The ratio of H/C is a useful parameter to predict adsorption of the herbicide metolachlor to biochars.

Biochar adsorbent was produced by pyrolyzing traditional Chinese medicinal herb residue at 300, 500 and 750 °C (referred to as biochar-300, biochar-500 and biochar-750). Basic physical and chemical analyses, Fourier transform infrared spectroscopy (FT-IR), and thermodynamic analyses were performed to elucidate adsorption and properties of biochar. Biochar adsorption capacity of herbicide metolochlor, as measured by batch-type adsorption experiments by Freundlich constant Kf (mg1-n Ln kg-1), followed the order: biochar-750 > biochar-300 > biochar-500. Thermodynamic analysis suggested that adsorption of metolachlor on biochar was a spontaneous process. The adsorption isotherm for the biochar produced at the highest pyrolysis temperature was characteristic for adsorption process driven by a high surface area of biochar (85.30 m2 g-1), while the adsorption process for the biochar produced at the lowest temperature was controlled by its higher content of organic matter (39.06%) and abundant functional groups. The FT-IR spectra also showed that the biochar prepared at the lowest temperature had the highest number of surface groups. In general, pore-filling induced by the large surface area of the biochar was the dominant adsorption mechanism. When the H/C value was >0.5, the adsorption mechanism of biochar was dominated by surface chemical bond, while pore-filling played a major role when the H/C value was <0.5.

Effect of roxarsone metabolites in chicken manure on soil biological property.

Roxarsone (ROX), an organoarsenic feed additive, occurs as itself and its metabolites including As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in animal manure. Animal manure improves soil biological property, whereas As compounds impact microorganisms. The integral influence of animal manure bearing ROX metabolites on soil biological quality is not clear yet. Herein, the effect of four chicken manures excreted by chickens fed with four diets containing 0, 40, 80 and 120 mg ROX kg-1, on soil biological attributes. ROX addition in chicken diets increased total As and ROX metabolites in manures, but decreased manure total N, ammonium and nitrate. The elevated ROX metabolites in manures increased soil total As, As species and total N, and increased first and then decreased soil nitrate and nitrite, but did not affect soil ammonium in manure-applied soils. The promoting role of both soil As(III) and ammonium on soil microbial biomass carbon and nitrogen, respiration and saccharase activity, were exceeded or balanced by the inhibiting effect of soil nitrate. The suppression of soil catalase activity by soil As(V) was surpassed by the enhancement caused by soil nitrate and nitrite. Soil urease, acid phosphatase and polyphenol oxidase activities were not suitable bioindicators in the four manure-amended soils. Soil DMA did not affect soil biological properties, and MMA was not detectable in all manure-amended soils. The above highlights the complexity of joint influence of soil As and N on biological attributes. Totally, when ROX is used at allowable dose in chicken diet, soil biological quality would be suppressed in manure-amended soil.

Biochar Derived from Urban Green Waste Can Enhance the Removal of Cd from Water and Reduce Soil Cd Bioavailability.

The beneficial utilization of potentially increasing urban green waste (UGW) is critical for sustainable urban development in China. In this study, UGW was pyrolyzed at different temperatures, and the resulting biochar was used to amend Cd-contaminated soils to grow cabbage. Our results showed that the Cd adsorption capacity of UGW-biochar was positively correlated with the surface area, O/C, and (O+N)/C value of biochar. Furthermore, UGW-biochar was incorporated into three Cd-contaminated soils, including one acidic soil and two neutral soils, to assess its impact on the availability of Cd. The most substantial reduction in the concentration of available Cd was observed in the acidic soil, of the three tested soils. In the neutral soils, a more substantial reduction was found in the heavily Cd-contaminated soil compared to the lightly Cd-contaminated soil. UGW-biochar amendments to the three Cd-contaminated soils resulted in an increase in the cabbage biomass in acidic soil, whereas in neutral soils, it increased in lightly contaminated soils but decreased in heavily contaminated soils. Additionally, the Cd bioaccumulation factor (BCF), translocation factor (TF), and removal efficiency (RE), as impacted by the biochar application, were calculated in the lightly Cd-contaminated soil-cabbage system. The BCF decreased from 5.84 to 3.80 as the dosage of the UGW-biochar increased from 0% to 3%, indicating that the UGW-biochar immobilized Cd and reduced its bioaccumulation in cabbage roots. Based on our investigations, UGW-biochar effectively immobilizes Cd by reducing its mobility and bioavailability in a lightly contaminated environment matrix.

Biochar protects hydrophilic dissolved organic matter against mineralization and enhances its microbial carbon use efficiency.

A combination of biochar with exogenous organic material in soils is often used in practical farmland management. The objective of this study was to determine how biochar affects organic matter decomposition by studying the decomposition of 13C-labelled hydrophilic (Hi-) and hydrophobic (Ho-) dissolved organic matter (DOM) in acid and neutral soils during a 60-day incubation experiment. The proportions of carbon (C) mineralization in Hi-DOM with or without biochar addition were 32.6% or 34.5% in acid soil (P > 0.05) and 15.4% or 22.3% in neutral soil (P < 0.05), respectively. In contrast, those proportions of Ho-DOM-C mineralization with or without biochar addition were 20.0% or 21.4% in acid soil and 19.0% or 20.5% in neutral soil (P > 0.05), respectively. These results showed that biochar could protect Hi-DOM against mineralization in neutral soil but exhibited less effect on Ho-DOM mineralization in both acid and neutral soils. Additionally, biochar did not affect microbial incorporation of Hi- or Ho-DOM in acid and neutral soils. However, biochar notably improved the microbial carbon use efficiency (CUE) of Hi-DOM while it significantly reduced the CUE of Ho-DOM in neutral soil (P < 0.05), indicating that the effect of biochar on microbial CUE was related to organic matter type and soil pH. This study suggests that Hi-DOM can outperform Ho-DOM to decrease C loss and improve microbial CUE in neutral soil with biochar addition. This phenomenon could be due mainly to the different chemical compositions of Hi-DOM and Ho-DOM and their distinct microbial preference. These findings can provide references for biochar's ability to regulate the decomposition of organic matter.

Influence of biochar and soil properties on soil and plant tissue concentrations of Cd and Pb: A meta-analysis.

The application of biochar to soils contaminated with potentially toxic elements (PTEs) has received particular attention due to its ability to reduce PTE uptake by the plants. Therefore, we conducted a meta-analysis to identify Cd and Pb concentrations in plant shoots and roots in response to biochar application and soil properties. We collected data from 65 peer-reviewed journal articles published from 2009 to 2020 in which 66% of manuscripts were published from 2015 to 2020. The data were processed using OpenMEE software. The results pinpointed that addition of biochar to soil caused a significant decrease in shoot and root Cd and Pb concentrations as compared to untreated soils with biochar (control), and the reduction rate was affected by plant types and both biochar and soil properties. The biochar size less than 2 mm, biochar pH higher than 10, pyrolysis temperature of 401-600 °C, and the application rate higher than 2% appeared to be effective in reducing shoot and root Cd and Pb concentration. Soil properties such as pH, SOC, and texture influenced the efficiency of biochar for reducing plant Cd and Pb uptake. Biochar application increased SOC (54.3%), CEC (48.0%), pH (0.08), and EC (59.4%), and reduced soil extractable Cd (42.1%) and Pb (47.1%) concentration in comparison to control. A detailed study on the rhizosphere chemistry and uptake mechanism will help to underpin the biochar application rates and their efficiency reducing PTE mobility and plant uptake.

Facile synthesis of polyoxometalate-modified metal organic frameworks for eliminating tetrabromobisphenol-A from water.

Removal of tetrabromobisphenol-A (TBBPA) from wastewater is of significance to protect the aquatic life. The present study reports the facile preparation of polyoxometalate-modified metal-organic framework (MOFs) materials for TBBPA removal from water. The polyoxometalate-modified MOFs exhibited significantly higher affinity towards TBBPA than the control MOFs. The experimental data were fitted with the Langmuir, Freundlich and Dubinin-Radushkevich models. The TBBPA adsorption onto modified MOFs fitted the pseudo-second-order kinetic model. The equilibrium adsorption isotherms showed that the adsorption of TBBPA can be fitted by the Langmuir model. The maximum adsorption capacity of adsorbent composites reached 3.65 mg/g, with 95 % removal of TBBPA. The thermodynamic parameters indicated that adsorption was spontaneous. A blue shift of phosphorus peaks obtained from XPS spectra implied the formation of intrinsic chemical bonding between TBBPA and MOFs composites. Moreover, response surface methodology was employed to characterize the TBBPA adsorption in the co-existence of different factors. BPA had strong competition for TBBPA adsorption in a wide range of pH, but not at the middle level of Ca2+ concentration. Polyoxometalate-modified MOFs can easily be recycled using a simple organic solvent washing. This study provides a novel strategy for developing cost effective adsorbents to remove TBBPA from contaminated water.

Soil calcium significantly promotes uptake of inorganic arsenic by garland chrysanthemum (ChrysanthemumL coronarium) fertilized with chicken manure bearing roxarsone and its metabolites.

Roxarsone (ROX), a widely used feed organoarsenic additive, occurs as itself and its metabolites in animal manure that is commonly land used as fertilizer. Soil property impacts arsenic (As) speciation and bioavailability. Fourteen soils across China were used to conduct culture experiments to investigate As uptake by garland chrysanthemum (ChrysanthemumL coronarium), with the soils fertilized with chicken manure bearing ROX and its metabolites. The results show As(III) was the sole As form in garland chrysanthemum shoots, and As(III) and As(V) occurred in roots. Only inorganic As was detected in all soils when the plants were harvested. Stepwise regression analysis shows soil-exchangeable Ca predominated shoot As(III) concentration (shoot As(III) = 1.60030 soil Ca, R 2 = 0.8832***). Therefore, ROX is transferred into the human food chain finally as inorganic As in plants. Application of animal manure bearing ROX and its metabolites is not recommended in Ca-rich soils to avoid excess inorganic As dietary exposure.

Biochar characteristics produced from rice husks and their sorption properties for the acetanilide herbicide metolachlor.

Rice husk biochar (RHBC) was prepared for use as adsorbents for the herbicide metolachlor. The characteristics and sorption properties of metolachlor adsorbed by the RHBC prepared at different pyrolysis temperatures were determined by analysis of physico-chemical characteristics, Fourier transform infrared spectroscopy (FTIR), Boehm titration, scanning electron microscopy (SEM), and thermodynamics and kinetics adsorption. With increasing pyrolysis temperature, the RHBC surface area greatly increased (from 2.57 to 53.08 m2 g-1). RHBC produced at the highest temperature (750 °C) had the greatest surface area; SEM also showed the formation of a porous surface on RH-750 biochar. The sorption capacity of RHBC also increased significantly with increasing pyrolysis temperature and was characterized by the Freundlich constant K f for the adsorption capacity increasing from 125.17-269.46 (pyrolysis at 300 °C) to 339.94-765.24 (pyrolysis at 750 °C). The results indicated that the surface area and pore diameter of RHBC produced with high pyrolysis temperature (i.e., 750 °C) had the greatest impact on the adsorption of metolachlor. The FTIR, Boehm titration, and SEM analysis showed that the greatest number of surface groups were on RHBC produced at the lowest temperature (300 °C). The biochars produced at different pyrolysis temperatures had different mechanisms of adsorbing metolachlor, which exhibited a transition from hydrogen bonds dominant at low pyrolytic temperature to pore-filling dominant at higher pyrolytic temperature.

Delivery of roxarsone via chicken diet→chicken→chicken manure→soil→rice plant.

Roxarsone (ROX), a widely used feed additive, occurs as itself and its metabolites in animal manure. Rice is prone to accumulate As than other staple food. Four diets with 0, 40, 80 and 120mgROXkg(-1) were fed in chickens, and four chicken manures (CMs) were collected to fertilize rice plants in a soil culture experiment. Linear regression analysis shows that the slopes of As species including 4-hydroxy-phenylarsonic acid, As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in CM versus dietary ROX were 0.033, 0.314, 0.033, 0.054 and 0.138, respectively. Both As(III) and DMA were determined in all rice grains, and As(III), As(V), MMA and DMA in rice hull, but detectable As forms in rice straws and soils increased with increasing ROX dose. Grain As(III) was unrelated to ROX dose but exceeded the Chinese rice As limit (0.15mgAs(III)kg(-1)). Dietary ROX enhanced straw As(III) mostly, with the slope of 0.020, followed by hull DMA (0.006) and grain DMA (0.002). The slopes of soil As(V) and As(III) were 0.003 and 0.001. This is the first report illustrating the quantitative delivery of ROX via food chain, which helps to evaluate health and environmental risks caused by ROX use in animal production.

Phosphate enhances uptake of As species in garland chrysanthemum (C. coronarium) applied with chicken manure bearing roxarsone and its metabolites.

Roxarsone (ROX), a world widely used feed organoarsenic additive in animal production, can be excreted as itself and its metabolites in animal manure. Animal manure is commonly land applied with phosphorous (P) fertilizer to enhance the P phytoavailability in agriculture. We investigated the accumulation of As species in garland chrysanthemum (C. coronarium) plants fertilized with 1% (w/w, manure/soil) chicken manure bearing ROX and its metabolites, plus 0, 0.05, 0.1, 0.2, 0.4, and 0.8 g P2O5/kg, respectively. The results show that As(III) was the sole As compound in garland chrysanthemum shoots, and As(III) and As(V) were detectable in roots. Elevated phosphate level supplied more As(V) for garland chrysanthemum roots through competitive desorption in rhizosphere, leading to significantly enhanced accumulation of As species in plants. As(III) was the predominant As form in plants (85.0∼90.6%). Phosphate could not change the allocation of As species in plants. Hence, the traditional practice that animal manure is applied with P fertilizer may inadvertently increase the potential risk of As contamination in crop via the way ROX → animal → animal manure → soil → crop.

Roxarsone and its metabolites in chicken manure significantly enhance the uptake of As species by vegetables.

Roxarsone is an organoarsenic feed additive which can be finally degraded to other higher toxic metabolites after excreted by animal. In this work, the uptake of As species by vegetables treated with chicken manure bearing roxarsone and its metabolites was investigated. It was showed that more than 96% of roxarsone added in chicken feed was degraded and converted to arsenite, monomethylarsonic acid, dimethylarsinic acid, arsenate, 4-hydroxyphenylarsonic acid and other unknown As species. Arsenite and arsenate could be found in roots of vegetables but only arsenite transported up to shoots. Chicken manure bearing roxarsone and its metabolites increased 33-175% of arsenite and 28% ∼ seven times of arsenate in vegetable roots, 68-175% of arsenite in edible vegetable shoots. Arsenite, the most toxic As form, was the major extractable As species in vegetables accounted for 79-98%. The results reflected that toxic element As could be absorbed by vegetables via the way: roxarsone in feed → animal → animal manure → soil → crop and the uptake of As species would be enhanced by using chicken manure bearing roxarsone and its metabolites as organic fertilizer.

Occurrence of arsenic impurities in organoarsenics and animal feeds.

Organoarsenics are widely used as excellent feed additives in animal production in the world. Roxarsone (ROX) and arsanilic acid (ASA) are two organoarsenics permitted to be used in China. We collected 146 animal feed samples to investigate the appearance of ROX, ASA, and potential metabolites, including 3-amino-4-hydroxyphenylarsonic acid (3-A-HPA), 4-hydroxyphenylarsonic acid (4-HPA), As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in feeds. The stability of ROX in both ROX additives and animal feeds was also examined. The results show that 25.4% of the 146 animal feeds contained organoarsenics, with average contents of ROX and ASA as 7.0 and 21.2 mg of As/kg, respectively. Unexpectedly, As(III) and MMA frequently occurred as As impurities in feeds bearing organoarsenics, with higher contents than organoarsenics in some samples. 3-A-HPA, 4-HPA, and DMA were not detected in all samples. ROX and As impurities in both ROX additives and feeds stayed unchanged in the shelf life. It suggests that As impurities in animal feeds bearing organoarsenics should generate from the use of organoarsenics containing As impurities. This constitutes the first report of As impurities in organoarsenics.

External inorganic N source enhances the uptake of As species in garland chrysanthemum (C. coronarium) amended with chicken manure bearing roxarsone and its metabolites.

Roxarsone (ROX), a widely used feed organoarsenic additive, is excreted as itself and its metabolites in animal manure. Animal manure is commonly applied with N fertilizer to meet the N demand of crop. We investigated the accumulation of As species in garland chrysanthemum plants fertilized with chicken manure (CM) bearing ROX and its metabolites, combined with different inorganic N sources (NH4(+), NO3(-) and urea), respectively. The change of pH, N forms and As species in soils was examined as well. The results show that As(V), As(III) and dimethylarsinic acid (DMA) were detectable in soils, and conversions between As species were affected by three inorganic N sources, irrespective of N form and soil pH. As(III) was the sole As species in garland chrysanthemum shoots, and As(III) and As(V) could be detected in roots. Urea, superior to NH4(+), significantly enhanced the uptake of As species in plants by promoting plant growth, while NO3(-) slightly reduced the As accumulation due to decreased biomass. As(III) was the dominant As compound (86.9-89.7%) in plants. Therefore, inorganic N fertilizers may inadvertently increase the risk of As contamination in plant from ROX via the way ROX→chicken→CM→soil→crop.

[Investigation of As, Cu and Zn species and concentrations in animal feeds].

Seventy chicken and seventy-six pig feeds were collected from the feed stores in Guangdong province, and the species and concentrations of As, Cu and Zn were determined. We also examined the stability of roxarsone (ROX), one of the most widely used organoarsenical additives, either in the additive or in the feed at room temperature. The results showed that, averagely, the chicken and pig feeds contained 3.6 and 6.5 mg.kg-1 (As), 18.2 and 119.4 mg.kg-1 (Cu),and 124.6 and 486.2 mg.kg-1 (Zn), respectively. The excessive dosages of As, Cu and As in animal feeds will lead to higher residue of As, Cu and Zn in animal manures. Based on the national limit criteria for feed or feed additive, it was supposed that organoarsenicals had been used, only few feed samples exceeded the As limit, however, the excessive Cu and Zn in pig feeds were much more common. Organoarsenicals were found in 25.4% of the total feed samples, and As(Ill) and As(V) were the two most commonly detected As impurities in feeds bearing organoarsenicals. The mean detectable ROX and arsenilic acid were 7.0 and 21.2 mg.kg-1, respectively. Organoarsenicals were detectable in 24. 3% of the chicken feed samples and 26. 3% of the pig feed samples. Moreover, ROX was commonly used in chicken feeds, while p-ASA in pig feeds. ROX and the inorganic As impurities, either in the commercial additive or in the feed, remained stable for at least 30 days at room temperature, indicating the higher As impurities in feeds probably originated from the As impurities in organoarsenical additives. This is a new As exposure pathway for the producer and user of organoarsenicals and feeds amending organoarsenicals.

[Pesticide residual status in litchi orchard soils in Guangdong, China].

Litchi is a famous tropical and subtropical fruit originated in South China. Guangdong is one of the most important litchi production areas in China. Two hundred and eight soil samples were collected in litchi orchards after harvesting the fruit, in which nine often-used pesticides including metalaxyl, mancozeb, carbendazim, deltamethrin, cypermethrin, cyhalothrin, dipterex, dimethoate and dichlorvos were detected. The results showed that the detectable rates of various pesticides were ranked cypermethrin (59.1%) > carbendazim (51.0%) > mancozeb (11.1%) > metalaxyl (6.7%) > cyhalothrin (3.4%). Dimethoate and dichlorvos were detectable in few soil samples, and deltamethrin and dipterex were undetectable in all samples. The percentages of soil samples where different pesticides could be detected in one sample followed the order: one pesticide detectable (40.4%) > two pesticides simultaneously detectable (31.3%) > pesticide undetectable (18.8%) > three pesticides simultaneously detectable (8.2%) > four pesticides simultaneously detectable (1.4%). The concentrations of mancozeb in detectable samples averaged 39.05 microg x kg(-1), and that of cypermethrin was 7.83 microg x kg(-1). The mean concentrations of the other five pesticides ranged from 0.19 microg x kg(-1) to 1.65 microg x kg(-1). Totally, the pesticide residue status in litchi orchards in Guangdong was venial.