Effects of rice straw biochar on sorption and desorption of di-n-butyl phthalate in different soil particle-size fractions.

Sorption of organic contaminants by biochar greatly affects their bioavailability and fate in soils. Nevertheless, very little information is available regarding the effects of biochar on sorption and desorption of organic contaminants in different soil particle-size fractions. In this study, di-n-butyl phthalate (DBP), a prevalent organic contaminant in agricultural soils, was taken as a model contaminant. The effects of biochar on DBP sorption and desorption in six particle-size fractions (i.e., coarse sand, fine sand, coarse silt, fine silt, clay, and humic acid fractions) of paddy soil were investigated using batch sorption-desorption experiments. A straw-derived biochar with high specific surface area (116 m2/g) and high content of organic matter (OM) rich in aromatic carbon (67%) was prepared. Addition of this biochar (1% and 5%) significantly promoted the sorption and retention of DBP in all the paddy soil particle-size fractions at environmentally relevant DBP concentrations (2-12 mg/L) with 1.2-132-fold increase of the Kd values. With increasing addition rates of biochar, DBP retention by the biochar enhanced. The biochar's effectiveness was remarkably influenced by the physicochemical properties of the soil particle-size fractions, especially, the OM contents and pore size showed the most striking effects. A parameter (rkd) reflecting the biochar's effectiveness showed negative and positive correlations with OM contents and pore size of the soil particle-size fractions, respectively. Accordingly, strong effect of the biochar was found in the soil fractions with low OM contents and high pore size. The findings of this study gave insight into the effects and influencing factors of biochar on sorption and desorption of organic contaminants in soils at scale of various particle-size factions.

Low-molecular-weight organic acids correlate with cultivar variation in ciprofloxacin accumulation in Brassica parachinensis L.

To understand the mechanism controlling cultivar differences in the accumulation of ciprofloxacin (CIP) in Chinese flowering cabbage (Brassica parachinensis L.), low-molecular-weight organic acids (LMWOAs) secreted from the roots of high- and low-CIP cultivars (Sijiu and Cutai, respectively) and their effects on the bioavailability of CIP in soil were investigated. Significant differences in the content of LMWOAs (especially maleic acid) between the two cultivars played a key role in the variation in CIP accumulation. Based on the Freundlich sorption coefficient (K f ) and distribution coefficient (K d ), the presence of LMWOAs reduced the CIP sorption onto soil particles, and higher concentrations of LMWOAs led to less CIP sorption onto soil. On the other hand, LMWOAs enhanced CIP desorption by lowering the solution pH, which changed the surface charge of soil particles and the degree of CIP ionization. LMWOAs promoted CIP desorption from soil by breaking cation bridges and dissolving metal cations, particularly Cu2+. These results implied that the LMWOAs (mainly maleic acid) secreted from Sijiu inhibited CIP sorption onto soil and improved CIP desorption from soil to a greater extent than those secreted from Cutai, resulting in higher bioavailability of CIP and more uptake and accumulation of CIP in the former.

Occurrence and risk assessment of tetracycline antibiotics in soil from organic vegetable farms in a subtropical city, south China.

This study investigated the occurrence of tetracycline antibiotics in soils from different organic vegetable farms in Guangzhou, a subtropical city, South China and evaluated their ecological risk. Four tetracycline compounds (oxytetracycline, tetracycline, chlortetracycline, and doxycycline) were extracted ultrasonically from soil samples (n = 69), with a solid-phase extraction cleanup, and were then measured by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The results showed that four compounds were detected in all samples, with the concentrations of the individual compounds ranging from 0.04 to 184.8 µg/kg (dry weight). The concentrations of tetracycline compounds in the soils from different vegetable farms varied greatly, but their patterns of distribution were similar. Doxycycline was the predominant compound with a mean of 21.87 µg/kg, followed by chlortetracycline. The concentrations of doxycycline and chlortetracycline in 7.46 % of the samples were higher than the ecotoxic effect trigger value (100 µg/kg) set by the Steering Committee of Veterinary International Committee on Harmonization. Additionally, the concentrations of tetracyclines in greenhouse soils were significantly lower than those in open-field soils. Risk assessment based on single compound exposure showed that doxycycline could pose medium or high risks. Compared with other studies, the levels of tetracyclines in this study were relatively low. The hypothesis that antibiotic residues in the soil of organic farms fertilized with manure are higher than in the soils of conventional farms was not supported in the area studied due to the high levels of moisture, temperature, and microbial activity.

Analysis of Trace Quaternary Ammonium Compounds (QACs) in Vegetables Using Ultrasonic-Assisted Extraction and Gas Chromatography-Mass Spectrometry.

A reliable, sensitive, and cost-effective method was developed for determining three quaternary ammonium compounds (QACs) including dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, and didodecyldimethylammonium chloride in various vegetables using ultrasonic-assisted extraction and gas chromatography-mass spectrometry. The variety and acidity of extraction solvents, extraction times, and cleanup efficiency of sorbents were estimated to obtain an optimized procedure for extraction of the QACs in nine vegetable matrices. Excellent linearities (R(2) > 0.992) were obtained for the analytes in the nine matrices. The limits of detection and quantitation were 0.7-6.0 and 2.3-20.0 µg/kg (dry weight, dw) in various matrices, respectively. The recoveries in the nine matrices ranged from 70.5% to 108.0% with relative standard deviations below 18.0%. The developed method was applied to determine the QACs in 27 vegetable samples collected from Guangzhou in southern China, showing very high detection frequency with a concentration of 23-180 µg/kg (dw).

Effects of the size and morphology of zinc oxide nanoparticles on the germination of Chinese cabbage seeds.

The toxicity of four zinc oxide nanoparticles (i.e., spheric ZnO-30, spheric ZnO-50, columnar ZnO-90, and hexagon rod-like ZnO-150) to the seed germination of Chinese cabbage (Brassica pekinensis L.) was investigated in this study. The results showed that zinc oxide nanoparticles (nano-ZnOs) did not affect germination rates at concentrations of 1-80 mg/L but significantly inhibited the root and shoot elongation of Chinese cabbage seedlings, with the roots being more sensitive. The inhibition was evident mainly during seed incubation rather than the seed soaking process. Both the production of free hydroxyl groups (·OH) and the Zn bioaccumulation in roots or shoots resulted in toxicity of nano-ZnOs to Chinese cabbage seedlings. The toxicity of nano-ZnOs was affected significantly by their primary particle sizes in the minimum dimensionality, but large columnar ZnO-90 and small spherical ZnO-50 had comparable toxicities. Therefore, both the particle size and morphology affected the toxicity of nano-ZnOs.

Distribution and risk assessment of quinolone antibiotics in the soils from organic vegetable farms of a subtropical city, Southern China.

Organic fertilizer or manure containing antibiotics has been widely used in organic farms, but the distribution and potential impacts of antibiotics to the local environment are not well understood. In this study, four quinolone antibiotics in soil samples (n=69) from five organic vegetable farms in a subtropical city, Southern China, were analyzed using high performance liquid chromatography-tandem mass spectrometry. Our results indicated that quinolone compounds were ubiquitous in soil samples (detection frequency>97% for all compounds), and their concentrations ranged from not detectable to 42.0 µg/kg. Among the targets, enrofloxacin (ENR) was the dominant compound, followed by ciprofloxacin (CIP) and norfloxacin (NOR). The average total concentrations of four compounds in the soils were affected by vegetable types and species cultivated, decreasing in the order of fruit>rhizome>leaf vegetables. Moreover, the average concentrations of quinolone compounds (except ENR) in open-field soils were higher than those in greenhouse soils. The concentrations of quinolone antibiotics in this study were lower than the ecotoxic effect trigger value (100 µg/kg) proposed by the Veterinary Medicine International Coordination commission. Risk assessment based on the calculated risk quotients indicated that NOR, CIP, and ENR posed mainly medium to low risks to bacteria.

[Concentrations of antibiotics in vegetables from manure-mended farm].

Sixteen typical antibiotics including four tetracyclines, four quinolones, and eight sulfonamides in vegetables from manure-amended farm were determined using the ultra high performance liquid chromatography-tandem mass spectrometry and their health risks to human via the diet pathway was assessed. Most antibiotics were frequently detected in vegetable samples, with the detection rate from 11% to 90%. Concentrations of a single compound were mainly less than 5 microg x kg(-1) (D. W.), with the maximum of 23.88 microg x kg(-1) and the average of 0.91 microg x kg(-1), respectively. Norfloxacin, ciprofloxacin, sulfamehtaoid and sulfadiazine were the dominant compounds. At least one antibiotic was detected in a single vegetable samples, and even up to ten antibiotics. The concentration of quinolones in underground parts was higher than those in aboveground parts. Intake dose of antibiotics via the consumption of the detected vegetables was lower than ADI, suggesting a lower health risk. But combination toxicity and resistance of antibiotics should not be ignored.

Heavy metal contamination of urban soils and dusts in Guangzhou, South China.

The heavy metal concentrations of soil and dust samples from roadside, residential areas, parks, campus sport grounds, and commercial sites were studied in Guangzhou, South China. Heavy metals in samples were determined by inductively coupled plasma atomic emission spectrophotometer following acidic digestion with HClO(4) + HF + HNO(3). High concentrations, especially of Cd, Pb, and Zn, were found with mean concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the urban dusts being 4.22 ± 1.21, 62.2 ± 27.1, 116 ± 30, 31.9 ± 12.6, 72.6 ± 17.9, and 504 ± 191 mg/kg dry weight, respectively. The respective levels in urban soils (0.23 ± 0.19, 22.4 ± 13.8, 41.6 ± 29.4, 11.1 ± 5.3, 65.4 ± 40.2, and 277 ± 214 mg/kg dry weight, respectively), were significantly lower. The integrated pollution index of six metals varied from 0.25 to 3.4 and from 2.5 to 8.4 in urban soils and dusts, respectively, with 61 % of urban soil samples being classified as moderately to highly polluted and all dust samples being classified as highly polluted. The statistical analysis results for the urban dust showed good agreement between principal component analysis and cluster analysis, but distinctly different elemental associations and clustering patterns were observed among heavy metals in the urban soils. The results of multivariate statistic analysis indicated that Cr and Ni concentrations were mainly of natural origin, while Cd, Cu, Pb, and Zn were derived from anthropogenic activities.

Occurrence of nonylphenol and nonylphenol monoethoxylate in soil and vegetables from vegetable farms in the Pearl River Delta, South China.

Low molecular-mass nonylphenol ethoxylates (NPEOs) and 4-nonylphenol (NP) are biodegradation products of higher molecular mass NPEOs used as surface active agents, and they are endocrine-disrupting contaminants. In this study, surface soil (0-20 cm) samples and different vegetable samples were collected from 27 representative vegetable farms located in Shenzhen, Dongguan, and Huizhou within the Pearl River Delta region, South China, and NP and nonylphenol monoethoxylate (NP(1)EO) were analyzed using high-performance liquid chromatography with ultraviolet detection. The results show that NP and NP(1)EO were detected in soil and vegetable samples. The concentrations of NP and NP(1)EO in soil samples ranged from nondetectable (ND) to 7.22 µg kg(-1) dry weight (dw) and from ND to 8.24 µg kg(-1) dw, respectively. The average concentrations of both NP and NP(1)EO in soil samples decreased in the following order: Dongguan > Huizhou > Shenzhen. The levels of NP and NP(1)EO in vegetable samples varied from 1.11 to 4.73 µg kg(-1) dw and from 1.32 to 5.33 µg kg(-1) dw, respectively. The greatest levels of both NP and NP(1)EO were observed in water spinach, and the lowest levels of NP and NP(1)EO were recorded in cowpea. The bioconcentration factors (the ratio of contaminant concentration in plant tissue to soil concentration) of NP and NP(1)EO were <1.0 (mean 0.535 and 0.550, respectively). The occurrences of NP and NP(1)EO in this study are compared with other studies, and their potential sources are discussed.

[Concentrations and distribution of tetracycline antibiotics in vegetable field soil chronically fertilized with manures].

Occurrence of antibiotics in the soils substantially fertilized with antibiotics-enriched animal manures is very of concern. This paper investigated the concentration and distribution of four tetracycline antibiotics in soils from vegetable field chronically fertilized with manures in subtropical area using solid-phase extraction followed by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-MS/MS). The sum concentrations of four tetracycline compounds ranged from 1.35 microg/kg to 22.52 microg/kg with an average of 7.35 microg/kg. There were thirty one to one hundred percent of the soil samples were detected with average concentrations of 0.63- 3.11 microg/kg for four tetracycline compounds which dominated mostly with oxytetracycline and secondly with deoxytetracycline. Composition and levels of tetracycline compounds varied obviously in both horizontal and vertical soils. The concentration of tetracycline compounds in soil profile decreased rapidly with the depth and some of the compounds were still detected in 60 to 80 centimeter depth of soil. It is concluded that tetracycline antibiotics in soils from vegetable field chronically fertilized with manures in subtropical area were generally lower and less ecotoxic risk for soil ecosystem. But it should not be ignored in view of combined toxic effect and resistance of various compounds.

[Occurrence of quinolone and sulfonamide antibiotics in swine and cattle manures from large-scale feeding operations of Guangdong Province].

The occurrence and distribution of four quinolones and four sulfonamides in swine and cattle feces sampled from twenty large-scale feeding operations in different areas of Guangdong province were detected using solid phase extraction (SPE) and high performance liquid chromatography (HPLC). Quinolone and sulfonamide compounds were observed in all pig dung samples. Their total concentrations ranged from 24.5 microg/kg to 1516.2 microg/kg (F. W.) with an average of 581.0 microg/kg and ranged from 1925.9-13399.5 microg/kg with an average of 4403.9 microg/kg respectively. The dominant compounds in pig feces were ciprofloxacin and enrofloxacin for quinolones and sulfamerazine and sulfamethoxazole for sulfonamides. Quinolone compounds which dominated with norfloxacin and ciprofloxacin were also observed in all cattle dung samples, its total concentrations ranged from 73.2 microg/kg to 1328.0 microg/kg which averaged 572.9 microg/kg. While the positive rates of sulfonamide compounds detected in cattle dung samples were above 90%, predominated by sulfamethoxazole and sulfamerazine. Concentration and distribution of both quinolone and sulfonamide compounds in swine and cattle dungs of different feeding operations varied greatly. Relatively high concentrations of the two kinds of antibiotics were found in both swine and cattle dungs from Guangzhou area, while sulfameter and sulfamethazine in cattle dungs from Foshan and Shenzhen areas were below the limit of detection.

Investigation of sulfonamide, tetracycline, and quinolone antibiotics in vegetable farmland soil in the Pearl River Delta area, southern China.

Thirteen antibiotics in soil from vegetable farmlands of the Pearl River Delta, southern China, were investigated. At least three antibiotics were detected in each sample. Six antibiotics including four quinolones, tetracycline, and sulfamethoxazole were detected in >94% of the samples. The total contents of three tetracyclines, eight sulfonamides, and four quinolones were not detected-242.6, 33.3-321.4, and 27.8-1537.4 µg/kg, respectively. The highest antibiotic concentrations were observed mainly in vegetable farmlands affiliated with livestock farms. Chlortetracycline, sulfameter, and quinolones in some samples exceed the ecotoxic effect trigger value (100 µg/kg) set by the Steering Committee of Veterinary International Committee on Harmonization. The composition and concentration of antibiotics in soil were correlated with vegetable species. This study has revealed an alarming condition of antibiotics in vegetable farmland soil. Further investigation including environmental fate, plant uptake, and human exposure to antibiotics by plant-derived food should be conducted.

[Preliminary study on occurrence and health risk assessment of quinolone antibiotics in vegetables from Guangzhou, China].

Quinolone antibiotics (QNs) including norfloxacin (NOR), enrofolxacin (ENR), ciprofloxacin (CIP) and lomefloxacin (LOM) in vegetable samples collected from Guangzhou were determined by high performance liquid chromatography (HPLC) coupled with fluorescent detector (FLD). The detected frequency of QNs was 96% in vegetables. The total concentration of quinolones (sigma QNs) detected in vegetable ranged from 1.0 microg/kg to 1 683.1 microg/kg (F.W.). Leafy vegetable topped the content of quinolones among the three types of vegetables, followed by the melon-fruit vegetable and rhizome vegetable. The detected frequency of the four quinolone antibiotics ranked as NOR > CIP > LOM > ENR. Except ENR, concentrations of CIP, NOR, LOM and sigma QNs in pollution-free vegetable, green vegetable and organic vegetable were higher than those in routine cultivated vegetables. The maximum contribution to ADI value (caculated by the sum of CIP and ENR) is estimated up to 41.5% and 83% for adults and children respectively via consumption of vegetables.

[Farm compost polluted water may induce pharyngo-esophageal, gastric and liver carcinoma in the chicken].

OBJECTIVE: To study farm compost polluted water that may induce pharyngo-esophageal, gastric and liver carcinoma in chickens. METHODS: 280 chickens were randomized into 4 groups: experiment group 100 chickens fed with compost water + NaNO(2) by stomach tube. The other 180 were evenly randomized into 3 control groups (60 each), fed with compost water, NaNO(2) and tap water in the same way. The farm compost was prepared with corn stalks, rice straws, excreta of men and livestock. The compost water, after being nitrosified and acidified, was fed through stomach tube 5 - 7.5 ml/session, twice a week. Besides, a solution consisting of the respective formula of each group added with 3 - 4 L water with pH adjusted to 3 - 4 by 1N HCL was given ad lib to all chickens in each group for 26.5 months. RESULTS: In the experiment group, there were pharyngo-esophageal carcinoma 16 (16.3%), gastric adenocarcinoma 5 (10.4%) and liver carcinoma 3 (6.3%), in contrast to none in the 3 control groups, showing significant differences (P < 0.01, P < 0.01, P < 0.05). CONCLUSION: Successful simulation of the layout of esophageal carcinoma high morbidity area and the mimic of chicken gastric fluid strongly support our compost etiological hypothesis that the nitrosified and acidified compost water are carcinogenic, very well causing esophageal, gastric and liver carcinoma.