The Effects of Partial Substitution of Fertilizer Using Different Organic Materials on Soil Nutrient Condition, Aggregate Stability and Enzyme Activity in a Tea Plantation.

Fertilization plays a crucial role in enhancing tea production. However, it has been demonstrated that the long-term single application of chemical fertilizer will reduce soil nutrient content and the formation of soil aggregates, which is not conducive to the sustainable development of soil and agriculture. Many studies have shown that partial substitution of chemical fertilizer with organic fertilizer can improve soil physicochemical properties and soil nutrient content. This study compared the effects of different organic materials as substitutes for chemical fertilizer. We partially replaced chemical fertilizer with rabbit manure, wine lees and rapeseed cake, amounting to 30% of the total annual nitrogen application in the field experiment, and we set nine different fertilization methods to assess and analyze the soil nutrient condition, aggregate stability and enzyme activity. The results showed that the experimental soil aggregate mean weight diameter (MWD) and geometric mean diameter (GMD) were significantly increased compared with control (p < 0.05); the aforementioned fertilization methods also decreased the soil aggregate fractal dimension (D), disruption rate (PAD), average weight-specific surface area (MWSSA) and soil erodibility factor (K). The application of the fertilizer containing organic materials and microbial agent increased soil organic carbon (SOC) by 20.7% to 22.6% and total nitrogen (TN) by 34.6% to 38.1%; it also significantly promoted sucrase, urease and protease activities in all aggregate sizes (p < 0.05) and increased the 2-5 mm aggregate content. The correlation coefficients between the SOC and the enzyme activities were 0.18-0.95, and most of them showed an extremely significant positive correlation (p < 0.01). In conclusion, the application of fertilizers containing organic materials and microbial agents can improve soil aggregate stability, aggregate enzyme activity and soil structural stability.

A new type of calcium-rich biochars derived from spent mushroom substrates and their efficient adsorption properties for cationic dyes.

Adsorption is commonly accepted as a most promising strategy in dye wastewater treatment, and the widespread use of adsorption emphasizes the need to explore low-cost but excellent adsorbents. Herein, a low-cost adsorbent (calcium-rich biochar) was developed, which was directly pyrolyzed from spent mushroom substate without any modification. This study evaluated the potential application of two calcium-rich biochars (GSBC and LSBC) derived from spent substrates of Ganoderma lucidum and Lentinus edodes, respectively. The effects of pyrolysis temperature on the calcium-rich biochars characteristics and their adsorption mechanism for cationic dyes (Malachite Green oxalate (MG) and Safranine T (ST)) were studied systematically. The increase in pyrolysis temperature from 350 to 750 °C led to an increase in both biochar ash, Ca content, and specific surface area, which made high-temperature biochars (GS750 and LS750) the superior adsorbents for cationic dyes. Batch adsorption results showed LS750 was more efficient to adsorb dyes than GS750 attributed to its higher Ca content and larger specific surface area. According to the Langmuir model, LS750 had high adsorption capacities of 9,388.04 and 3,871.48 mg g-1 for Malachite green and ST, respectively. The adsorption mechanism of dye MG could be attributed to pore filling, hydrogen bonding, electrostatic interaction, ion exchange, and π-π stacking, while ST adsorption mainly involved pore filling, electrostatic interaction, ion exchange, and π-π stacking. Attributed to their excellent adsorption performance, cheap source, and good reusability, biochars obtained from SMSs were very promising in dyeing wastewater treatment.

Activated biochar derived from spent Auricularia auricula substrate for the efficient adsorption of cationic azo dyes from single and binary adsorptive systems.

In this study, spent Auricularia auricula substrate (AS)-derived biochar (ASBCs) and activated biochar with NaOH (A-ASBC) were evaluated for the adsorption of cationic azo dyes, including methylene blue (MB), rhodamine B (RB), and crystal violet (CV), from single and binary adsorptive systems. A-ASBC showed a higher maximum adsorption capacity for these dyes (MB: 53.62 mg·g-1, RB: 32.33 mg·g-1, CV: 735.73 mg·g-1) than ASBCs in a single system because it had a greater specific surface area and more oxygen containing-functional groups on the surface. The adsorption process of the three dyes onto the adsorbents was in good agreement with the Freundlich adsorption isotherm and fit the pseudo-second-order kinetic model, which revealed sorbate polymolecular layer formation over the adsorbent surface and the involvement of chemisorption. The adsorption mechanism showed that the adsorption of three dyes on adsorbents could be postulated as a multistep process with extraordinary affinity-induced adsorption in terms of both physisorption and chemisorption. In the binary adsorptive system, the results showed that all MB, RB, and CV had antagonistic/competitive effects on each other's adsorption (QBinary/QSingle < 1). Furthermore, a phytotoxic assay affirmed the effectiveness of the adsorbent in adsorbing dye species from aqueous solutions using Brassica pekinensis L. seeds as the model. Therefore, activated biochar prepared from AS can be used as a potentially economical and effective adsorbent for treating printing and dyeing wastewater.

Efficient Removal of Cu(II), Zn(II), and Cd(II) from Aqueous Solutions by a Mineral-Rich Biochar Derived from a Spent Mushroom (Agaricus bisporus) Substrate.

This study evaluated the novel application of a mineral-rich biochar derived from a spent Agaricus bisporus substrate (SAS). Biochars with various pyrolysis temperatures (350-750 °C) were used to remove Cu(II), Zn(II), and Cd(II) from aqueous solutions. The adsorption characteristics and removal mechanisms of the biochars were investigated. The adsorption kinetics and isotherm data were fitted well by pseudo-second-order and Freundlich models. The Langmuir maximum removal capacity (Qmax) values of Cu(II), Zn(II), and Cd(II) were ordered as SAS750 > SAS350 > SAS550, and the Qmax values of SAS750 were 68.1, 55.2, and 64.8 mg·g-1, respectively. Overall, the removal mechanisms of biochar at a low production temperature (350 °C) to Cu(II), Zn(II), and Cd(II) were mainly via ion exchange (54.0, 56.0, and 43.0%), and at a moderate production temperature (550 °C), removal mechanisms were mainly via coordination with π electrons (38.3, 45.9, and 55.0%), while mineral precipitation (65.2, 44.4, and 76.3%, respectively) was the dominant mechanism at a high produced temperature (750 °C). The variation of the mutual effect of minerals and heavy metals was the predominant factor in the sorption mechanism of mineral precipitation and ion exchange. The results demonstrated that spent Agaricus bisporus substrate biochar is a potential candidate for the efficient removal of heavy metals, which provides a utilization route for spent mushroom substrates.

Phytoremediation of soil heavy metals (Cd and Zn) by castor seedlings: Tolerance, accumulation and subcellular distribution.

Cd and Zn pollution was observed to often occur simultaneously in soils. However, previous studies focused on single heavy metal instead of Cd and Zn combined pollution. Castor (Ricinus communis) is considered to have great potential for contaminated soil remediation. The resistance of castor seedlings to heavy metals and the mechanism behind it remain unknown. In this study, the tolerance and accumulation ability of castor seedlings to Cd and Zn were investigated, and the accumulation mechanism involving the subcellular distribution in different tissues was further explored. The results on biomass and chlorophyll revealed that castor seedlings have good tolerance to the pollution with 0-5 mg/kg Cd and 380 mg/kg Zn, while not to the heavy pollution with 25 mg/kg Cd and 380 mg/kg Zn. The maximum accumulation concentrations of Cd and Zn, 175.3 mg Cd/kg and 386.8 mg/kg Zn, appeared in castor seedling root instead of stem and leaf, indicating that root played a significant part in accumulating Zn and Cd. The relative low dosage of Cd (0-5 mg/kg) promoted the accumulation of Zn in the subcellular component, while high dosage (25 mg/kg) inhibited the accumulation of Zn. In subcellular accumulation and distribution of castor seedlings, Cd (27.1%-69.4%) and Zn (39.6%-66.6%) in the cell wall was the highest. With the increase of Cd addition, the accumulation of Cd increased in cell wall while decreased in organelle and soluble fraction. Hydroxyl, amino, amides and carboxyl functional groups on cell wall might provided the main binding sites for Cd and Zn.

Effect of spent mushroom substrate on strengthening the phytoremediation potential of Ricinus communis to Cd- and Zn-polluted soil.

Phytoremediation is a kind of efficient strategy for remediating soils polluted with heavy metals. The aim of this study was to investigate the influence of spent mushroom substrate (SMS) on the phytoremediation potential of Ricinus communis in Cd- and Zn-polluted soil. We treated the soil with SMS before growing plants and analyzed the contents, distribution of heavy metals, and response of plants after growth. SMS increased the contents of Cd (5%-13%) and Zn (16%-20%) in the cell wall. This finding suggested that high amounts of Cd and Zn were absorbed and bonded to the cell wall through metabolism adaption and formed stable compounds, which reduced the damage of the heavy metal to cells. SMS also decreased the levels of superoxide dismutase, peroxidase, and catalase by 9.5%-27.7%, 8.8%-30.0% and 8.5%-28.1%, respectively. Treatment of SMS alleviated the toxicity of heavy metal in plants and increased the extracted amounts of Zn and Cd by 101%-227% and 51%-189%, respectively. Hence, SMS treatment could reduce the toxicity of heavy metals to plants and strengthen the phytoremediation potential.

Dioxin distribution characteristics and health risk assessment in different size particles of fly ash from MSWIs in China.

During the process of treating and recycling Municipal Solid Waste Incinerators (MSWIs) fly ash, polychlorinated dibenzo-p-dioxins (PCDD/Fs) and polychlorinated dibenzofurans (dl-PCBs) in fly ash may potentially mobilize in the atmosphere and be widely distributed in the environment because of the inevitable re-suspension. Thus, this work presents the distributions of PCDD/Fs and dl-PCBs in inhalable coarse particles (Dp10-2.5 (particle diameter in µm)), fine particles (Dp<2.5) of fly ash and original fly ash from four MSWI plants in China. The results show that PCDD/Fs and dl-PCBs preferentially concentrated in Dp10-2.5 and Dp<2.5. Their mass concentrations and TEQ were significantly higher than those in the original fly ash, but the distribution of PCDD/Fs congeners in Dp10-2.5 and Dp<2.5 was close to that in the original fly ash. The main TEQ contribution included 1,2,3,7,8-PeCDD, 2,3,7,8-TeCDD in PCDDs and 2,3,4,7,8-PeCDF in PCDFs for Dp10-2.5, Dp<2.5 fractions and the original fly ash. Furthermore, the mass and TEQ contribution of dl-PCBs was relatively low. In addition, compared with the fluidized bed, the samples from the grate-type furnaces had significantly lower dioxin concentrations. In terms of potential health risk, the non-carcinogenic risk of PCDD/Fs in Dp10-2.5 and Dp<2.5 were estimated at 9.87 × 10(-1) to 4.81 and 1.19-7.95. For the carcinogenic risk of PCDD/Fs, both accumulation of Hazard Quotients (HQ) in Dp10-2.5 and Dp<2.5 exceeded the threshold limit and should be considered as unacceptable risk for onsite workers. The above findings could provide data to support the risk management of MSWI fly ash during the process of recycle and disposal.

Enrichment of heavy metals in fine particles of municipal solid waste incinerator (MSWI) fly ash and associated health risk.

During the pretreatment and recycling processes, the re-suspended dust from municipal solid waste incinerator (MSWI) fly ash might pose a significant health risk to onsite workers due to its toxic heavy metal content. In this work, the morphological and mineralogical characteristics of fly ash in different particle sizes are presented. The concentrations of seven trace elements (Zn, Pb, Cu, Cd, Cr, Fe and Mn) in these samples were determined. The results show that volatile metals, such as Zn, Pb, Cu and Cd, were easily concentrated in the fine particles, especially in Dp2.5-1 and Dp1, with soluble and exchangeable substances as the main chemical species. The health risk assessment illustrated that the cumulative hazard indexes for non-carcinogenic metals in Dp10-5, Dp5-2.5, Dp2.5-1, and Dp1 were 1.69, 1.41, 1.78 and 2.64, respectively, which were higher than the acceptable threshold values (1.0). The cumulative carcinogenic risk was also higher than the threshold value (10(-6)). For the onsite workers, the relatively apparent non-carcinogenic and carcinogenic effects were from Pb and Cr, respectively. The above findings suggest that fine-grained fly ash contained a considerable amount of heavy metals and exhibited a great health risk.

Use of Energy Crop (Ricinus communis L.) for Phytoextraction of Heavy Metals Assisted with Citric Acid.

Ricinus communis L. is a bioenergetic crop with high-biomass production and tolerance to cadmium (Cd) and lead (Pb), thus, the plant is a candidate crop for phytoremediation. Pot experiments were performed to study the effects of citric acid in enhancing phytoextraction of Cd/Pb by Ricinus communis L. Citric acid increased Cd and Pb contents in plant shoots in all treatments by about 78% and 18-45%, respectively, at the dosage of 10 mM kg(-1) soil without affecting aboveground biomass production. Addition of citric acid reduced CEC, weakened soil adsorption of heavy metals and activated Cd and Pb in soil solutions. The acid-exchangeable fraction (BCR-1) of Pb remained lower than 7% and significantly increased with citric acid amendment. Respective increases in soil evaluation index induces by 14% and 19% under the Cd1Pb50 and Cd1Pb250 treatments upon addition of citric acid resulted in soil quality improvement. Ricinus communis L. has great potential in citric acid-assisted phytoextraction for Cd and Pb remediation.

Accumulation of de-icing salts and its short-term effect on metal mobility in urban roadside soils.

In this study, a field investigation combined with a laboratory column leaching experiment were carried out to assess the effects of de-icing salts application on the heavy metal mobilization in roadside soils in an old and large industrial zone in Northeastern China. In the field investigation, 41 roadside soils were collected from the industrial zone, and the results showed a strong rise in deicing salts related concentrations of Na (352-513 mg/kg) and Cl (577-2,353 mg/kg) and high values of Cd (1.2-7.6 mg/kg) and Pb (28.7-101.6 mg/kg). The most serious contaminated roadside soil was used for column leaching experiment alternately with de-icing salts solution and deionized water to simulate the runoff of de-icing salts into roadside soils followed by snowmelt or rainwater. The results showed that an extensive mobilization of Cd (20.90 % of the total Cd in the soil) occurred in the salt leachate, and a high correlation with Cl were found, indicating that Cl complexes are important for the mobilization. Conversely, only 2.34 % of the total amount of Pb in the soil was leached, confirming the usual hypotheses about the high immobility of Pb in soils. However, it was found that high Pb concentration coincided with peaks in Fe and TOC concentrations, and the proportion of Pb in the >0.45 µm phase was much low, which implied an extensive Pb mobilization with small-sized colloids.

Characteristics of dioxins content in fly ash from municipal solid waste incinerators in China.

MSWI fly ashes sampled from 15 large-scale commercial municipal solid waste incineration plants in China were analyzed for seventeen polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDFs) as well as twelve dioxin-like polychlorinated biphenyls (dl-PCBs). The concentration of PCDD/PCDFs and dl-PCBs in fly ash samples ranged from 2.8 to 190ngg(-1), and 59.6ngg(-1) on average. The toxic equivalent (TEQ) ranged from 34 to 2500ng WHO(2005)-PCDD/PCDF-PCB-TEQkg(-1), and 790ng WHO(2005)-PCDD/PCDF-PCB-TEQkg(-1) on average. For PCDDs, hexa-chlorinated homolog was the dominant compound except two fly ash samples. Tetra-chlorinated homolog was dominant for PCDFs except one sample. The ratio of PCDDs/PCDFs ranged from 0.32 to 2.44 (average 0.97). The contribution of dl-PCBs to total concentration and TEQ was relatively minimal. Correlation between the concentration of three congeners and total TEQ values of fly ashes was also established. The findings obtained in this work provided overview information on the PCDD/PCDF-PCB content characterization of MSWI fly ash in China, which can be available for MSWI fly ash management in the environment.

[Spatial distribution of three endocrine disrupting chemicals in sediments of the Suzhou Creek and their environmental risks].

Three environmental endocrine disrupting chemicals (EDCs), named nonylphenol (NP), octylphenol (4-t-OP) and bisphenol A (BPA), in sediments of the Suzhou Creek and its branches were detected using gas chromatography-mass spectrometry (GC-MS) method. The results showed that the concentration of three chemicals varied greatly from site to site, which ranged from < 1.0-5 800, < 0.10-39 and 0.90-180 microg x kg(-1), respectively. In general, the accumulation of pollutants in sediments closely related to the intensity of anthropogenic activities: the concentration of three chemicals in sediments of municipal section of the creek are significantly higher than those in the sections of suburb of Shanghai city and Jiangsu province; the chemical concentrations in sediments of branches are significantly higher than those of the main stream of the creek. Significant correlations between each two of the three chemicals in sediments were observed, implying their similar source provenance. Taking nonylphenol as an example, the environmental risks of the EDCs in sediments were assessed. The result indicated that this chemical in the entire creek except the Wujiagang Bridge point had posed potential toxic risks to ecological system. Therefore, more countermeasures should be taken to prevent EDCs from entering the creek.

Preparation of SnO2 nanowires by solvent-free method using mesoporous silica template and their gas sensitive properties.

In this paper, a facile method was presented to synthesize tin dioxide (SnO2) nanowires by solvent-free method using SnCl2 x 2H2O as precursor and mesoporous silica SBA-15 as the hard template. No solvent was used in the processing. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and N2 adsorption/desorption isotherms. The results indicated that SnO2 nanowires fabricated by this method have a diameter of about 8 nm and a relatively high surface area 73.0 m2/g. The gas sensing properties of SnO2 nanowires were measured. The response and recovery time of this sensor were 6 s and 12 s, respectively. With the concentration of toluene increasing, the response of the sensor doubled increase. Compared with bulk SnO2, SnO2 nanowires showed much higher response to toluene.

Biodegradation of chlordane and hexachlorobenzenes in river sediment.

Contamination of river sediments by persistent organic pollutants (POPs) is a worldwide concern, and microbial degradation is regarded as an important process for removal of POPs from river sediments. To date, there is still a lack of systematic study on chlordane biodegradation in river sediments, and the information on hexachlorobenzene (HCB) biodegradation in river sediments is very limited in Japan. We investigated the anaerobic biodegradation potential of trans-chlordane (TC), cis-chlordane (CC), and HCB in sediment samples collected at three sites along the Kamogawa River in Saitama Prefecture, Japan. Lag period and biodegradation rates of TC and CC in the three sediments varied greatly with their properties and contamination by TC and CC. In contrast, biodegradation of HCB in all three sediments started immediately with the start of the experiment without lag period, and major differences in biodegradation rates among the sediments were not observed. At the end of 20-week anaerobic incubation in the dark at 30 degrees C temperature, degradation rates ranged from 0.0% to 33.0% for TC, 0.0% to 12.0% for CC, and 47.6% to 59.4% for HCB. Results showed that the high-to-low order of biodegradation in the river sediments was HCB>TC>CC. Although the sediments were collected in the same river, their biodegradation potential varied with properties. Sediment with rich organic content and contamination by TC and CC or HCB was observed to have high biodegradation rates for these pollutants. In addition, biodegradation of TC, CC and HCB was companied by obvious methane generation and drop of oxidation-reduction potential (ORP).

Hydroxyl radical generation and oxidative stress in Carassius auratus liver as affected by 2,4,6-trichlorophenol.

With Carassius auratus, one of the main economic fish species in Eastern China as test material, this paper studied the hydroxyl radical generation and oxidative stress in its liver under the effect of 2,4,6-trichlorophenol (2,4,6-TCP). Different doses of 2,4,6-TCP were injected intraperitoneally into the fishes, and the Electron paramagnetic resonance (EPR) spectra of hepatic free radicals, activities of superoxide dismutase (SOD), catalase (CAT) and glutathione-s-transferase (GST), levels of reduced glutathione (GSH) and oxidized glutathione (GSSG), and malondialdehyde (MDA) contents were determined 24h after injection. The results showed that under the effects of 2,4,6-TCP, the generation of free radical that was considered to be hydroxyl radical increased significantly, the activities of antioxidant enzymes decreased, with CAT most strongly affected and followed by SOD and GST, the GSH level decreased significantly while GSSG level had little difference, resulting in a decreased GSH/GSSG ratio, and the MDA content increased significantly. All the test parameters showed that C. auratus was subjected to oxidative stress and damage when exposed to 2,4,6-TCP.