nanoparticles.

Stabilized iron sulfide (FeS) nanoparticles have been proven effective in the adsorption of Hg from the water environment. However, previous work with these nanoparticles determined that the separation from the treated water was difficult and time-consuming. In this study, nanoscale FeS-Fe3O4 nanocomposites were firstly synthesized with chitosan as the stabilizer (CTO-MFeS). Then, the Hg adsorption capacity and mechanism were studied. Results showed that the size of the prepared nanoparticles was about 20nm and the specific surface area was 21.3m2/g. Hg removal by the CTO-MFeS nanoparticles involved both adsorption and precipitation. Further investigation with XPS showed that Hg2+ was adsorbed on the surface of the CTO-MFeS nanoparticles and reacted with CTO-MFeS to form HgS and [Fe(1-x)Hgx]S. It was also found as pH decreased below 4, the adsorption capacity of CTO-MFeS was significantly reduced that might be due to the dissolving of Fe. Additionally, the presence of Cl- resulted in the transformation of Hg2+ to HgClx2-x (x=1, 2, 3, 4) that competed with OH in solution for Hg2+ and therefore inhibited the adsorption of Hg. Our findings provide additional information that may be useful for a theoretical basis for Hg treatment in water environment.

Exploration of biodegradation mechanisms of black carbon-bound nonylphenol in black carbon-amended sediment.

The present study aimed to investigate biodegradation mechanisms of black carbon (BC)-bound contaminants in BC-amended sediment when BC was applied to control organic pollution. The single-point Tenax desorption technique was applied to track the species changes of nonylphenol (NP) during biodegradation process in the rice straw carbon (RC)-amended sediment. And the correlation between the biodegradation and desorption of NP was analyzed. Results showed that microorganisms firstly degraded the rapid-desorbing NP (6 h Tenax desorption) in RC-amended sediment. The biodegradation facilitated the desorption of slow-desorbing NP, which was subsequently degraded as well (192 h Tenax desorption). Notably, the final amount of NP degradation was greater than that of NP desorption, indicating that absorbed NP by RC amendment can be degraded by microorganisms. Finally, the residual NP amount in RC-amended sediment was decided by RC content and its physicochemical property. Moreover, the presence of the biofilm was observed by the confocal laser scanning microscope (CLSM) and scanning electron microscope (SEM) so that microorganisms were able to overcome the mass transfer resistance and directly utilized the absorbed NP. Therefore, single-point Tenax desorption alone may not be an adequate basis for the prediction of the bioaccessibility of contaminants to microorganisms or bioremediation potential in BC-amended sediment.

Role of biochar in biodegradation of nonylphenol in sediment: Increasing microbial activity versus decreasing bioavailability.

The observed strong sorption of hydrophobic organic contaminants (HOCs) to biochar presents potential implications for HOCs bioavailability and bioaccessibility in sediments, while biochar could impact sediment microbial ecology. However, the comprehensive study on the effects of biochar on HOC biodegradation coupled with bioavailability and microbial ecology are rarely documented. In this paper, the effects of biochar on the biodegradation of nonylphenol (NP) were investigated using 3 different NP concentrations (20, 50 and 500 mg/Kg) in sediments amended with different percentage of rice straw biochar (RC). Results showed that the influence of RC on NP biodegradation varied with different NP concentrations. At low NP concentrations, RC suppressed NP biodegradation by reducing NP bioavailability, while at high NP concentrations, moderate RC addition promoted biodegradation by reducing toxicity of NP to microbes. The effects of NP on microbial community structures were significant (P < 0.01), but those of RC were not significant (P > 0.05). The RC affected microorganisms through altering NP toxicity, microbial quantity and activity, but not microbial community structures. This study indicated that there could be an optimal biochar percentage in biochar-sediment systems at different HOC concentrations, which strengthened HOC biodegradation process and accelerated biodegradation rate, forming adsorption-biodegradation coupled bioremediation.

Effect of rice-straw biochar on selective biodegradation of nonylphenols in isomer specificity.

In a previous study, we found that rice-straw biochar degraded and removed hydrophobic organic contaminants (HOCs) through coupled adsorption-biodegradation. However, few studies have determined whether biochar affects HOC isomer degradation and isomer-selective biodegradation or whether biochar can alter HOC isomer features, resulting in changes to HOC isomer residues in water environments. In this study, the effects of biochar at two dosages (0.001 and 0.01 g) on the biodegradation of ten isomers of a typical xenoestrogen of nonylphenol (NP) were evaluated. The results revealed that there were no effects of biochar on the adsorption of NP isomers. However, biochar addition affected the biodegradation of a specific isomer without altering the features of the NP isomers. The treatment of NP isomers with Pseudoxanthomonas sp. yielded degradation ratios ranging from 60.7 to 100%. At 0.001 g biochar treatment, the degradation of eight NP isomers was enhanced (except for NP194 and NP193a+b) due to their bulky structures. The degradation of the ten NP isomers was inhibited when 0.01 g biochar was added. These findings characterized the effects of biochar on NP isomer contaminants and provided basic information for the application of biochar for the remediation of NP isomer contaminants.

Application of Rice-Straw Biochar and Microorganisms in Nonylphenol Remediation: Adsorption-Biodegradation Coupling Relationship and Mechanism.

Biochar adsorption presents a potential remediation method for the control of hydrophobic organic compounds (HOCs) pollution in the environment. It has been found that HOCs bound on biochar become less bioavailable, so speculations have been proposed that HOCs will persist for longer half-life periods in biochar-amended soil/sediment. To investigate how biochar application affects coupled adsorption-biodegradation, nonylphenol was selected as the target contaminant, and biochar derived from rice straw was applied as the adsorbent. The results showed that there was an optimal dosage of biochar in the presence of both adsorption and biodegradation for a given nonylphenol concentration, thus allowing the transformation of nonylphenol to be optimized. Approximately 47.6% of the nonylphenol was biodegraded in two days when 0.005 g biochar was added to 50 mg/L of nonylphenol, which was 125% higher than the relative quantity biodegraded without biochar, though the resistant desorption component of nonylphenol reached 87.1%. All adsorptive forms of nonylphenol (frap, fslow, fr) decreased gradually during the biodegradation experiment, and the resistant desorption fraction of nonylphenol (fr) on biochar could also be biodegraded. It was concluded that an appropriate amount of biochar could stimulate biodegradation, not only illustrating that the dosage of biochar had an enormous influence on the half-life periods of HOCs but also alleviating concerns that enhanced HOCs binding by biochar may cause secondary pollution in biochar-modified environment.

Investigation into the feasibility of black carbon for remediation of nonylphenol polluted sediment through desorption kinetics after different order spiking.

The binding order of sorbent, sediment and organic compounds, as well as binding time is important factors determining the potential success of sorbent amendment, which should be considered when the practicability of sorbents was assessed. But until now, relevant research was rare. In this study, desorption in three practical conditions were simulated, by three mixing spiking orders among nonylphenol (NP), rice straw black carbon (RC) and sediment (the order of mixing spiking is (RC+Sediment)+NP, (Sediment+NP)+RC and (RC+NP)+Sediment, for situation I, II and III, respectively), to discuss the feasibility of using RC to remedy NP pollution. Results demonstrated that amendment of RC into sediment decreased desorption fractions of NP, and increased the resistant desorption fraction (Fr), implying strong affinity of NP to RC and efficient sequestration by RC. No significant differences were observed for desorption among the three fresh situations, meaning NP may be adsorbed on RC exterior surface sites and inter-phase diffusion is faster than desorption. However, Fr for three aged situations was in the order: situation I0.5, suggesting RC is an effective sorbent for remedying NP pollution in the aquatic environment. Overall, we proposed a practical and analytical method for properly assessing the validity of a sorbent.

Release of pentachlorophenol from black carbon-inclusive sediments under different environmental conditions.

To investigate the feasibility of using black carbon (BC) in the control of hydrophobic organic contaminants (HOCs) in sediment, we added BCs from various sources (rice straw charcoal (RC), fly ash (FC) and soot (SC)) to sediment to create different BC-inclusive sediments and studied the release of pentachlorophenol (PCP) in the sediments under different condition. Different pH values had no obvious effect on the release of PCP in BC-inclusive sediment, but solid/liquid ratio, temperature, salinity and dissolved organic matter (DOM) content had significant influences on the release of PCP in all sediments except the RC-inclusive sediment. Adding 2% RC to sediment resulted in a 90% decrease in PCP release, which was a greater decrease than observed with FC- and SC-inclusive sediments. Therefore, from the standpoint of HOC release, the application of RC is feasible for organic pollution control in the water environment.

The sorption of pentachlorophenol by aged sediment supplemented with black carbon produced from rice straw and fly ash.

Black carbon (BC) is a potential material for controlling hydrophobic organic contaminants in sediment because it has a high sorption capacity. In the present study, the sorption of pentachlorophenol (PCP) onto sediments supplemented with rice straw biochar (RC) and fly ash (FC) aged for different times and at temperatures were investigated. The sorption of PCP increased with increasing amounts of BC and decreased with aging time and storage temperature of the BC-supplemented sediments. The sorption of PCP onto RC-supplemented sediments was higher than those supplemented with FC regardless of whether or not BCs were aged in sediments. For aged sediments containing 2% BCs, the sorption capacity was 9.15- and 2.87-fold higher than that of FC when supplemented with RC aged at 25 and 45°C, respectively. Therefore, biochar is better than fly ash for controlling organic pollutants even when the RC was present in sediment for a long time.

The influence of acid demineralization on surface characteristics of black carbon and its sorption for pentachlorophenol.

Acid treatment is a routine demineralization process to obtain black carbon (BC), but there has been little systematic research about its influence on BC's characteristics. In this study, elemental analysis, SEM, FTIR, and Boehm titration were used to investigate that effect. Our results showed that the acid treatment had little influence on the sorption of fly ash and soot to pentachlorophenol (PCP), but it greatly increased the sorption of rice chars to PCP. There were two competing effects of acid demineralization on the adsorption capacity of BC. On one hand, it increased the amount of the acidic functional groups, which decreased the adsorption capacity. On the other hand, it increased the surface and pore volume of BC and caused the emergence of hidden carbon enclosed by minerals, which in turn increased the sorptivity significantly. Especially for rice chars (600°C), after acid treatment, their surface area increased from 3.52 to 235 m(2) g(-1) and the sorption capacity coefficient increased from 2.12 to 4.10.