Insights into the photosensitivity and photobleaching of dissolved organic matter from microplastics: Structure-activity relationship and transformation mechanism.

Revealing the structure-activity relationship between physicochemical properties and photoactivities of microplastic dissolved organic matter (MPDOM) is significant for understanding the environmental fate of MPs. Here, we systematically analyzed the physicochemical properties and molecular composition of DOM derived from MPs including polystyrene (PS), polyethylene glycol terephthalate (PET), polyadipate/butylene terephthalate (PBAT), polylactic acid (PLA), polypropylene (PP), and compared their photosensitivity and photobleaching behaviors. Results indicated that PSDOM and PETDOM had more similar properties and compositions, and showed stronger photosensitivity and photobleaching effects than PBATDOM, PLADOM and PPDOM. The [3DOM∗]SS and [1O2]SS varied in the range of 0.31-13.03 × 10-14 and 1.71-5.49 × 10-13 M, respectively, which were within the reported range of DOM from other sources. The SUVA254, HIX, AImodwa, Xcwa and lignin/CRAM-like component showed positive correlation with the [3DOM∗]SS, [1O2]SS and Φ3DOM*. The negative correlation between E2/E3 and [3DOM∗]SS was due to the higher proportion of low-molecular weight components in MPDOM. The lignin/CRAM-like component was identified to be the crucial photobleaching-component. The lignin/CRAM-like in PSDOM showed a deepened oxidation degree, while its change trend in PETDOM was from unsaturated to saturated. These findings provide new insights into the relevant photochemical fate of MPDOM.

The mechanism differences between sulfadiazine degradation and antibiotic resistant bacteria inactivation by iron-based graphitic biochar and peroxydisulfate system.

In this study, the activation of peroxydisulfate (PS) by K2FeO4-activation biochar (KFeB) and acid-picking K2FeO4-activation biochar (AKFeB) was investigated to reveal the mechanism differences between iron site and graphitic structure in sulfadiazine (SDZ) degradation and ARB inactivation, respectively. KFeB/PS and AKFeB/PS systems had similar degradation property towards SDZ, but only KFeB/PS system showed excellent bactericidal property. The mechanism study demonstrated that dissolved SDZ was degraded through electron transfer pathway mediated by graphitic structure, while suspended ARB was inactivated through free radicals generated by iron-activated PS, accompanied by excellent removal on antibiotic resistance genes (ARGs). The significant decrease in conjugative transfer frequency indicated the reduced horizontal gene transfer risk of ARGs after treatment with KFeB/PS system. Transcriptome data suggested that membrane protein channel disruption and adenosine triphosphate synthesis inhibition were key reasons for conjugative transfer frequency reduction. Continuous flow reactor of KFeB/PS system can efficiently remove antibiotics and ARB, implying the potential application in practical wastewater purification. In conclusion, this study provides novel insights for classified and collaborative control of antibiotics and ARB by carbon-based catalysts driven persulfate advanced oxidation technology.

From waste corn straw to graphitic porous carbon: A trade-off between specific surface area and graphitization degree for efficient peroxydisulfate activation.

Electron transfer pathways have been verified as overriding regimes when peroxydisulfate (PDS) was activated by porous carbon. The incorporation of graphitic structure into carbon matrix was favorable to the rapid electron transfer, but excessive graphitization would deteriorate the specific surface area (SSA), weakening the catalytic performance. The reasonable trade-off between SSA and graphitization degree was necessary and challenging for the preparation of efficient carbon based PS-activators. Herein, a series of graphitic porous carbon with discrepant SSA and graphitic structure were fabricated. The incorporation of graphitization tracks into ultra-thin edges on porous carbon film was verified by multifarious structural characterization. After trade-off, the optimum catalyst exhibited superior catalytic performance with degradation rate constant (kobs) exceeding that of ungraphitized precursor by up to 16.0 times. Mechanistic investigations substantiated that the sufficient SSA of catalyst provided favorable conditions for its affinity towards PDS and sulfadiazine (SDZ), resulting in the formation of PDS* complexes and SDZ adsorption, while the appropriate graphitization degree ensured the reinforced electron transfer rate, which collectively accelerated SDZ oxidation through electron-transfer pathway. The multivariate linear regression model linking kobs to SSA and graphitization degree was established providing basis to construct efficient catalysts for PDS activation.

Efficient adsorption of chloroquine phosphate by a novel sodium alginate/tannic acid double-network hydrogel in a wide pH range.

In this work, a novel double-network composite hydrogel (SA/TA), composed of sodium alginate (SA) and tannic acid (TA), was designed and fabricated by a successive cross-linking method using Ti(IV) and Ca(II) as crosslinkers. SA/TA exhibited reinforced mechanical strength and anti-swelling properties because of the double-network structure. SA/TA was used as an adsorbent for removal of a popular antiviral drug, chloroquine phosphate (CQ), in water. The adsorption performance of SA/TA was systematically investigated, to study various effects including those of TA mass content, solution pH, adsorption time, and initial CQ concentration. Adsorption was also examined in presence of inorganic and organic coexisting substances commonly found in wastewater, and under different actual water samples. Batch experimental results indicated that SA/TA could maintain higher and more stable CQ uptakes within a wide solution pH range from 3.0 to 10.0, compared to its precursor, SA hydrogel, owing to the addition of TA-Ti(IV) coordination network. The maximum experimental CQ uptake exhibited by the 1:1 (by wt) SA/TA (SA/TA2) was as high as 0.699 mmol/g at the initial pH of 9.0. A high concentration of coexisting NaCl evidently reduced the CQ uptakes of SA/TA2 due to the electrostatic shielding effect, moreover, divalent cations including Ca(II) and Mg(II) also inhibited the adsorption of CQ due to competitive adsorption. However, humic acid had little effect on this adsorption. Considering the apparent adsorption performance, the aforementioned effects of various factors and the spectroscopic characterizations, multi-interactions are suggested for adsorption including chelation, electrostatic interactions, π-π electron donor-acceptor interaction and hydrogen bonding. SA/TA showed a slight loss in adsorption capacity toward CQ and sustained physicochemical structural stability, even after six adsorption-desorption cycles. In addition to CQ, SA/TA could be efficiently used for adsorption of two other antivirus drugs, namely, hydroxychloroquine sulfate and oseltamivir phosphate. This work provides an effective strategy for the design and fabrication of novel adsorbents that can effectively adsorb antiviral drugs over a wide pH range.

Fabrication of environmentally-friendly composited sponges for efficient removal of fluoroquinolones antibiotics from water.

In this study, two environmentally-friendly macroscopically formal (PVF) composited sponges (PL and PLS) functionalized with lignin and lignosulfonate, respectively, were fabricated by a one-step mechanical foaming method. PLS, obtained with the fed mass ratio of 0.3:1 lignosulfonate to PVF in the preparation process, possessed a large specific surface area of approximately 22.396 m2/g, a three-dimensional skeleton structure with a skeletal density of 3.236 g/cm3, and 0.338 mmol/g of acidic oxygen-containing groups. Thus, it showed a high adsorption capacity of 0.16-0.24 mmol/g in removing seven antibiotics, of the popular fluoroquinolones (FQs) family from water. The contributions of hydrogen bonding, electrostatic attraction (EA) and π-π electron donor-acceptor interaction to the adsorption of FQs onto the PL and PLS sponges were analyzed systematically by investigating the pH dependence of the adsorption capacity, and the changes in adsorption of two sub structural analogs of FQs as molecular probes, and by performing theoretical calculations. The EA between the acidic oxygen-containing groups on the sponges and the amino groups of FQs played a dominant role in adsorption in near neutral conditions, leading to a superior adsorption performance for PLS. Overall, the composited sponges have the advantages of simple production, environmental-friendliness, convenient recycle, and low cost, which renders them potentially viable in treating real wastewater containing FQs.

Selective adsorption of ofloxacin and ciprofloxacin from a binary system using lignin-based adsorbents: Quantitative analysis, adsorption mechanisms, and structure-activity relationship.

A series of actinia-shaped lignin-based adsorbents (LNAEs) featuring lignin (LN) as the core and grafted poly(acrylic acid) (PAA) as the tentacle were designed and fabricated. Two fluoroquinolones (FQs) with similar molecular structures, ofloxacin (OFL) and ciprofloxacin (CIP), were used as targets to study the selective adsorption performance of LNAEs associated with the structural effects of the LN-based adsorbents in FQs binary aqueous system. The adsorption of the two FQs by LNAEs complied with the competitive Langmuir isothermal model, and showed selective removal of CIP over OFL due to the additional negative charge-assisted hydrogen bond (CAHB) formed between the carboxyl group of LNAEs and the secondary amino group of CIP, in addition to the effects of electrostatic attraction and normal hydrogen bonds, according to quantitative studies and density functional theory analysis. A binary nonlinear model based on phenomenological theory was applied to study the effects of PAA branched-chain length and distribution on the selective adsorption performance of the LN-based adsorbents. Accordingly, the branched-chain distribution played a more important role and higher distribution density of branched PAA could expose more adsorption sites on LNAEs' surface and improve the adsorptive selectivity. This study offers a well understanding of the structure-activity relationship of the surface grafting-modified adsorbents in binary pollutant systems and fundamental guidance for the exploitation and design of novel and efficient adsorbents.

Removal of fluoroquinolone antibiotics using actinia-shaped lignin-based adsorbents: Role of the length and distribution of branched-chains.

A series of actinia-shaped lignin-based adsorbents (LNAEs) featuring lignin(LN) as the core and grafted poly(acrylic acid) (PAA) as the tentacle were designed and fabricated. LNAEs were applied to remove ofloxacin and ciprofloxacin from water, and their maximum adsorption capacities were 0.835 and 0.965 mmol/g at pH 6.0, respectively. However, their adsorption capacities were up to about 20 % and 31 % reductions in the present of NaCl and humic acid, respectively. Electrostatic attraction (EA) and hydrogen bonding (HB), including ordinary HB and negative charged auxiliary HB, were mainly involved in adsorption. Experimental and calculation results indicated HB contributes more than EA. The effects of two structural factors of LNAEs, namely, PAA branched-chain length(L) and distribution density(D), on the adsorption performance associated with HB and EA, were quantitatively discussed using a binary nonlinear model based on phenomenological theory. The fitting results were completely consistent with the experimental findings. D was more efficient than L in promoting HB and EA in adsorption due to the cooperative effects of adjacent branched-chains and enhanced activity of terminal groups. This study provides a better understanding of the structure-activity relationship of surface grafting-modified adsorbents and fundamental guidance for the exploitation and design of novel and efficient adsorbents.

Evaluation of the selective adsorption of silica-sand/anionized-starch composite for removal of dyes and Cupper(II) from their aqueous mixtures.

A silica-sand/anionized-starch composite (CMS-SS) was prepared simply. CMS-SS was used as an efficient adsorbent for removal of cationic dyes [methyl blue (MB) and crystal violet (CV)] and metal ions [cupper(II), Cu(II)] from water in respective single and binary systems. Compared with the anionized-starch without silica sand, CMS-SS shows evidently improved adsorption capacities, i.e. approximately 653.31 ± 27.30, 1246.40 ± 34.10, and 383.08 ± 13.50 mg·g-1, for MB, CV, and Cu(II), respectively, ascribed to the additional carboxyl groups. The isotherms and kinetics study indicated that the Langmuir model and the pseudo-second-order model were more suitable. The adsorption process is thus a homogeneous monolayer chemisorption. The adsorptions of these three pollutants are spontaneous and exothermal processes driven by increasing entropy. The adsorption behaviors of CMS-SS have high pH dependence, and electrostatic attraction play an important role in adsorption. Dyes showed higher affinity to CMS-SS than metal ions causing a preferential adsorption of dye over Cu(II) in their aqueous mixture. This adsorbent after saturated adsorption could be rapidly separated from water due to its enlarged density after embedded silica sand; moreover, those rapidly recovered adsorbents were tried to use as new adsorbents for removal of an anionic dye from water due to the complete changes in their surface structures after saturated adsorption.

Investigation of multiple adsorption mechanisms for efficient removal of ofloxacin from water using lignin-based adsorbents.

Two series of lignin (LN)-based adsorbents, namely, cross-linked lignin (LNEs) with different crosslinking densities and carboxymethyl cross-linked lignin (LNECs) with various degrees of carboxymethyl substitution, were prepared to remove ofloxacin (OFL), a popular fluoroquinolone (FQ) antibiotic, from water. LNEs and LNECs exhibited satisfactory performance in OFL adsorption. Both of them had high adsorption capacity (the maximum contribution of 0.828 mmol/g), good anti-interference to some inorganic salts, and efficient regeneration and reuse performance. The crosslinking density and degree of carboxymethyl substitution strongly affected the content and distribution of oxygen-containing groups in these LN-based adsorbents, which played important roles in OFL adsorption. The pH dependencies of the adsorption performance of LNEs and LNECs indicated the involvement of multiple adsorption mechanisms, including hydrogen bond, electrostatic attraction, π-π electron-donor-acceptor interactions, and negative charge-assisted hydrogen bond. Different mechanisms were dominant under various pH levels, in a near neutral pH, the synergistic effect of electrostatic attraction and π-π interaction allows LINEs and LINECs to reach maximum adsorption capacity. Five FQs with similar structures and their two sub structural analogs were compared in terms of adsorption behavior and electrostatic potential by density functional theory using quantum chemical calculation. FQs with secondary amino groups and low π electron cloud density readily bound to LN-based adsorbents. Hence, LNEs and LNECs were efficient and environment-friendly adsorbents.

Coagulation/flocculation in dewatering of sludge: A review.

Sludge disposal is an integral part of wastewater treatment systems, and its cost usually accounts for more than half of the total operation cost. Sludge disposal technology is facing challenges and opportunities simultaneously and can still be improved. Sludge dewatering is an essential process in sludge disposal, and it is important for the effective reduction of the final processing cost. Coagulation/flocculation is a relatively mature, cost-effective, user-friendly sludge dewatering technology. In this work, coagulation/flocculation and their combinations with other pretreatments, including dewatering mechanisms, are reviewed. Various coagulants/flocculants used in sludge dewatering, including inorganic coagulants, organic synthetic and natural polymeric flocculants, and bioflocculants, are introduced in detail because coagulants/flocculants are the key in coagulation/flocculation. The different factors that influence the dewatering performance of these coagulants/flocculants are also presented briefly. Moreover, aiming at the complicated composition of sludge and its treatment difficulty, the prospects and technical developments of coagulation/flocculation in sludge dewatering are discussed.