Coeffect of pyrolysis temperature and potassium phosphate impregnation on characteristics, stability, and adsorption mechanism of phosphorus-enriched biochar.

Potassium phosphate (K3PO4)-impregnated bamboo was pyrolyzed at temperatures ranging from 350 to 950 °C to explore the coeffect of pyrolysis temperature and K3PO4 impregnation on biochar's characteristics and adsorption behavior. The degree of aromatization and graphitization in phosphorus-enriched biochars (PRBCs) rose as temperature increased, whereas H/C and O/C ratios, pH value, and O-containing group content decreased. The pre-aging impact of K3PO4 impregnation results in increased stability and adsorption performance of PRBCs. Adsorption mechanism of PRBCs to heavy metal varies from pyrolysis temperature. Micropores dominate medium-temperature PRBCs (prepared at 550 âˆ¼ 750 °C), possessing the highest P-containing group content (116 % that of PRBC-350) and maximal adsorption capacity (greater than289 mg/g). The medium-temperature PRBCs adsorb Cd (II) via the role of O-containing groups, PO43-, and P2O74-, mainly by reactions of organic complexation, precipitation and inorganic complexation, respectively. 550 °C is the optimal pyrolysis temperature for both energy saving and heavy metal adsorption.

Effects of phosphorous precursors and speciation on reducing bioavailability of heavy metal in paddy soil by engineered biochars.

Ammonium phosphate (AP), phosphoric acid (PC), and potassium phosphate (TKP) were used for the modification of biochar for enhanced heavy metal passivation in soil. The effect of various phosphorus (P) precursors on adsorption-related properties, P speciation distribution pattern, and the passivation mechanism was investigated by BET, FTIR, XRD, XPS, and 31P NMR analysis. The mobility and bio-availability of cadmium (Cd) were studied by extraction experiments, and the P release kinetics was also determined. Results showed that the immobilization efficiency of Cd (II) by biochars followed the order: TKP-BC > PC-BC > AP-BC > BC, and TKP-BC reduced available Cd content by 81% treated with 2% addition. The P speciation shows a significant effect on the P-enriched biochars' passivation performance, especially orthophosphate, which is essential for the immobilization of Cd2+ by forming phosphate precipitation. Pyrophosphate and orthophosphate monoester in AP-BC and PC-BC can promote Cd2+ passivation via the formation of P-Cd complexes or organometallic chelates. It is also shown that PC-BC has the lowest P release rate while TKP-BC has the highest percentage of P (15.50%) remaining in the biochar. The results may contribute to the development of modified biochar for soil remediation based on P-related technologies.

Characteristics and Evolution of Nitrogen in the Heavy Components of Algae Pyrolysis Bio-Oil.

Algae pyrolytic bio-oil contains a large quantity of N-containing components (NCCs), which can be processed as valuable chemicals, while the harmful gases can also be released during bio-oil upgrading. However, the characteristics of NCCs in the bio-oil, especially the composition of heavy NCCs (molecular weight ≥200 Da), have not been fully studied due to the limitation of advanced analytical methods. In this study, three kinds of algae rich in lipids, proteins, and carbohydrates were rapidly pyrolyzed (10-25 °C/s) at different temperatures (300-700 °C). The bio-oil was analyzed using a Fourier transform ion cyclotron resonance mass spectrometer equipped with electrospray ionization, and the characteristics and evolution of nitrogen in heavy components were first obtained. The results indicated that the molecular weight of most heavy NCCs was distributed in the 200-400 Da range. N1-3 compounds account for over 60% in lipid and protein-rich samples, while N0 and N4 components are prominent in carbohydrate-rich samples. As temperature increases, most NCCs become more aromatic and contain less O due to the strong Maillard and deoxygenation reactions. Moreover, the heavier NCCs were promoted to form lighter compounds with more nitrogen atoms through decomposition (mainly denitrogenation and deoxygenation). Finally, some strategies to deal with the NCCs for high-quality bio-oil production were proposed.

Synthesis and characterization of magnesium oxide nanoparticle-containing biochar composites for efficient phosphorus removal from aqueous solution.

The effective removal and recovery of phosphorus from aquatic environments are highly important for successful eutrophication control and phosphorus recycling. Herein, we prepared biochar containing MgO nanoparticles (MgO-biochar) by fast pyrolysis of MgCl2-impregnated corn stalks, probed its phosphate adsorption performance. Through the fast pyrolysis, the MgCl2 promoted the formation of micropores and mesoporous, and decomposed into MgO nanoparticles with the size smaller than 100 nm. The adsorption experiments showed that the adsorption property increased with the increase of Mg content, and had a strong correlation with the external surface area. And the phosphate adsorption was well described by the Langmuir-Freundlich model (maximum adsorption capacity was determined as 60.95 mg P/g). Kinetic analysis and characterization analysis of MgO-biochar for different adsorption time indicated that phosphate adsorption onto MgO-biochar was mainly controlled by rapid binding to the external surface (about 75% of the equilibrium adsorption amount), and the uptake rate was limited by the slow diffusion of phosphate into the biochar interior (about 25% of the equilibrium adsorption amount). The results suggested that the synthesized MgO-biochar with enough MgO active site dispersed on a higher external surface can be used as a potential adsorbent for phosphate removal and recovery from aqueous solution.

Effect of phosphorus-modified biochars on immobilization of Cu (II), Cd (II), and As (V) in paddy soil.

Novel phosphorus-modified biochars were produced by pyrolyzing biomass feedstocks (wood, bamboo, cornstalk and rice husk) pre-impregnated with potassium phosphate (K3PO4). The soil heavy metal immobilization performance and mechanisms of modified biochars were investigated. Incubation experiments showed that impregnation with phosphorous can decrease the extraction of Cu (II) and Cd (II) by 2 to 3 times. Phosphorus-modified biochars enhanced the transformation of Cu (II) and Cd (II) ions from acid soluble to more stable forms. Characterization results showed that phosphorus (P) compounds in modified biochar played a vital role to immobilize Cu (II) and Cd (II) by forming precipitates or complexes with them. Additionally, the modified rice husk and cornstalk biochars have in the average 14-24% and 19-33% higher immobilization efficiency for Cd (II) and Cu (II) than the other two P-assisted biochars. However, regardless of the feedstock, both the extraction and mobility of As (V) were increased by phosphorous. This study indicates that the P-modified biochar can serve as a novel remediation agent for heavy metal polluted soils.

The effect of combined pretreatments on the pyrolysis of corn stalk.

Untreated corn stalk (CS), deionized water washed CS (WCS), aqueous phase bio-oil washed CS (LCS), and 5% acetic acid washed CS (CCS) were torrefied at 230, 260, and 290 °C. The influences of washing, torrefaction, and combined washing-torrefaction pretreatments on corn stalk pyrolysis were investigated. The combined pretreatments, especially aqueous phase bio-oil washing-torrefaction improved fuel properties of pretreated samples largely by increasing their volatile and hydrogen contents. Absorption peaks of O-H and CO groups in combined pretreatment samples increased when torrefaction temperature increased. In addition, CO, H2, and CH4 contents of pyrolysis gas increased, while CO2 decreased after combined pretreatments. The bio-oil yields from WCS290, LCS290, and CCS290 increased by 134.04%, 127.66%, and 129.79% respectively, compared with that from CS290. Similarly, their relative sugar contents (rich in levoglucosan) increased to 36.63%, 45.89%, and 52.34%, respectively. Aqueous phase oil washing-torrefaction is a promising pretreatment and acetic acid plays the most important role.

Effects of biomass pyrolysis derived wood vinegar on microbial activity and communities of activated sludge.

The effects of wood vinegar (WVG) on microbial activity and communities of activated sludge were investigated in a sequencing batch reactor (SBR) process. Results showed that the optimal WVG concentration was 4 µL/L when the pollutants removal efficiency and microbial activity were promoted by a WVG dilution factor of 1000. WVG could reduce the increase in microbial species richness, which led to a more notable variety of microbial species diversity. The enhanced microbial activity and communities were addressed to the promotion of 7 main classes of microbes in Proteobacteria, Bacteroidetes, Acidobacteria, and Nitrospirae phyla. The growth of ammonia-oxidizing bacteria (AOB), nitrite-oxidizing bacteria (NOB), and main genera of denitrifying bacteria (DNB), phosphorus-accumulating organisms (PAOs), and glycogen-accumulating organisms (GAOs) could be promoted by WVG, which improved the sewage treatment effectiveness in a SBR.

Catalytic fast pyrolysis of biomass: Selective deoxygenation to balance the quality and yield of bio-oil.

Firstly, the operating conditions were screened for biomass pyrolysis in a fixed bed with respect to higher oil yield. A temperature of 600 °C with an N2 flow of 80 ml/min exhibited the highest bio-oil yield. Then, the catalytic pyrolysis of biomass with various catalysts (Al2O3, CaO, MgO, CuO, Fe2O3, NiO, ZnO, ZrO2, TiO2, HZSM-5 and MCM-41) was studied to identify the selective deoxygenation method with respect to improve bio-oil quality with smaller drop in bio-oil yield. With the addition of CaO, the oxygen was mainly removed in the form of CO2, while, in other cases, more oxygen was removed in the form of H2O. Furthermore, more decarboxylation or less dehydration is better for the balance between yield and deoxygenation amount, and the preferred decarboxylation would lead to a higher pH and lower moisture content of bio-oil.

Comparative study of wet and dry torrefaction of corn stalk and the effect on biomass pyrolysis polygeneration.

Wet torrefaction (WT) possesses some advantages over dry torrefaction (DT). In this study, a comparative analysis of torrefied corn stalk from WT and DT was conducted along with an investigation of their pyrolysis properties under optimal conditions for biomass pyrolysis polygeneration. Compared with DT, WT removed 98% of the ash and retained twice the amount of hydrogen. The impacts of DT and WT on the biomass macromolecular structure was also found to be different using two-dimensional perturbation correlation infrared spectroscopy (2D-PCIS). WT preserved the active hydroxyl groups and rearranged the macromolecule structure to allow cellulose to be more ordered, while DT removed these active hydroxyl groups and formed inter-crosslinking structures in macromolecules. Correspondingly, the bio-char yield after WT was lower than DT but the bio-char quality was upgraded due to high ash removal. Furthermore, higher bio-oil yield, higher sugar content, and higher H2 generation, were obtained after WT.

Investigation on biomass nitrogen-enriched pyrolysis: Influence of temperature.

Biomass (bamboo waste) nitrogen-enriched pyrolysis was carried out in a fixed bed with NH3 atmosphere at 400-800 °C, and formation mechanism of N-containing species was explored in depth. Results showed that N-enriched pyrolysis greatly increased bio-oil and gas yields. H2 yield increased sharply to 130 mL/g (32.93 vol%) and became the main composition at higher temperature, while CH4 and CO yields deceased, and the lower heating value of gas reached ∼14 MJ/Nm3. For bio-oil, the content of phenols (main compositions) and N-containing species increased significantly, and the maximums reached 61.33% and 11.47%, respectively. While that of acetic acid (disappeared), O-containing species (aldehydes/ketones/furans/esters) and aromatics decreased largely accordingly. For biochar, Nitrogen content increased, and it contained abundant pyridininc-N, pyrrolic-N, quaternary-N, and pyridone-N-oxide. Possible reaction pathways of biomass N-enriched pyrolysis was proposed based on products evolution. In conclusion, biomass N-enriched pyrolysis could obtain high-valued N-containing chemical species and functional biochar.

Co-pyrolysis of lignocellulosic biomass and microalgae: Products characteristics and interaction effect.

Co-pyrolysis of biomass has a potential to change the quality of pyrolytic bio-oil. In this work, co-pyrolysis of bamboo, a typical lignocellulosic biomass, and Nannochloropsis sp. (NS), a microalgae, was carried out in a fixed bed reactor at a range of mixing ratio of NS and bamboo, to find out whether the quality of pyrolytic bio-oil was improved. A significant improvement on bio-oil after co-pyrolysis of bamboo and NS was observed that bio-oil yield increased up to 66.63wt% (at 1:1) and the content of long-chain fatty acids in bio-oil also dramatically increased (the maximum up to 50.92% (13.57wt%) at 1:1) whereas acetic acid, O-containing species, and N-containing compounds decreased greatly. Nitrogen transformation mechanism during co-pyrolysis also was explored. Results showed that nitrogen in microalgae preferred to transform into solid char and gas phase during co-pyrolysis, while more pyrrolic-N and quaternary-N generated with diminishing protein-N and pyridinic-N in char.

[Clinical efficacy on xerosis conjunctivitis of liver and kidney yin deficiency treated with SHI's acupuncture manipulation].

OBJECTIVE: To compare the efficacy of the patients of xerosis conjunctivitis with liver and kidney yin deficiency among the combined therapy of acupuncture and Shi's manipulation, common acupuncture and artificial tears therapy. METHODS: One hundred and eight patients were randomized into an acupuncture group, a SHI's manipulation group and an artificial tears group, 36 cases in each group. A total of 15 cases dropped out before the end of the study, including 4 cases in the acupuncture group, 6 cases in the SHI's manipulation group, and 5 cases in the artificial tears group. In the acupuncture group, acupuncture was applied to Jingming (BL 1) and Qiuhou (EX-HN 7) on the affected side, and the bilateral Sanyinjiao (SP 6) and Taixi (KI 3). The needles were retained for 20 min. In the SHI's manipulation group, on the basis of the treatment as the acupuncture group, Shuigou (GV26) was added and stimulated with SHI's acupuncture manipulation. In these two groups, acupuncture was given 3 times a week totally for 3 weeks. In the artificial tears group, sodium hyaluronate eye drops were used, 5 times a day, for 3 weeks totally. Separately, before treatment, at the moment after the 1st treatment and 3 weeks after treatment, the subjective symptom score, Schirmer I test, breakup time (BUT) of tear film were observed in each group. RESULTS: (1) Subjective symptom score: at the moment after the 1st treatment and 3 weeks after treatment, the scores in each group were all reduced significantly as compared with those before treatment (all P < 0.05). At the moment after the 1st treatment, the score in the SHI's manipulation group and the artificial tears group was reduced apparently as compared with that in the acupuncture group (both P < 0.05). In 3 weeks of treatment, the score in the SHI's manipulation group was reduced apparently as compared with the acupuncture group and the artificial tears group (both P < 0.05). (2) For Schirmer I test, at the moment of the 1st treatment, the result in the SHI's manipulation group and the artificial tears group was improved significantly as compared with that before treatment (both P < 0.05). In 3 weeks of treatment, the result in the acupuncture group and the SHI's manipulation group group was improved significantly as compared with that before treatment (both P < 0.05). At the moment of the 1st treatment, the result in the artificial tears group was improved significantly as compared with the acupuncture group and the SHI's manipulation group (both P < 0.05). In 3 weeks of treatment, the result in the acupuncture group and the SHI's manipulation group was better than that in the artifi-cial tears group separately (both P < 0.05). (3) For BUT, the result in the acupuncture group and the SHI's manipulation group was prolonged significantly as compared with that before treatment and was prolonged apparently as compared with that in the artificial tears group (both P < 0.05) in 3 weeks of treatment. CONCLUSION: The intervention of SHI's acupuncture manipulation relieves the subjective symptoms of xerosis conjunctivitis of liver and kidney yin deficiency and achieves the same efficacy as the common acupuncture and artificial tears treatment. It does not present the apparent advantages as the common acupuncture in the short term for promoting the tear secretion and tears film repair.

Considerations for use of acupuncture as supplemental therapy for patients with allergic asthma.

This study examines the clinical and immunomodulatory effects of acupuncture in the treatment of patients with allergic asthma. The acupuncture points GV14, BL12, and BL13 were selected based on the theory of traditional Chinese medicine in treating asthma. Manual acupuncture was performed once every other day (three times per week) for 5 weeks. The needles were twisted approximately 360° evenly at the rate of 60 times/min for 20 s, manipulated every 10 min and withdrawn after 30 min. Concentrations of sIgA and total IgA in secretions were determined by the combination of sucrose density gradient ultracentrifugation and RIA. Levels of cortisol in the plasma were measured by RIA. Total IgE in the sera was examined by ELISA. Flow cytometry was used to detect the numbers of CD3+, CD4+, CD8+, and IL-2R + T lymphocytes in the peripheral blood. The absolute and differential numbers of eosinophils in peripheral blood were counted with eosin staining. The total efficacy of the acupuncture treatment in patients with allergic asthma at the end of one course of treatment was 85 %. After treatment, the concentrations of sIgA and total IgA in the saliva (P<0.01, P<0.02) and nasal secretions (P<0.02, P<0.02) were significantly decreased in patients with allergic asthma. The levels of total IgE in sera (P<0.001), the counts of IL-2R + T lymphocytes (P<0.001), and the absolute and differential numbers of eosinophils (P<0.01, P<0.01) in the peripheral blood were also significantly decreased. The numbers of CD3+, CD4+, and CD8+ T lymphocytes in the peripheral blood were significantly increased in the allergic asthmatics treated by acupuncture (P<0.001, P<0.01, and P<0.001, respectively). The concentration of cortisol in the plasma of asthmatic patients did not change significantly after the acupuncture treatment (P>0.05). Acupuncture has regulatory effects on mucosal and cellular immunity in patients with allergic asthma and may be an adjunctive therapy for allergic asthma.

Effects of "moxibustion serum" on proliferation and phenotypes of tumor infiltrating lymphocytes.

Tumor infiltrating lymphocytes (TIL) were cultured with "moxibustion serum" (MS), and the results were examined by flow cytometry. The results indicated that MS could enhance the proliferation of TIL, accelerate it to reach the exponential growth phase, and assist recombinant interleukin 2 (rIL-2) to enhance successively the percentage of CD3+ positive cells, maintain the number of CD4+ positive T cells, promote greatly the percentage of CD8+ positive T cells among TILs, and reverse the CD4+/CD8+ ratio. Such cooperative effects rely on relative specificity of acupoints. It is suggested that MS is beneficial to the growth of TIL both in the aspects of proliferation and phenotypes.

Expression of interleukin-6 mRNA in ischemic rat brain after electroacupuncture stimulation.

Interleukin-6 (IL-6) is a potent, pleiotropic cytokine that plays a central role in host defense and acute inflammatory responses, exhibiting pro- and anti-inflammatory activities. However, little is known about the effect of acupuncture on IL-6 in inflammatory responses caused by cerebral ischemia-reperfusion. The objective of present study was to investigate the influence of electroacupuncture (EA) on IL-6 mRNA expression in ischemic rat brain, by means of reverse transcription-polymerase chain reaction (RT-PCR) and in situ hybridization. Data showed that EA stimulation significantly upregulated IL-6 mRNA levels in rat cortex and striatum following cerebral ischmia-reperfusion (P<0.05 vs. cerebral ischemia group, respectively), but nothing for sham-EA treatment. The result suggests that EA may partially participate in the regulation of inflammatory processes, and the mechanism of neuroprotective action of EA is implicated in modulation of IL-6 gene expression in cerebral ischemic injury.

Morphological study on colonic pathology in ulcerative colitis treated by moxibustion.

AIM:To observe the therapeutic effect of moxibustion on ulcerative colitis and its influence on the colonic mucosal morphology.METHODS:Forty-six patients with ulcerative colitis were randomly divided into the moxibustion with herbal medicine underneath group and the western medicine group. Thirty patients were treated with the above moxibustion and 16 patients with Salicylaye fapyridine (SASP).The colonic mucosa of 13 patients in the moxibustion group was observed by colonoscopy before and after the treatment. Mucin was also analyzed by H.E and AB-PAS staining.RESULTS:Seventeen patients were clinically cured,12 were improved and 1 unchanged in the moxibustion group. In the control group, 5 patients were clinically cured,7 improved and 4 unchanged. Thirteen patients with active UC were taken as the subjects for histopathologic analysis in this study. The colonic mucosal lesions were remarkably improved and the characteristic of the mucin also changed. In most sections, the chronic inflammation of mucosa was geatly ameliorated (P< 0.01). The inflammatory cell infiltratation much decreased and neutrophils, disapeared in most sections (P<0.001). The goblet cells significantly increased (P<0.001); crypt paracrypt abscess or mucosal ulceration was seen(P<0.001).CONCLUSION:The rate of cure of ulcerative colitis by moxibustion with herbal medicine beneath is superior to that by SASP. This sort of moxibustion can effectively improve the colonic mucosal lesions and restore the proportion of mucoprotein to near normal.

Study of the mechanisms of acupuncture and moxibustion treatment for ulcerative colitis rats in view of the gene expression of cytokines.

AIM:To observe the effect of acupuncture and moxibustion on the expression of IL-1beta and IL-6 mRNA in ulcerative colitis rats.METHODS:The SD rat ulcerative colitis model was created by immunological method associated with local stimulation. Colonic mucosa was prepared from human fresh surgical colonic specimens, homogenized by adding appropriate amount of normal saline and centrifuged at 3000r/min. The supernatant was collected for measurement of protein conentration and then mixed with Freund adjuvant. This antigen fluid was first injected into the plantae of the model group rats, and then into their plantae, dorsa, inguina and abdominal cavities (noFreund adjuvant for the last injection) again on the 10th, 17th, 24th and 31st day. When a certain titer of serum anti colonic antibody was reached, 2% formalin and antigen fluid (no Freund adjuvant) were administered separately by enema. The ulcerative colitis rat model was thus set up. The animals were randomly divided into four groups: model control group (MC, n = 8), electro acupuncture group (EA, n = 8), herbs partition moxibustion group (HPM 8), normal control group (NC,n = 8). HPM: Moxa cones made of refined mugwort floss were placed on the medicinal pad (medicinal pad dispensing: Radix Aconiti praeparata, cortex Cinnamomi, etc) for Qihai (RN 6) and Tianshu (ST 25, bilateral) and ignited. Two moxa cones were used for each acupoint once a day and 14 times in all. EA: Tianshu (bilateral) and Qihai were stimulated by the intermittent pulse with 2Hz frequency, 4mA intensity for 20 minutes once a day and 14 times in all. After treatment, rats of all four groups were killed simultaneously. The spleen was separated and the distal colon was dissected. Total tissue RNA was isolated by the guanidinium thiocyanate phenol chloroform extraction method. RT-PCR technique was used to study the expression of IL-1 beta and IL-6 mRNA.RESULTS:IL-1 beta and IL-6 mRNAs were not detected in the spleen and colonic mucosa of the NC rats, whereas they were significantly expressed in that of the MC rats.IL-1 beta and IL-6 mRNAs were markedly lower in the EA and HPM rats than that in MC rats. There was no significant difference between the levels of IL-1 beta and IL-6 mRNAs in the EA and HPM rats. The expressions of IL-1 beta and IL-6 mRNAs were nearly the same in the spleen and colon of all groups.CONCLUSION:Acupuncture and moxibustion greatly inhibited the expression of IL-1 beta and IL-6 mRNA in the experimental ulcerative colitis rats.