Decarbonizing paper mill sludge waste into micro and nanofibrillated cellulose via enzyme hydrolysis and dual asymmetric centrifugation.

The production of micro- and nano-fibrillated cellulose (MNFC) from paper mill sludge (PS) using simple enzymatic and mechanical treatments has been evaluated for their performance as value-added materials in packaging and other applications. Sludge from a US paper mill was analyzed for the viability of this conversion process. The enzymatic treatment was conducted at variable concentrations using an enzyme cocktail of exoglucanase and endoglucanase, followed by mechanical dual asymmetric centrifugation (DAC) treatment. The presence of inorganics and lignin facilitated the mechanical defibrillation of the fibers, making the MNFC production more energy-efficient. The prepared MNFC was characterized for fibrillation, charge, crystallinity, and surface morphology. Scanning electron microscopic (SEM) images show the highly fibrillated MNFC and the distribution of inorganic nanoparticles on the fiber surface. The X-ray diffractometric (XRD) analysis shows 44-65 % crystallinity. Furthermore, MNFC-based films derived from PS demonstrated excellent strength and flexibility, making them suitable for packaging and other applications. Overall, this conversion approach can save the paper industry millions of dollars in disposal costs while upcycling waste and reducing greenhouse gas (GHG) emissions associated with waste streams.

Environmental and economic analysis of the transformation of paper mill sludge treatment technologies in China.

Paper mill sludge (PMS) is featured with a high content of cellulose and hemicellulose, and using its characteristics to make paperboard can achieve a high-value utilization of PMS, which has attracted growing interest. In this study, currently prevalent landfill, incineration technologies (generating heat and electricity by incineration), and three paperboard technologies (medium density fiberboard, pulp board, and corrugated paper) were evaluated and compared via life cycle assessment (LCA) and life cycle costing (LCC) methods. LCA results show that the PMS-to-pulp board outperforms others with an energy conservation and emission reduction (ECER) value of - 2.86 × 10-8, while the landfill exhibits the highest overall environmental impact with an ECER value of 4.80 × 10-9. LCC results reveal that the PMS-to-pulp board delivers the highest economic profit with $257.357, while the landfill is the lowest with $ - 35.63. The PMS paperboard technologies are more economically friendly than the incineration technologies due to additional electricity/steam consumption during the PMS pre-drying process in incineration. In addition, different scenarios were set up to explore national GHG emission reduction potential by increasing paperboard technologies application rate and reducing the proportion of landfill and incineration. The scenario analysis suggests that replacing 90% of landfill and incineration ratio with PMS paperboard technologies could tremendously improve the overall emission reduction performance with - 9.08 × 1010 kg CO2 eq. This result indicates that the PMS treatment technology transformation has a significant favorable impact on the achievement of the "carbon neutrality" target.

The influence of biochar from animal and plant on the transformation of phosphorus during paper mill sludge composting.

Biochar has effect on phosphorus adsorption, release, and transformation. This study compared the influence of biochar derived from animal (AB) and plant (PB) during paper mill sludge composting. Results indicated AB not only accelerated sludge decomposition but also had significantly higher levels of available phosphorus (AP) than PB and CK (no biochar), with AP contents in the order of AB > PB > CK. Compared to CK, AB was found to increase the relative abundance of thermophilic bacteria, and PB diversified the microbial community. Based on Pearson and RDA results, TOC/TN ratio (C/N) and organic matter (OM) explained above 50% of the variance in microbial community and phosphorus fractions. Thermophilic bacteria with high levels of OM and C/N promoted the conversion among labile and moderately labile organic phosphorus, moderately labile inorganic phosphorus, and AP. Biochar could enhance the AP conversion pathway, leading to increased levels of AP.

Comprehensive kinetic modeling and product distribution for pyrolysis of pulp and paper mill sludge.

Pyrolysis holds immense potential for clean treatment of pulp and paper mill sludge (PPMS), enabling efficient energy and chemical recovery. However, current understanding of PPMS pyrolysis kinetics and product characteristics remains incomplete. This study conducted detailed modeling of pyrolysis kinetics for two typical PPMSs from a wastepaper pulp and paper mill, namely, deinking sludge (PPMS-DS) and sewage sludge (PPMS-SS), and analyzed comprehensively pyrolysis products. The results show that apparent activation energy of PPMS-DS (169.25-226.82 kJ/mol) and PPMS-SS (189.29-411.21 kJ/mol) pyrolysis undergoes significant change, with numerous parallel reactions present. A distributed activation energy model with dual logistic distributions proves to be suitable for modeling thermal decomposition kinetics of both PPMS-DS and PPMS-SS, with coefficient of determination >0.999 and relative root mean square error <1.99 %. High temperature promotes decomposition of solid organic materials in PPMS, and maximum tar yield for both PPMS-DS (53.90 wt%, daf) and PPMS-SS (56.48 wt%, daf) is achieved at around 500 °C. Higher levels of styrene (24.45 % for PPMS-DS and 14.71 % for PPMS-SS) and ethylbenzene (8.61 % for PPMS-DS and 8.33 % for PPMS-SS) are detected in tar and could be used as chemicals. This work shows great potential to propel development of PPMS pyrolysis technology, enabling green and sustainable production in pulp and paper industry.

Correction factors for large-scale greenhouse gas assessment from pulp and paper mill sludge landfill sites.

Assessments of greenhouse gas (GHG) emissions in managed areas are facing various challenges. A non-flow-through, non-steady-state (NFT-NSS) chamber coupled to a frame permanently inserted into the landfilled substrates is a standard method for quantifying GHG emissions in managed areas, such as pulp and paper mill sludge (PPMS) landfill sites. Frequent measurements are needed to minimize uncertainties on GHG emission factors at the landfill site scale. However, maintaining a frame inserted into the substrates for a long time period is often impossible due to landfilling management operations. Therefore, GHG measurements using NFT-NSS chambers placed directly on substrates' surface could be an interesting option. Our objectives were to determine the relationships between CO2, CH4, and N2O fluxes measured with (F + ) and without (F-) a frame inserted in the substrates' surface and to develop correction factors for fluxes measured without a frame. Measurements were made at different PPMS landfill sites in the province of Québec, Canada. Stronger GHG flux relationships were observed at the provincial (across sites) than the specific site scale: the variance in GHG fluxes from F- chambers explained up to 80 % of variance in fluxes from F + chambers. The measured CO2, CH4, and N2O fluxes in F- chambers were on average 53, 78, and 63 % lower, respectively, than those estimated by the models at provincial scale. The correction factors developed with this approach could greatly extend the number of sites where in situ GHG measurements can be done and would help refining GHG inventories at the provincial and national levels.

Development of value-added sustainable products from paper mill sludge: An experimental approach.

The disposal of paper mill sludge waste generated by the paper industry is a tough and challenging task. In this work, an attempt is made to develop various value-added products namely bricks, briquettes, ground chakra base, and eco-friendly composites from the secondary paper mill sludge (PMS). The secondary PMS was initially dewatered to remove the moisture content, ground to powder, and mixed with cement, MSand. quarry dust, and fly ash to produce bricks. The brick specimens were tested for compressive strength, water absorption, and efflorescence as per the standards and found to be 5.29 ± 0.11 N/mm2, 3.84 ± 0.13% respectively, and have NIL efflorescence. The PMS is mixed with paraffin wax and compressed in a squeeze moulding to form briquettes and observed that the percentage of ash content in the briquette is 66.6% which is less than that of the PMS. Further, a ground chakra base is produced using a slurry of starch and dried in a heater at 60° exhibiting better properties. An eco-friendly composite pottery product was developed by mixing PMS, clay, and starch and tested for breakage.

Lignin-Degrading Bacteria in Paper Mill Sludge.

The effluents generated in the paper industry, such as black liquor, have a high content of lignin and other toxic components; however, they represent a source of lignin-degrading bacteria with biotechnological potential. Therefore, the present study aimed to isolate and identify lignin-degrading bacteria species in paper mill sludge. A primary isolation was carried out from samples of sludge present in environments around a paper company located in the province of Ascope (Peru). Bacteria selection was made by the degradation of Lignin Kraft as the only carbon source in a solid medium. Finally, the laccase activity (Um-L-1) of each selected bacteria was determined by oxidation of 2,2'-azinobis-(3-etilbencenotiazolina-6-sulfonate) (ABTS). Bacterial species with laccase activity were identified by molecular biology techniques. Seven species of bacteria with laccase activity and the ability to degrade lignin were identified. The bacteria Agrobacterium tumefasciens (2), Klebsiella grimontii (1), and Beijeinckia fluminensis (1) were reported for first time. K. grimowntii and B. fluminensis presented the highest laccase activity, with values of 0.319 ± 0.005 UmL-1 and 0.329 ± 0.004 UmL-1, respectively. In conclusion, paper mill sludge may represent a source of lignin-degrading bacteria with laccase activity, and they could have potential biotechnological applications.

Integrated enzyme hydrolysis assisted cellulose nanofibril (CNF) fabrication: A sustainable approach to paper mill sludge (PMS) management.

The landfilling of paper mill sludge (PMS) has been restricted or even banned in many countries due to the raised concern about greenhouse gas (GHG) emissions and contamination of the soil and water, calling for a sustainable PMS management approach. The potential valorization of PMS to nanomaterials combined with traditional biorefinery was examined in this work. Three types of PMS-derived cellulose nanofibrils (CNFs) were prepared and evaluated: enzymatically assisted CNF (AU: with in-house produced enzyme and CT: with commercial enzyme), mechanically pretreated CNF (BT), and chemically pretreated CNF by TEMPO oxidation (TEMPO). It was found that enzyme-assisted mechanical fibrillation-derived CNFs had a comparable average diameter (27.9 nm for AU and 22.7 nm for CT) with that produced from mechanical pretreatment (26.5 nm for BT) and TEMPO oxidation pretreatment (20.0 nm for TEMPO), and they showed the best drainage properties among the three types of CNF. The CNFs resulting from enzymatic pretreatment reduced 15% of energy consumption compared to the mechanical method and had better thermostability than TEMPO oxidation method. In addition, the on-site produced enzyme showed similar performance to the commercial enzymes towards the CNF properties. These findings provide new insights into a promising integrated strategy in engineering CNF from PMS with on-site enzyme production as a novel and sustainable approach for PMS management and valorization.

Ex-situ magnetic activated carbon for the adsorption of three pharmaceuticals with distinct physicochemical properties from real wastewater.

Pharmaceuticals are able to evade conventional wastewater treatments and therefore, are recurrently found in the environment with proven potential to cause harm to human and wildlife. Adsorption onto activated carbon (AC) is a promising complement. However, AC production from non-renewable resources and its difficult after-use recuperation are prohibitive. Hence, a waste-based magnetic activated carbon (MAC) was produced from paper mill sludge, via an ex-situ synthesis, for the adsorptive removal of carbamazepine (CBZ), sulfamethoxazole (SMX) and ibuprofen (IBU) from ultrapure water and wastewater. The MAC was obtained through the promotion of electrostatic interactions between magnetic and activated carbon particles in a water suspension at controlled pH between the points of zero charge of both surfaces. The optimized condition (MACX3) presented remarkable properties regarding specific surface area (SBET=795 m2 g-1) and saturation magnetization (MS=19 emu g-1). Kinetic and equilibrium adsorption studies were performed under batch conditions. Adsorption equilibrium was reached in up to 30 min for all pharmaceuticals in both matrices, proving the low dependence on the adsorbate and the broad applicability of MACX3 in pharmaceutical adsorption. Regarding equilibrium experiments, high Langmuir maximum adsorption capacities (qm) were achieved in ultrapure water (up to 711 ± 40 µmol g-1). Equilibrium studies in wastewater revealed a decay in qm when compared to ultrapure water: 28% for CBZ (468 ± 20 µmol g-1 (111 ± 5 mg g-1)), 78% for SMX (145 ± 10 µmol g-1 (37 ± 3 mg g-1)) and 62% for IBU (273 ± 8 µmol g-1 (56 ± 2 mg g-1)), attributed to the wastewater pH, which dictates the speciation of the pharmaceuticals and controls electrostatic interactions between pharmaceuticals and MAC, and to competition effects by organic matter. It was demonstrated the promising applicability of a waste-based ex-situ MAC, rapidly retrievable from water, as an alternative tertiary wastewater treatment for pharmaceuticals removal.

Challenges in developing strategies for the valorization of lignin-a major pollutant of the paper mill industry.

Apart from protecting the environment from undesired waste impacts, wastewater treatment is a crucial platform for recovery. The exploitation of suitable technology to transform the wastes from pulp and paper industries (PPI) to value-added products is vital from an environmental and socio-economic point of view that will impact everyday life. As the volume and complexity of wastewater increase in a rapidly urbanizing world, the challenge of maintaining efficient wastewater treatment in a cost-effective and environmentally friendly manner must be met. In addition to producing treated water, the wastewater treatment plant (WWTP) has a large amount of paper mill sludge (PMS) daily. Sludge management and disposal are significant problems associated with wastewater treatment plants. Applying the biorefinery concept is necessary for PPI from an environmental point of view and because of the piles of valuables contained therein in the form of waste. This will provide a renewable source for producing valuables and bio-energy and aid in making the overall process more economical and environmentally sustainable. Therefore, it is compulsory to continue inquiry on different applications of wastes, with proper justification of the environmental and economic factors. This review discusses current trends and challenges in wastewater management and the bio-valorization of paper mills. Lignin has been highlighted as a critical component for generating valuables, and its recovery prospects from solid and liquid PPI waste have been suggested.

Facile extraction and characterization of calcium hydroxide from paper mill waste sludge of Bangladesh.

Herein, paper mill waste sludge (PMS) from two different sources has been investigated to extract calcium hydroxide, Ca(OH)2 by a facile and inexpensive extraction process. PMS samples, collected from local paper mill plants of Bangladesh, were the main precursors wherein HCl and NaOH were used for chemical treatment. The as-synthesized products were analysed by a variety of characterization tools including X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) elemental analyses. Our studies confirm that the extracted product contains Ca(OH)2 as a major content, albeit it also includes CaCO3 phase owing to the inescapable carbonation process from the surrounding environment. The particle size of the synthesized products is in the range of 450-500 nm estimated from SEM micrographs. The crystallite domain size of the same estimated from XRD analyses and was found to be approximately 47 and 31 nm respectively for product-A and product-B considering major (101) Bragg peak of Ca(OH)2. The yield percentage of the isolated products is about 65% for samples collected from both sources.

Evaluating land application of pulp and paper mill sludge: A review.

It is estimated that >400 Mt of board and paper are produced globally per year, and that 4.3-40 kg (dw) of sludge like material, pulp and paper mill sludge (PPMS), is generated for every tonne of product. PPMS are now more widely reused in agriculture as a soil amendment due to their high organic content of 40-50% by weight, perceived low toxicity and possible liming capabilities. Within this review article historic and recent literature on PPMS land spreading are combined with knowledge of European and UK regulation to explore the benefits, potential impacts and viability of land spreading PPMS. The review reveals that risks relating to potential N immobilisation in soils post-application can be readily mitigated, if desired, by coapplication of an N source, or even pre-treatment of sludge via composting. The benefits to crops have been demonstrated emphatically, while negative ecological impacts under typical field application rates have not been observed to date. The case is therefore strong for continued land application of the material as an environmentally responsible and sustainable use option. However, there are currently gaps in the literature regarding longer-term implications of PPMS applications in agriculture and in regards to the possible presence of emerging contaminants in some PPMS materials, both of which have been identified as areas that merit further research.

Cellulase activity of a novel bacterial strain Arthrobacter woluwensis TDS9: its application on bioconversion of paper mill sludge.

BACKGROUND: Lignocellulosic biomasses produced from agriculture and forest-based industries are the cheapest or negative-cost biomass with a great potential for biotransformation to value-added bioproducts. Paper mill sludge, an important lignocellulosic biomass creates an environmental threat, which requires financial input for disposal. Thus, this study was aimed to isolate a novel bacterial strain capable of degrading cellulosic biomass including paper mill sludge to produce reducing sugar and other value-added bioproducts. RESULTS: A novel bacterial strain Arthrobacter woluwensis TDS9 isolated from the soil was screened for its cellulolytic activity using carboxymethyl cellulose (CMC) as the sole carbon source. The incubation period, temperature, pH, carbon, and nitrogen sources are the most important factors ruling the CMCase and sugar productions of the strain A. woluwensis TDS9, and an alkaline pH (pH 8.0) led to enhanced sugar production up to 1100.09 µg/mL after 72 h of incubation at 25°C in a medium containing 1.5% CMC and 1.25% beef extract. The optimal conditions for maximum CMCase activity were defined, and the potassium ion boosted the CMCase activity up to 1.06 U/mL when the enzymatic reaction was performed for 30 min at 50°C and pH 8 using CMC as a substrate. Moreover, the strain A. woluwensis TDS9 produced 433.33 µg/mL reducing sugar from 1% pretreated paper mill sludge. Significant alterations in the structural arrangement of cellulosic fiber of paper mill sludge observed under microscope after each step of chemical treatment process helped for loosening the cellulose fibers and increased the saccharification for enzymatic hydrolysis. Endoglucanase IV (33 KDa) and beta-glucosidase II (53 KDa) were identified in crude enzyme based on the zymogram analysis and substrate specificity. CONCLUSIONS: The research has for the first time proved that this A. woluwensis TDS9 strain can efficiently convert cellulose. Therefore, the strain TDS9 could be a potential candidate for cellulase production in an industrial biotransformation process of paper mill sludge to produce reducing sugar. This sugar stream can be further used as a substrate to produce biofuels and other organic acids using another microorganism, which represents a greener alternative to add value to the paper production helping paper mill industries.

Paper mill sludge-based carbon quantum dots as a specifically ratiometric fluorescent probe for the sensitive and selective detection of coptisine.

Coptisine (COP), one of the bioactive components in Rhizoma Coptidis, has many pharmacological effects. Meanwhile, the determination of COP is essential in pharmacological and clinical applications. Herein, we prepared carbon quantum dots (CQDs) by one-step oil-thermal method using paper mill sludge (PMS) as precursor, and developed a ratiometric fluorescence method for the determination of COP. The structural and optical properties of PMS-CQDs were evaluated through high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), ultraviolet-visible (UV-vis), fluorescence, zeta potential and fluorescence lifetime experiments. Fluorescence intensity ratio at 550 nm and 425 nm (I550 /I425 ) was recorded as an index for quantitative detection of COP. The detection concentration of COP ranges from 0.1 to 50 µM in good linear correlation (R2  = 0.9974) with a limit of detection of 0.028 µM (3σ/k). The quenching mechanism was deduced to be inner filter effect and static quenching. The ratiometric fluorescent probe showed impressive selectivity and sensitivity towards COP, and was successfully applied to the detection of COP in human urine with expected recoveries (95.22-111.00%) and relative standard deviations (0.46-2.95%), indicating that our developed method has a great application prospect in actual sample detection.

Synergistic role of inherent calcium and iron minerals in paper mill sludge biochar for phosphate adsorption.

Phosphate adsorption using metal-based biochar has awakened much attention and triggered extensive research. In this study, novel Ca/Fe-rich biochars were prepared via a one-step process of pyrolyzing paper mill sludge (PMS) at various temperatures (300, 500, 700, and 800 °C) under a CO2 atmosphere for phosphate removal. Batch adsorption experiments showed that the biochar obtained at 800 °C (PB-800), which could be easily separated magnetically, exhibited the best phosphate adsorption capacity in a wide range of solution pH (5-11). Based on the Langmuir model, the maximum phosphate adsorption capacity for PB-800 was 17.33 mg/g. Besides, the effects of ambient temperature as well as coexisting ions on phosphate removal were also investigated. Kinetic and thermodynamic analysis revealed that chemisorption dominated the adsorption process. The calcium carbonate and ferric salts in the sludge were converted into CaO and Fe3O4 through pyrolysis at 800 °C. The CaO inherent in PB-800 was proved to serve as active sites for the chemical precipitation, showing its synergistic effect with iron oxide compounds (i.e., Fe3O4, α-Fe2O3) on phosphate removal through chemical precipitation, ligand exchange, and complexation. This study not only provides a feasible waste-to-wealth strategy for converting PMS into a Ca/Fe-rich magnetic biochar that can be used as an effective phosphate adsorbent, but also offers new insights into the synergistic effect of calcium and iron species for the adsorption of phosphate using biochar.

Simultaneous recovery of phosphate and degradation of antibiotics by waste sludge-derived biochar.

Recovery of phosphorus (P) from wastewater has led to growing public concern considering its scarcity and future availability as well as its detrimental environmental impacts. However, the recovered P is inevitably contaminated with co-existing antibiotics like tetracycline (TC) and sulfamethazine (SMT) which will pose serious risks to the health of human and animals after being spread to the environment. In this study, we propose a novel scheme that can recover P from synthetic wastewater and at the same time degrade the co-existing antibiotics. To achieve such a goal, a series of biochar (BC) were prepared from calcination of waste sludge and were used both as the adsorbent for P recovery and as the catalyst for peroxymonosulfate (PMS) activation and antibiotic degradation. Results showed that the sludge source (i.e. Sm: municipal sludge, Sp: paper mill sludge), calcination atmosphere (i.e. air-deficient, N2, vacuum) and temperature (i.e. 600 and 800 °C) exhibited significant influence on P adsorption capacity. Generally, the BC calcined in N2 showed better P uptake, and increase of calcination temperature from 600 °C to 800 °C could further improve P uptake. Though BCp-N-600 (prepared from Sp in N2 at 600 °C) showed faster and higher P uptake (56.3 mg/g) than its counterpart BCm-N-600 (33.2 mg/g), BCm-N-600 showed stronger catalytic activity and more stable performance in the complex pollutant system (P + SMT). It was proposed that P was recovered primarily through the chemisorption and precipitation mechanism, while SMT was nearly completely degraded primarily by the ROS generated from PMS activation.

Removal of phosphate from water by paper mill sludge biochar.

Biochar modification by metals and metal oxides is considered a practical approach for enhancing the adsorption capacity of anionic compounds such as phosphate (P). This study obtained paper mill sludge (PMS) biochar (PMSB) via a one-step process by pyrolyzing PMS waste containing ferric salt to remove anionic P from water. The ferric salt in the sludge was transformed into ferric oxide and zero-valent-iron (Fe0) in N2 atmosphere at pyrolysis temperatures ranging from 300 to 800 °C. The maximum adsorption (Qm) of the PMSBs for P ranged from 9.75 to 25.19 mg P/g. Adsorption is a spontaneous and endothermic process, which implies chemisorption. PMSB obtained at 800 °C (PMSB800) exhibited the best performance for P removal. Fe0 in PMSB800 plays a vital role in P removal via adsorption and coprecipitation, such as forming the ≡Fe-O-P ternary complex. Furthermore, the possible chemical precipitation of P by CaO decomposed from calcite (CaCO3; an additive of paper production that remains in PMS) may also contribute to the removal of P by PMSB800. Moreover, PMSBs can be easily separated magnetically from water after application and adsorption. This study achieved a waste-to-wealth strategy by turning waste PMS into a metal/metal oxide-embedded biochar with excellent P removal capability and simple magnetic separation properties via a one-step pyrolysis process.

Integrated production of optically pure l-lactic acid from paper mill sludge by simultaneous saccharification and co-fermentation (SSCF).

Paper mill sludge (PMS) raises critical environmental issues due to its disposal problem, but its high sugar content and well-dispersed structure make it a great feedstock for biochemical production. The technical feasibility of integrating cellulase enzyme production into lactic acid (LA) fermentation from PMS was investigated in this study. The low ash content of PMS suggests a great potential for cellulase production. The enzyme produced using PMS without any treatment gave an activity of 7.8 FPU/ml, a performance comparable to the commercial enzyme, Cellic CTec 2. The LA yield from PMS with in-house enzyme was 64.7% and 73.7% at the enzyme loading of 10 and 15 FPU/g-glucan, respectively. The LA obtained was optically pure L- isomer with over 99% purity. The optimal condition of LA production by Bacillus coagulans was found to be 50 °C and pH 5.3 (with 50 g/L CaCO3). The nutrient effect of yeast extract (YE) and corn steep liquor (CSL) was substrate dependent, and CSL could substitute YE as an inexpensive nutrient when using PMS as a substrate.

Biochar heavy metal removal in aqueous solution depends on feedstock type and pyrolysis purging gas.

The effectiveness of biochar as a sorptive material to remove contaminants, particularly heavy metals, from water is dependent on biomass type and pyrolysis condition. Biochars were produced from pulp mill sludge (PMS) and rice straw (RS) with nitrogen (N2) or carbon dioxide (CO2) as the purging gas. The sorptive capacity of the biochars for cadmium(II), copper(II), nickel(II) and lead(II) was studied. The heavy metal adsorption capacity was mainly affected by biomass type, with biochars adsorption capacities higher for lead(II) (109.9-256.4 mg g-1) than for nickel(II) (40.2-64.1 mg g-1), cadmium(II) (29.5-42.7 mg g-1) and copper(II) (18.5-39.4 mg g-1) based on the Langmuir adsorption model. The highest lead(II) adsorption capacities for PMS and RS biochars were 256.4 and 133.3 mg g-1, respectively, when generated using N2 as the purging gas. The corresponding lead(II) adsorption capacities were 250.0 and 109.9 mg g-1, respectively, when generated using CO2 as the purging gas. According to the intraparticle diffusion model, 30-62% of heavy metal adsorption was achieved in 1 h; film diffusion was the rate-dominating step, whereas pore diffusion was a rate-limiting step. Ion exchange and complexation between heavy metals and biochar surface functional groups such as carbonyl and hydroxyl groups were effective mechanisms for heavy metal sorption from the aqueous solution. We conclude that proper selection of both the feedstock type and the purging gas is important in designing biochars for the effective removal of potentially toxic metals from wastewater.

From wastes to functions: A paper mill sludge-based calcium-containing porous biochar adsorbent for phosphorus removal.

With the increased awareness of reusing solid wastes for higher sustainability and the concern of water pollution associated with phosphorus over-emission, there are strong interests in developing solid waste based adsorbents for purifying phosphorus-containing wastewater. As a rich calcium resource, paper mill sludge (i.e., a major solid waste from pulping industry) can be used as phosphorus removal adsorbent after calcination. Thus, in this work, a simple and clean thermally treating route has been proposed for preparing calcium-containing biochar from paper mill sludge. The effect of the physicochemical properties of paper mill sludge and its carbonization condition on phosphorus adsorption has been analyzed. Moreover, the influence of some key adsorption parameters, e.g., biochar dosage, initial pH of solution, co-existing anions, initial phosphorus concentration and contact time has also been investigated. The results showed that the phosphorus adsorption data could be fitted well with pseudo-second-order kinetic and Langmuir isothermal models. The calculated maximum adsorption capacity of the as-prepared optimal calcium-containing biochar could reach to 68.49 mg·g-1 at 25 °C. Combined with the characterization results, it can be reasonably inferred that the adsorption process was chemisorption-dominated. Lastly, the application of this spent adsorbent in agriculture field has also been discussed. In brief, this work provided a feasible strategy for converting paper mill solid waste to an environmental functional material (i.e., calcium-rich biochar) for remediation of eutrophic water.