Sludge-derived iron-carbon material enhancing the removal of refractory organics in landfill leachate: Characteristics optimization, removal mechanism, and molecular-level investigation.

Mature landfill leachate is a refractory organic wastewater, and needs physical and chemical pretreatments contemporaneously, e.g. iron-carbon micro-electrolysis (IC-ME). In this study, a novel iron-carbon (Fe-C) material was synthesized from waste activated sludge to be utilized in IC-ME for landfill leachate treatment. The pyrolysis temperature, mass ratio of iron to carbon, and solid-liquid ratio in leachate treatment were optimized as 900 °C with 1.59 and 34.7 g/L. Under these optimal conditions, the chemical oxygen demand (COD) removal efficiency reached 79.44 %, which was 2.6 times higher than that of commercial Fe-C material (30.1%). This excellent COD removal performance was indicated to a better mesoporous structure, and uniform distribution of zero-valent iron in novel Fe-C material derived from sludge. The contribution order of COD removal in IC-ME treatment for landfill leachate was proven as coagulation, adsorption, and redox effects by a contrast experiment. The removal of COD includes synthetic organic compounds, e.g. carcinogens, pharmaceuticals and personal care products. The contents of CHO, CHON, and CHOS compounds of dissolved organic matter (DOM) in the leachate were decreased, and both the molecular weight and unsaturation of lipids, lignin, and tannic acids concentration were also reduced. Some newly generated small molecular DOM in the treated leachate further confirmed the existence of the redox effect to degrade DOM in leachate. The total cost of sludge-derived Fe-C material was only USD$ 152.8/t, which could save 76% of total compared with that of commercial Fe-C materials. This study expands the prominent source of Fe-C materials with excellent performance, and deepens the understanding of its application for leachate treatment.

Enhanced silicon bioavailability of biochar derived from sludge conditioned with Fenton's reagent and lime.

Biological wastewater treatment generates a large quantity of sewage sludge that requires proper treatments. In this study, the biochar pyrolyzed by sludge conditioned with Fenton's reagent and lime (referred to as Fenton-lime system) was first used as an efficient silicon fertilizer for rice cultivation. When the pyrolysis temperature was 750 °C, the dissolved silicon and available silicon contents in biochar derived from sludge conditioned with Fenton-lime system were much higher than those in raw sludge derived biochar without conditioning (3.49 vs. 0.72, 77.25 vs. 2.33 mg/g dry solid, respectively). The enhanced available silicon content was attributed to the newly formed calcium aluminosilicate from the reactions between the added lime and silicon-rich phases in sludge. The rice cultivated with biochar derived from Fenton-lime conditioned sludge showed improved biomass of stem and root by 76.85% and 36.11%, respectively, compared to blank group without the addition of Si source. Heavy metals and the reactive oxygen species (ROS) accumulation in rice were not observed after a culture period of 30 days in the application of sludge-derived biochar as silicon fertilizer. This study provides a promising approach for sewage sludge recycling as an efficient silicon fertilizer in silicon-deficiency land.

Recirculation of reject water in deep-dewatering process to influent of wastewater treatment plant and dewaterability of sludge conditioned with Fe2+/H2O2, Fe2+/Ca(ClO)2, and Fe2+/Na2S2O8: From bench to pilot-scale study.

Deep dewatering of sewage sludge pretreated with advanced oxidation processes (AOPs) is a strategy for efficient sludge reduction and subsequent disposal. The pretreatment and dewatering performance of sludge conditioned with three types of AOPs (Fe2+/H2O2, Fe2+/Ca(ClO)2, and Fe2+/Na2S2O8), compared with sludge conditioned with traditional conditioner (Fe3+/CaO), were investigated in both bench and pilot-scale tests. All of those conditioner systems could reduce the water content of dewatered sludge cake to below 60 wt% in bench-scale (about 16 kg raw sludge per round) and pilot-scale (approximate 800 kg raw sludge per round) diaphragm filter press dewatering. Compared with raw sludge, the deep-dewatering filtrate after different conditioning and dewatering processes had higher ammonia nitrogen (NH4+-N) and chemical oxygen demand (COD) contents due to the degradation of organic matter, and much lower total phosphorus (TP) content due to the formation of iron phosphate precipitate. A better biodegradability (i.e. higher BOD5/COD ratio) was found in the deep-dewatering filtrate of sludge conditioned with Fe2+/H2O2 (25.2 %) and Fe2+/Ca(ClO)2 (17.4 %). Most of the heavy metals (Cr, Cu, Ni, and Pb) (>79 wt%) have remained in the dewatered sludge cake, and most of the Cl element (>90 wt%) in the sludge pretreated by Fe2+/Ca(ClO)2 and Fe3+/CaO was kept in the filtrate, rather than the dewatered sludge cake. Based on the pilot-scale experimental results, if all the filtrate in the deep-dewatering process returned to the influent of WWTP, the loading ratios of TP, NH4+-N, COD in the four conditioner systems were less than 3 wt%. The above results proved that the AOPs conditioned sludge could achieve deep-dewatering in pilot-scale and the direct recirculation of deep-dewatering filtrate to the influent of wastewater treatment plant was feasible.

Enhancing waste activated sludge dewaterability by reducing interaction energy of sludge flocs.

How to efficiently improve waste activated sludge (WAS) dewaterability is a common challenge in WAS treatment and management throughout world. The interaction energy of sludge flocs is of great importance for sludge dewaterability. In this study, the relationship among the repulsive force of sludge flocs, hydrophilic/hydrophobic characteristics of sludge flocs, and sludge dewaterability have been quantitatively and qualitatively investigated based on extended Derjaguin-Landau-Verwey-Overbeek theory for the first time. The energy barrier of sludge flocs has good correlations with sludge dewaterability (p < 0.05). Trivalent cations (Al3+ and Fe3+) and Fenton's reagent reduced the interfacial free energy (ΔG) from 9.4 mJ/m2 of raw sludge to -34.2 (Al3+), -60.5 (Fe3+), and -63.2 (Fenton) mJ/m2, respectively, indicating that the hydrophilic surfaces of the sludge flocs converted to hydrophobic (△G < 0), and decreasing Lewis acid-base interaction energy (WAB) of sludge flocs. In addition, most of the trivalent cations (Al3+ and Fe3+) were attached to sludge flocs, leading to neutralize negative charges and mitigate electrostatic interaction energy (WR) of sludge flocs. The reduction of WAB and WR eliminated energy barrier of sludge flocs and repulsive force between sludge flocs. In comparison, monovalent (Na+ and K+) and bivalent (Ca2+ and Mn2+) cations cannot completely change the hydrophilic surface characteristic and negative charge of sludge flocs. The existed energy barrier prevented sludge flocs to agglomerate with each other, thus resulting in a worse dewaterability. This study illustrated that reducing interaction energy of sludge flocs played a critical role to improve sludge dewaterability.

Improvement of sludge dewaterability by ammonium sulfate and the potential reuse of sludge as nitrogen fertilizer.

A novel method to enhance sludge dewaterability with ammonium sulfate ((NH4)2SO4) was proposed, and the potential reuse of dewatered sludge cake and filtrate as nitrogen fertilizers was evaluated. Compared with raw sludge, 87.91% reduction of capillary suction time (CST) and 88.02% reduction of specific resistance to filtration (SRF) after adding 80% (m/m) (NH4)2SO4 were achieved, with 38.49% of protein precipitated simultaneously. The (NH4)2SO4 dose destroyed cell membrane, resulting in the release of intracellular water by converting bound water into free water, thus enhancing sludge dewaterability. In the solid phase, the content of protein-N increased, and larger protein aggregates were formed. The (NH4)2SO4 dose destroyed the hydration shell, making proteins to exhibit hydrophobic interactions, and to be aggregated, and precipitated from the liquid phase. When incubated Pennisetum alopecuroides L. with the dewatered sludge cake and filtrate after dewatering and conditioning with (NH4)2SO4, the germination rate of grass seed and shoot lengths both increased while compared with those incubated with dewatered sludge cake and filtrate of the raw sludge. This study might provide insights into sustainable sludge treatment by integrating sludge dewatering and the potential reuse of dewatered sludge cake and filtrate as nitrogen fertilizer via treatment with (NH4)2SO4.

Enhanced sludge dewaterability with sludge-derived biochar activating hydrogen peroxide: Synergism of Fe and Al elements in biochar.

Reuse of sludge-derived Fe-rich biochar as sludge conditioner is an attractive route for management of waste activated sludge at source. Homogeneous and heterogeneous Fenton reactions have been proved in sludge conditioning with Fe-rich biochar activating H2O2 to enhance sludge dewaterability. The FeAl2O4 phase in Fe-rich biochar was first identified during pyrolysis of sewage sludge after adding both Fe2O3 and Al2O3, since Fe and Al elements are two of major metal elements in Fe-rich sludge. Compared with the Fe-rich biochar that did not comprise FeAl2O4 phase, the capillary suction time (CST) and specific resistance to filterability (SRF) of the sludge conditioned with the Fe-rich biochar comprising FeAl2O4 phase could be efficiently decreased by 23% and 44%, respectively. The results indicated that FeAl2O4 phase in Fe-rich biochar could improve sludge dewaterability by enhancing heterogeneous Fenton reaction. Synergistic effect between Fe and Al in FeAl2O4 contributed to weak the O-O bond in H2O2 and reduce the activation energy of H2O2 decomposition for enhancing ·OH generation, which could be explained by density functional theory (DFT) calculations for the first time. Thus, the decomposition rate of H2O2 and the amount of ·OH generation were obviously promoted by FeAl2O4 phase in sludge-derived biochar during sludge conditioning, attributing to the destruction of sludge flocs, the release of bound water, and the improvement of sludge dewaterability.

Sludge-derived biochar with multivalent iron as an efficient Fenton catalyst for degradation of 4-Chlorophenol.

Fe-rich biochar with multivalent iron compounds (Fe0, Fe0.95C0.05, Fe3O4, and FeAl2O4) pyrolyzed from sludge cake conditioned with Fenton's reagent and red mud was utilized as an efficient Fenton catalyst for the degradation of 4-chlorophenol (4-CP). Effects of pyrolysis temperature and sludge conditioner composition on the transformation of iron compounds were studied. Both homogeneous Fenton reaction initiated by Fe2+ leached from both low-valent Fe0 and Fe0.95C0.05, and heterogeneous Fenton reaction initiated by solid iron phases of Fe3O4 and FeAl2O4 were revealed to contribute to the degradation of 4-CP. The removal efficiency of 4-CP remained 100% after five successive degradation rounds. The homogeneous Fenton reaction mainly works in the first degradation round, and the heterogeneous Fenton reaction dominates in subsequent degradation rounds. The findings of this study suggest that sewage sludge derived Fe-rich biochar could be utilized as an efficient Fenton catalyst for recalcitrant organics degradation.

Profiling of amino acids and their interactions with proteinaceous compounds for sewage sludge dewatering by Fenton oxidation treatment.

During advanced oxidation treatment for enhancing sludge dewaterability, the peptide chains of protein can be decomposed into amino acids. Protein exhibits a great impact on sewage sludge dewaterability. However, the role of amino acids in sludge dewatering remains unclear. In this study, among the 23 types of amino acids investigated, tryptophane (Trp) and lysine (Lys) were identified as the key amino acids affecting sludge dewaterability during Fenton oxidation treatment. The content of lysine showed positive correlations with capillary suction time (CST), specific resistance to filtration (SRF), and bound water content, and the concentrations of total protein, low molecular weight protein, amines and amides, and 3-turn helix of proteinaceous compounds in bound extracellular polymeric substances (EPS), while the content of tryptophane showed negative correlations with the above parameters. The amino acids may be sourced from damage of the membrane and ribosomal proteins by hydroxyl radicals, and the peptide bonds connected with tryptophane were more inclined to be decomposed than other amino acids. Particularly, more amino acids of tryptophane can result in more hydrophobic interaction, and less necessary energy barrier for aggregation of particles. As such, regulating protein degradation towards production of tryptophane may be related with enhanced sludge dewaterability by Fenton oxidation treatment.

A one-step acidification strategy for sewage sludge dewatering with oxalic acid.

Sewage sludge dewatering is an efficient approach to reduce the volume of sludge for the subsequent disposal. In this study, a novel one-step acidification sludge dewatering method was developed with using oxalic acid as a conditioner. In laboratory-scale experiments with the dosage of 200 mg/g dry solid (DS), the normalized capillary suction time and the specific resistance to filtration were respectively decreased by 78.7% and 60.0% after 30 min of oxalic acid conditioning, much more efficient than those conditioned with sulfuric acid and hydrochloric acid at the same pH value. This superior dewatering performance was attributed to two factors. One was that oxalic acid could more efficiently promote the hydrolysis of polysaccharide, especially pectins, to release bound water. The other was that OA could dissolve more Fe3+ and Al3+, as well as form precipitate with Ca2+ in sludge, which may act as flocculants or co-precipitator for the subsequent sludge particles coagulation. In pilot-scale experiments, the water content of oxalic acid conditioned sludge cake was reduced to 60% under the optimum conditions, while the reagent cost was as low as 110.0 USD/t DS. This work provides a cost-effective and easy-operated sewage sludge disposal technique, and also sheds light on the potential of oxalic acid in environmental waste treatment.

A comparison between sulfuric acid and oxalic acid leaching with subsequent purification and precipitation for phosphorus recovery from sewage sludge incineration ash.

Wet chemical approach is widely applied for P extraction from incinerated sewage sludge ash (ISSA) due to the relatively simple process and low lost. In this study, H2SO4 and H2C2O4 were compared to recover P from ISSA through three steps of acid leaching, cation exchange resin (CER) purification and precipitation. Transformations of P speciation and mineral phases in ISSA from 600 to 900 °C were studied. The results showed that the ISSA samples were mainly composed of inorganic P (IP), and part of non-apatite IP (NAIP, mainly AlPO4) would transform to apatite P (AP, Ca3(PO4)2) with the increase in temperature. The ratio of NAIP to IP dropped from 71.9% at 600 °C to 53.7% at 900 °C. Effect of acid concentration on the leaching efficiency of P from the ISSA samples incinerated at different temperatures by H2SO4 and H2C2O4 was investigated, and the leaching behaviors of key elements of P, Ca, Al and Fe were compared. H2C2O4 exhibited a better performance than H2SO4 for the leaching efficiency of P. Severe sintering of ash particles occurred at temperature >800 °C inhibited the P leaching by H2SO4. During CER purification, the impurity elements in the H2SO4 leachate were easily removed by CER, whereas the Al and Fe elements in the H2C2O4 leachate were hardly removed due to the formation of anionic complexes between Al3+/Fe3+ and oxalic ions. Finally, high-purity struvite product was synthesized from the purified H2SO4 leachate, which could be directly utilized as a fertilizer with negligible environmental risk. Amorphous aluminum and iron hydroxyphosphates were obtained from the H2C2O4 leachate. This study provides insights for P recovery from ISSA samples by different acid leaching systems.

Correlation between oxidation-reduction potential values and sludge dewaterability during pre-oxidation.

Pre-oxidation is effective in enhancing sludge dewaterability. Different types and doses of oxidants are used to improve sludge dewaterability in pre-oxidation. Rapid evaluation of the sludge dewaterability is vital for optimizing the type and dose of oxidants in pre-oxidation. It normally takes more time to evaluate sludge dewaterability by measuring typical indicators such as specific resistance to filtration (SRF), content of bound water, and composition of EPS. This study presented a rapid parameter, oxidation-reduction potential (ORP), to correlate it with the dewaterability of pre-oxidized sludge samples. An index of ΔORP (ΔORP = ORPt=0.5 min-ORPt=0 min) showed positive correlations with SRF (r = 0.89, p < 0.05), content of total organic carbon in soluble and loosely-bound EPS (r = 0.86 and 0.84, p < 0.05), zeta potential (r = 0.86, p < 0.05), and content of Fe(III) in the sludge cake (r = 0.92, p < 0.01). However, the ΔORP index showed negative correlations with tryptophan-like proteins, tyrosine-like proteins, microbial byproduct-like materials in tightly-bound EPS (r = -0.85, -0.90 and -0.90, p < 0.05), and sludge particle sizes (p < 0.01). A multiple linear regression model was developed to further reflect the linear correlation between the ΔORP values and the key factors reflecting sludge dewaterability. An optimal dose of oxone (0.4 mmol/g VS) for sludge pre-oxidation with the ΔORP value of 387 mV combined with Fe(III) coagulation conditioning system were verified by the results of dewatering experiments using a laboratory-scale diaphragm filter press. This study demonstrated the feasibility of using ΔORP as a potential rapid evaluation tool for sludge dewaterability.

Unraveling oxidation behaviors for intracellular and extracellular from different oxidants (HOCl vs. H2O2) catalyzed by ferrous iron in waste activated sludge dewatering.

Cell lysis in sludge pretreatment by advanced oxidation process (AOP) has a great effect on sludge dewaterability. Cell lysis caused by reactive radicals (e.g. hydroxyl radical) was dependent on the reaction site of AOP. However, little is known about the accurate radical generation site of AOP in sludge pretreatment. In this study, two kinds of oxidation behaviors from different oxidants (HOCl vs. H2O2) catalyzed by ferrous iron were comparatively investigated. Higher amount of living cells (84.3%) and hydroxyl radicals (9.86 × 10-5 M), and more fragmentized sludge flocs (particle sizes of D50 was 50.1 vs. 57.3 µm of RS) were detected in sludge conditioned by Fe2+/H2O2, which implied that Fenton reaction mainly happened at surface and outside of sludge flocs (such as EPS layer and liquid phase). Thus, it could be regarded as "extracellular oxidation". Fewer living cells (undetectable), fewer amount of hydroxyl radicals (undetectable in sludge), and more integrated sludge flocs (particle size of D50 was 56.1 vs. 57.3 µm of RS) were determined in sludge conditioned by Fe2+/Ca(ClO)2. Hence, it could be regarded as "Intracellular oxidation". In addition, sludge pretreatment based on Fe2+/Ca(ClO)2 could achieve simultaneous deep-dewatering performance and total coliforms inactivation. Based on response surface methodology, the optimal dosages of Fe2+ and Ca(ClO)2 were proposed as 106.1 and 234.5 mg/g volatile solids respectively, without any acidification of sludge. Under these optimal dosages, the water content of dewatered sludge cake was 51.9 ±â€¯0.1 wt% and the pH of the final filtrate was 5.8 ±â€¯0.2. Total coliforms of sludge could be inactivated in 10 s after Fe2+/Ca(ClO)2 addition.

Visible Light Driven Organic Pollutants Degradation with Hydrothermally Carbonized Sewage Sludge and Oxalate Via Molecular Oxygen Activation.

Converting sewage sludge into functional environmental materials has become an attractive sewage sludge disposal route. In this study, we synthesize a sewage sludge-based material via a facile one-pot hydrothermal carbonization method and construct a visible light molecular oxygen activation system with hydrothermally carbonized sewage sludge (HTC-S) and oxalate to degrade various organic pollutants. It was found that iron species of HTC-S could chelate with oxalate to generate H2O2 via molecular oxygen activation under visible light, and also promote the H2O2 decomposition to produce •OH for the fast organic pollutants degradation. Taking sulfadimidine as the example, the apparent degradation rate of HTC-S/oxalate system was almost 5-20 times that of iron oxides/oxalate system. This outstanding degradation performance was attributed to the presence of iron-containing clay minerals in HTC-S, as confirmed by X-ray diffraction measurements and Mössbauer spectrometry. In the oxalate solution, these iron-containing clay minerals could be excited more easily than common iron oxides under visible light, because the silicon species strongly interacted with iron species in HTC-S to form Fe-O-Si bond, which lowered the excitation energy of Fe-oxalate complex. This work provides an alternative sewage sludge conversion pathway and also sheds light on the environmental remediation applications of sewage sludge-based materials.

A comparatively optimization of dosages of oxidation agents based on volatile solids and dry solids content in dewatering of sewage sludge.

Organic content of sludge is a major factor influencing its dewaterability. Conditioning sewage sludge with oxidation reagents (Fenton's reagent or Fe2+/persulfate) can effectively improve sludge dewaterability. In traditional conditioning process of sewage sludge, the optimization of conditioner dosage were commonly based on volume of sludge (referred as mg/L) or mass of dry solid (DS) of sludge (referred as mg/g DS). However, inconsistency of the oxidation dose mode existed for different sewage sludge sources. In this study, sludge samples of different volatile solids (VS) contents were used to derive optimal dosages of Fenton's reagent and Fe2+/persulfate, using the response surface methodology (RSM). For the case of Fenton's reagent, the optimal dosages of Fe2+ and H2O2 were 107-110 mg/g VS and 86-88 mg/g VS, respectively. For Fe2+/persulfate, the optimal dosages of Fe2+ and persulfate were 49 mg/g VS and 269-271 mg/g VS, respectively. The optimal dosages of the oxidation reagents based on VS contents were proved to be consistent and effective for different sewage sludge with different organic matter contents from different wastewater treatment plants (WWTPs). In contrast, the optimal dosages of oxidation reagents, based on DS, fluctuated significantly for different sludge sources. Furthermore, sewage sludge dewaterability was significantly related to the degradation and the content of loosely bound extracellular polymeric substances (LB-EPS) in the organic matters of conditioned sludge (R2 > 0.9, p < 0.01). Thus, the improvement of sludge dewaterability could be related with the destruction of the VS in sludge with the conditioners of oxidant reagent. It indicated that optimization of oxidation reagent based on VS content is more plausible than that of based on DS content for different sewage sludge with different organic matter contents.