Residues and potential ecological risks of veterinary antibiotics in manures and composts associated with protected vegetable farming

Veterinary antibiotics (VAs) are emerging contaminants and enter into soil principally by agricultural application of organic fertilizer. A total of 33 solid animal manures and 17 compost samples from protected vegetable farms in nine areas of China were analyzed for the antibiotic classes of tetracyclines, fluoroquinolones, sulfonamides, and macrolides (17 substances in total). Oxytetracycline was found as a dominant compound in the samples, and its highest concentration reached 416.8 mg kg(-1) in a chicken manure sample from Shouguang, Shandong Province. Among the samples, animal manures (especially pig manure) contained higher VA residues than composts. However, fluoroquinolones exhibited higher persistence in the compost samples than other antibiotic classes. This is particularly the case in the rice husk compost, which contained the highest level of ofloxacin and ciprofloxacin (1334.5 and 1717.4 mu g kg(-1) on average, respectively). The veterinary antibiotic profile in the risk husk compost had a good relationship with that in the corresponding manures. The refined commercial compost had the lowest VA residues among the compost samples in general. This implied that composting process might be important to reduce the antibiotic residue. High residue of antibiotics in soil was assumed to be a hazard to ecosystem. This is especially noticeable under current application rates (150 t ha(-1) a(-1)) in protected vegetable farming because over half of the samples exhibited a risk quotient (RQ) > 1 for one or more antibiotics.Veterinary antibiotics (VAs) are emerging contaminants and enter into soil principally by agricultural application of organic fertilizer. A total of 33 solid animal manures and 17 compost samples from protected vegetable farms in nine areas of China were analyzed for the antibiotic classes of tetracyclines, fluoroquinolones, sulfonamides, and macrolides (17 substances in total). Oxytetracycline was found as a dominant compound in the samples, and its highest concentration reached 416.8 mg kg(-1) in a chicken manure sample from Shouguang, Shandong Province. Among the samples, animal manures (especially pig manure) contained higher VA residues than composts. However, fluoroquinolones exhibited higher persistence in the compost samples than other antibiotic classes. This is particularly the case in the rice husk compost, which contained the highest level of ofloxacin and ciprofloxacin (1334.5 and 1717.4 mu g kg(-1) on average, respectively). The veterinary antibiotic profile in the risk husk compost had a good relationship with that in the corresponding manures. The refined commercial compost had the lowest VA residues among the compost samples in general. This implied that composting process might be important to reduce the antibiotic residue. High residue of antibiotics in soil was assumed to be a hazard to ecosystem. This is especially noticeable under current application rates (150 t ha(-1) a(-1)) in protected vegetable farming because over half of the samples exhibited a risk quotient (RQ) > 1 for one or more antibiotics

Fabrication, characterization and evaluation of mesoporous activated carbons from agricultural waste: Jerusalem artichoke stalk as an example

This work explores the feasibility of Jerusalem artichoke stem (JAS), an agricultural waste, as an alternative precursor for fabrication of mesoporous activated carbon (MAC) via conventional ZnCl2 activation. The as-prepared JAS-MACs were characterized by thermogravimetric, nitrogen gas adsorption isotherm and high resolution scanning electron microscopy analysis. The interacting effects of chemical dosage, activation temperature and time on the mesoporosity, mesopore volume and carbon yield were investigated, and further optimized by response surface methodology (RSM). The Brunauer-Emmett-Teller surface area, mesoporosity and mesopore volume of the JAS-MAC prepared under optimum condition were identified to be 1631 m(2)center dot g(-1), 90.16% and 1.11 cm(3)center dot g(-1), respectively. Compared with commercial activated carbons, this carbon exhibited a comparable monolayer adsorption capacity of 374.5 mg center dot g(-1) for Methylene Blue dye. The findings suggest that RSM could be an effective approach for optimizing the pore structure of fabricated activated carbons.This work explores the feasibility of Jerusalem artichoke stem (JAS), an agricultural waste, as an alternative precursor for fabrication of mesoporous activated carbon (MAC) via conventional ZnCl2 activation. The as-prepared JAS-MACs were characterized by thermogravimetric, nitrogen gas adsorption isotherm and high resolution scanning electron microscopy analysis. The interacting effects of chemical dosage, activation temperature and time on the mesoporosity, mesopore volume and carbon yield were investigated, and further optimized by response surface methodology (RSM). The Brunauer-Emmett-Teller surface area, mesoporosity and mesopore volume of the JAS-MAC prepared under optimum condition were identified to be 1631 m(2)center dot g(-1), 90.16% and 1.11 cm(3)center dot g(-1), respectively. Compared with commercial activated carbons, this carbon exhibited a comparable monolayer adsorption capacity of 374.5 mg center dot g(-1) for Methylene Blue dye. The findings suggest that RSM could be an effective approach for optimizing the pore structure of fabricated activated carbons

Simultaneous determination of diphenylarsinic and phenylarsinic acids in amended soils by optimized solvent extraction coupled to HPLC-MS/MS

A solvent extraction method coupled to high-performance liquid chromatography with tandem mass spectrometry detection (HPLC-MS/MS) was developed and validated for the simultaneous determination of soil diphenylarsinic acid (DPAA) and phenylarsinic acid (PAA). Several extraction solvents were evaluated with respect to the degree of soil extract-induced matrix effects and the recovery values for DPAA and PAA in the four studied soil matrices. Validation data showed that solvent extraction had a negligible impact on the accurate quantification of DPAA. In contrast, only with disodium hydrogen phosphate extraction did the method give both limited matrix effects (102-107%) with a coefficient of variation 74.03%) were obtained for both analytes. The results show that the proposed solvent extraction method coupled to HPLC-MS/MS analysis can provide accurate and reliable determinations of DPAA and PAA in soil samples. (C) 2015 Elsevier B.V. All rights reserved

Occurrence of red clay horizon in soil profiles of the Yellow River Delta: Implications for accumulation of heavy metals

The source-area weathering and pedogenesis processes in the alluvial soil profiles might affect depth distribution of heavy metals. Red clay horizon (RCH) with a thickness of 5-50 cm in a 1 m soil profile has been found ubiquitously in the Yellow River Delta (YRD). The occurrence of this RCH was supposed to be related with the frequent shifting of the Yellow River tail channel in the Yellow River Delta (YRD). The geochemical features of the RCH were distinct from its upper or lower yellow silt horizon (YSH). The average median grain size of the RCH (10.5 pm) was almost three times lower than that of the YSH (29.9 mu m). Meanwhile, the RCH was characterized of higher chemical index of alteration (CIA), magnetic susceptibility (chi(lf)) and frequency-dependent magnetic susceptibility (chi(fd)) values than the YSH, which implied a stronger source-area weathering and pedogenesis intensity of the RCH. Besides the distinctive characteristics of the RCH, it also accumulated significantly (p < 0.05) higher mean contents of Cu, Zn, Pb, Cr, Ni and Co, and maximum content of Cd in the RCH than that in the YSH. The principal component analysis (PCA) suggested that distribution of the heavy metals in the YRD soil profiles was significantly related to the content of aluminosilicates, oxides, clay fraction, chi(lf) and chi(fd), however, such a correlation was not found except for Pb in the YSH. In addition, result of BCR sequential extraction indicated that a higher percentage of Fe-Mn oxides associated fraction was in the RCH than in the YSH for the heavy metals of Pb and Co. Cadmium was observed at higher percentage of exchangeable fraction in the RCH than in the YSH, implying a higher environmental risk of the Cd in the RCH. (C) 2015 Elsevier B.V. All rights reserved

Phthalate esters contamination in soil and plants on agricultural land near an electronic waste recycling site

The accumulation of phthalic acid esters (PAEs) in soil and plants in agricultural land near an electronic waste recycling site in east China has become a great threat to the neighboring environmental quality and human health. Soil and plant samples collected from land under different utilization, including fallow plots, vegetable plots, plots with alfalfa (Medicago sativa L.) as green manure, fallow plots under long-term flooding and fallow plots under alternating wet and dry periods, together with plant samples from relative plots were analyzed for six PAE compounds nominated as prior pollutants by USEPA. In the determined samples, the concentrations of six target PAE pollutants ranged from 0.31-2.39 mg/kg in soil to 1.81-5.77 mg/kg in various plants (dry weight/DW), and their bioconcentration factors (BCFs) ranged from 5.8 to 17.9. Health risk assessments were conducted on target PAEs, known as typical environmental estrogen analogs, based on their accumulation in the edible parts of vegetables. Preliminary risk assessment to human health from soil and daily vegetable intake indicated that DEHP may present a high-exposure risk on all ages of the population in the area by soil ingestion or vegetable consumption. The potential damage that the target PAE compounds may pose to human health should be taken into account in further comprehensive risk assessments in e-waste recycling sites areas. Moreover, alfalfa removed substantial amounts of PAEs from the soil, and its use can be considered a good strategy for in situ remediation of PAEs

Adsorption and desorption characteristics of diphenylarsenicals in two contrasting soils

Diphenylarsinic acid (DPAA) is formed during the leakage of aromatic arsenic chemical weapons in soils, is persistent in nature, and results in arsenic contamination in the field. The adsorption and desorption characteristics of DPAA were investigated in two typical Chinese soils, an Acrisol (a variable-charge soil) and a Phaeozem (a constant-charge soil). Their thermodynamics and some of the factors influencing them (i.e., initial pH value, ionic strength and phosphate) were also evaluated using the batch method in order to understand the environmental fate of DPAA in soils. The results indicate that Acrisol had a stronger adsorption capacity for DPAA than Phaeozem. Soil DPAA adsorption was a spontaneous and endothermic process and the amount of DPAA adsorbed was affected significantly by variation in soil pH and phosphate. In contrast, soil organic matter and ionic strength had no significant effect on adsorption. This suggests that DPAA adsorption may be due to specific adsorption on soil mineral surfaces. Therefore, monitoring the fate of DPAA in soils is recommended in areas contaminated by leakage from chemical weapons.Diphenylarsinic acid (DPAA) is formed during the leakage of aromatic arsenic chemical weapons in soils, is persistent in nature, and results in arsenic contamination in the field. The adsorption and desorption characteristics of DPAA were investigated in two typical Chinese soils, an Acrisol (a variable-charge soil) and a Phaeozem (a constant-charge soil). Their thermodynamics and some of the factors influencing them (i.e., initial pH value, ionic strength and phosphate) were also evaluated using the batch method in order to understand the environmental fate of DPAA in soils. The results indicate that Acrisol had a stronger adsorption capacity for DPAA than Phaeozem. Soil DPAA adsorption was a spontaneous and endothermic process and the amount of DPAA adsorbed was affected significantly by variation in soil pH and phosphate. In contrast, soil organic matter and ionic strength had no significant effect on adsorption. This suggests that DPAA adsorption may be due to specific adsorption on soil mineral surfaces. Therefore, monitoring the fate of DPAA in soils is recommended in areas contaminated by leakage from chemical weapons

Separation of microplastics from a coastal soil and their surface microscopic features

微塑料(&lt;5 mm)作为海岸带地区的新型污染物正越来越受到关注. 本研究以我国河北省曹妃甸围填海区潮滩土壤为例, 采用自行改进设计的连续流动-气浮分离一体化装置, 有效分离和提取了潮滩土壤样品中微塑料,并结合扫描电子显微镜-能谱仪(SEM-EDS)对微塑料表面的微观特性进行了表征. 研究结果表明, 供试土壤中微塑料丰度达到317 n/500 g(其中n表示微塑料个数), 平均粒径为1.56&plusmn;0.63 mm, 其中&lt;1 mm的微塑料占49.8%; 微塑料丰度上整体呈现随粒径变小而增加的趋势. 在土壤中分离到碎片、颗粒、纤维和薄膜四类微塑料, 其中, 黑色碎片类微塑料为首次报道的类型. 颗粒类微塑料丰度最大但平均粒径最小. 土壤中微塑料表面均有不同程度的风化痕迹, 具有不同形态和大小的微孔结构. 在部分微塑料中还发现其表面附着稳定的铁氧化物. 未来需要深入研究了解基于微塑料表面特性的污染物结合机制、生物积累与生态毒性, 尤其更需关注丰度较高、颗粒更细的&lt;1 mm的这部分微塑料(MP1).</p

Residues and risks of veterinary antibiotics in protected vegetable soils following application of different manures

The protected vegetable farming is a style of high frequent rotation farming which requires a huge amount of fertilizers to maintain soil fertility. A total of 125 surface soils covering from east to west of China were sampled for the analysis of 17 antibiotics in order to identify antibiotics contamination caused by long-term manures application. The results indicate that the agricultural land has accumulated a statistically significantly higher antibiotics concentration than conventional open croplands. The maximum oxytetracycline concentration was 8400 mu g kg(-1), the highest level that has ever been reported for oxytetracycline in soils. The residual concentration is decided by both plant duration and manure type. Short-term (<5 years) planting shows the highest residues of tetracyclines and fluoroquinolones in the soils. The organic farming characteristic of applying commercial compost as a single fertilizer in planting shows the lowest antibiotics residue in the soils on the whole. Principal component analysis suggests that the various combinations of antibiotic compounds in the soil may be used to trace the manure source. The antibiotics in soil may threaten water quality through contamination by diffusion. Ciprofloxacin and sulfachinoxalin are calculated to be a higher migration risk to surface waters, hence their environmental fate requires further study. (C) 2016 Elsevier Ltd. All rights reserved

Rape (Brassica chinensis L.) seed germination, seedling growth, and physiology in soil polluted with di-n-butyl phthalate and bis(2-ethylhexyl) phthalate

Phthalic acid esters (PAEs) pollution in agricultural soils caused by widely employed plastic products is becoming more and more widespread in China. PAEs polluted soil can lead to phytotoxicity in higher plants and potential health risks to human being. We evaluated the individual toxicity of di-n-butyl phthalate (DnBP) and bis(2-ethylhexyl) phthalate (DEHP), two representative PAEs, to sown rape (Brassica chinensis L.) seeds within 72 h (as germination stage) and seedlings after germination for 14 days by monitoring responses and trends of different biological parameters. No significant effects of six concentrations of PAE ranging from 0 (not treated/NT) to 500 mg kg(-1) on germination rate in soil were observed. However, root length, shoot length, and biomass (fresh weight) were inhibited by both pollutants (except root length and biomass under DEHP). Stimulatory effects of both target pollutants on malondialdehyde (MDA) content, superoxide dismutase (SODase) activity, ascorbate peroxidase (APXase) content, and polyphenoloxidase (PPOase) activity in shoots and roots (SODase activity in shoots excluded) were in the same trend with the promotion of proline (Pro) but differed with acetylcholinesterase activity (except in shoots under DnBP) for analyzed samples treated for 72 h and 14 days. Responses of representative storage compounds free amino acids (FAA) and total soluble sugar (TSS) under both PAEs were raised. Sensitivity of APXase and Pro in roots demonstrates their possibility in estimation of PAE phytotoxicity and the higher toxicity of DnBP, which has also been approved by the morphological photos of seedlings at day 14. Higher sensitivity of the roots was also observed. The recommended soil allowable concentration is 5 mg DnBP kg(-1) soil for the development of rape. We still need to know the phytotoxicity of DEHP at whole seedling stage for both the growing and development; on the other hand, soil criteria for PAE compounds are urgently required in China

Levels, distributions and sources of veterinary antibiotics in the sediments of the Bohai Sea in China and surrounding estuaries

Veterinary antibiotics are emerging contaminants of concern. A total of 139 samples comprising 104 marine sediments and 35 estuarine sediments were collected from the Bohai Sea area and analyzed for seventeen antibiotics. The results reveal that the presence and concentration of antibiotics were generally higher in the estuaries than in the sea. The highest antibiotic concentration, 4695 mu g kg(-1) of oxytetracycline, occurred in the estuarine sediment from Ziya New River. Bohai Bay and Laizhou Bay and the surrounding estuaries had higher concentrations of antibiotics. However, low levels of antibiotics detected were detected in Liaodong Bay in contrast to the high concentrations present in the surrounding estuaries. Spatial heterogeneity and principal component analysis suggest a large impact of terrestrial sources of the antibiotics contaminating the Bohai Sea. Risk quotients indicate that current levels of norfloxacin and oxytetracycline might be potentially hazardous to sensitive biota both in the Bohai Sea and in its surrounding estuaries. (C) 2016 Published by Elsevier Ltd