Yujuan Huang

Simultaneous extraction of four classes of antibiotics in soil, manure and sewage sludge and analysis by liquid chromatography-tandem mass spectrometry with the isotope-labelled internal standard method

An analytical method for the analysis of four classes of antibiotics (tetracyclines, sulfonamides, fluoroquinolones and macrolides) has been developed and validated in this work. After optimizing the extraction and purification, the solvent consisting of a (EDTA-sodium phosphate buffer with acetonitrile : Mg(NO3)(2)-NH3 center dot H2O ,v/v, 3 : 1) was used as the extraction buffer, these antibiotics were extracted from agricultural soil, manure, and sewage sludge using ultrasonic-assisted extraction aided by mechanical shaking and followed by solid phase extraction (SPE) clean-up with hydrophilic-lipophilic balance (HLB) cartridges. The chromatographic separation was optimized, the analytes were separated and detected by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) and quantified by the isotope-labelled internal standard method. Mass spectral acquisition was done in the positive ion mode by applying multiple reaction monitoring (MRM) of two fragmentation transitions per analyte to provide a high degree of sensitivity and specificity. The calibration range used for all the antibiotics was 5.0-300.0 mu g L-1 and each calibration curve was linear with a coefficient of determination (R-2) > 0.997, the instrument detection limits (IDLs) and quantification limits (IQLs) ranged from 0.09 to 3.57 and 0.49 to 11.9 mu g L-1, respectively. Spiked recoveries were obtained in the range 60-140% for these antibiotics from three different matrices, with the exception of NFC and OFC in soil (52-55%). Lower relative standard deviation (RSD < 17%) for seven replicates from each matrix at 50 mu g kg(-1) spiking level and the method detection limits (MDLs) obtained in the ranges 0.5-14.8 mu g kg(-1) from soil, 0.5-14.1 mu g kg(-1) from manure and 1.3-17.3 mu g kg(-1) from sludge for all the antibiotics studied indicate that the method was reliable and sensitive for extraction and determination of the target compounds in soil, manure and sludge matrices. Finally, the method was applied to analyse soil, manure and sewage sludge samples. Fluoroquinolones were the most dominant antibiotics and there were smaller amounts of sulfonamides in the soil, sludge and manure samples collected.

Water management affects arsenic and cadmium accumulation in different rice cultivars

Paddy rice (Oryza sativa L.) is a staple food and one of the major sources of dietary arsenic (As) and cadmium (Cd) in Asia. A field experiment was conducted to investigate the effects of four water management regimes (aerobic, intermittent irrigation, conventional irrigation and flooding) on As and Cd accumulation in seven major rice cultivars grown in Zhejiang province, east China. With increasing irrigation from aerobic to flooded conditions, the soil HCl-extractable As concentrations increased significantly and the HCl-extractable Cd concentrations decreased significantly. These trends were consistent with the As and Cd concentrations in the straw, husk and brown rice. Water management both before and after the full tillering stage affected As and Cd accumulation in the grains. The intermittent and conventional treatments produced higher grain yields than the aerobic and flooded treatments. Cd concentrations in brown rice varied 13.1–40.8 times and As varied 1.75–8.80 times among the four water management regimes. Cd and As accumulation in brown rice varied among the rice cultivars, with Guodao 6 (GD6) was a low Cd but high-As-accumulating cultivar while Indonesia (IR) and Yongyou 9 (YY9) were low As but high-Cd-accumulating cultivars. Brown rice Cd and As concentrations in the 7 cultivars were significantly negatively correlated. The results indicate that As and Cd accumulated in rice grains with opposite trends that were influenced by both water management and rice cultivar. Production of ‘safe’ rice with respect to As and Cd might be possible by balancing water management and rice cultivar according to the severity of soil pollution.

PHYTOREMEDIATION OF SOIL CONTAMINATED WITH CADMIUM, COPPER AND POLYCHLORINATED BIPHENYLS

A pot experiment and a field trial were conducted to study the remediation of an aged field soil contaminated with cadmium, copper and polychlorinated biphenyls (PCBs) (7.67 ± 0.51 mg kg−1 Cd, 369 ± 1 mg kg−1 Cu in pot experiment; 8.46 ± 0.31 mg kg−1 Cd, 468 ± 7 mg kg−1 Cu, 323 ± 12 μg kg−1 PCBs for field experiment) under different cropping patterns. In the pot experiment Sedum plumbizincicola showed pronounced Cd phytoextraction. After two periods (14 months) of cropping the Cd removal rates in these two treatments were 52.2 ± 12.0 and 56.1 ± 9.1%, respectively. Total soil PCBs in unplanted control pots decreased from 323 ± 11 to 49.3 ± 6.6 μg kg−1, but with no significant difference between treatments. The field microcosm experiment intercropping of three plant species reduced the yield of S. plumbizincicola, with a consequent decrease in soil Cd removal. S. plumbizincicola intercropped with E. splendens had the highest shoot Cd uptake (18.5 ± 1.8 mg pot−1) after 6 months planting followed by intercropping with M. sativa (15.9 ± 1.9 mg pot−1). Liming with S. plumbizincicola intercropped with M. sativa significantly promoted soil PCB degradation by 25.2%. Thus, adjustment of soil pH to 5.56 combined with intercropping with S. plumbizincicola and M. sativa gave high removal rates of Cd, Cu, and PCBs.

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 μg 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.

Determination of low levels of polycyclic aromatic hydrocarbons in soil by high performance liquid chromatography with tandem fluorescence and diode-array detectors

Risk assessment of polycyclic aromatic hydrocarbons (PAHs) contaminated soil and source apportionment require accurate analysis of the concentration of each PAH congener in the soil. However, determination of low level PAH congeners in soil is difficult because of similarity in the chemical properties of 16 PAHs and severe matrix interferences due to complex composition of soils. It is therefore imperative to develop a sensitive and accurate method for determination of low level PAHs in soil. In this work, high performance liquid chromatography equipped with fluorescence and diode-array detectors (HPLC-FLD-DAD) was used to determine the concentration of 16 PAHs in soil. The separation of the 16 PAHs was achieved by optimization of the mobile phase gradient elution program and FLD wavelength switching program. Qualitative analysis of the 16 PAHs was based on the retention time (RT) and each PAH specific spectrum obtained from DAD. In contrast, the quantitative analysis of individual PAH congeners was based on the peak areas at the specific wavelength with DAD and FLD. Under optimal conditions the detection limit was in the range 1.0-9.5 μg L(-1) for 16 PAHs with DAD and 0.01-0.1 μg L(-1) for 15 PAHs with FLD, and the RSD of PAHs was less than 5% with DAD and 3% with FLD. The spiked recoveries were in the range 61-96%, with the exception of NaP (<40%). The results show that HPLC-FLD-DAD can provide more accurate and reliable analysis of low level PAH congeners in soil samples.

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, 4695μgkg(-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.

A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils

An optimized procedure based on gas chromatography-mass spectrometry (GC-MS) combined with accelerated solvent extraction (ASE) is developed for the analysis of six phthalic acid esters (PAEs), which are priority soil pollutants nominated by United States Environmental Protection Agency (USEPA). Quantification of PAEs in soil employs ultrasonic extraction (UE) (USEPA 3550) and ASE (USEPA 3545), followed by clean up procedures involving three different chromatography columns and two combined elution methods. GC-MS conditions under selected ion monitoring (SIM) mode are described and quality assurance and quality control (QA/QC) criteria with high accuracy and sensitivity for target analytes were achieved. Method reliability is assured with the use of an isotopically labeled PAE, di-n-butyl phthalate-d4 (DnBP-D4), as a surrogate, and benzyl benzoate (BB) as an internal standard, and with the analysis of certified reference materials (CRM). QA/QC for the developed procedure was tested in four PAE-spiked soils and one PAE-contaminated soil. The four spiked soils were originated from typical Chinese agricultural fields and the contaminated soil was obtained from an electronic waste dismantling area. Instrument detection limits (IDLs) for the six PAEs ranged 0.10–0.31 μg·L−1 and method detection limits (MDLs) of the four spiked soils varied from a range of 20–70 μg·kg−1 to a range of 90–290 μg·kg−1. Linearity of response between 20 μg·L−1 and 2 mg·L−1 was also established and the correlation coefficients (R) were all>0.998. Spiked soil matrix showed relative recovery rates between 75 and 120% for the six target compounds and about 93% for the surrogate substance. The developed procedure is anticipated to be highly applicable for field surveys of soil PAE pollution in China.

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 contaminated soil remediation by titanium dioxide (P25) photocatalysis: Degradation pathway, optimization of operating parameters and effects of soil properties

Diphenylarsinic acid (DPAA) is formed during the leakage of arsenic chemical weapons in sites and poses a high risk to biota. However, remediation methods for DPAA contaminated soils are rare. Here, the photocatalytic oxidation (PCO) process by nano-sized titanium dioxide (TiO2) was applied to degrade DPAA in soil. The degradation pathway was firstly studied, and arsenate was identified as the final product. Then, an orthogonal array experimental design of L9(3)(4), only 9 experiments were needed, instead of 81 experiments in a conventional one-factor-at-a-time, was used to optimize the operational parameters soil:water ratio, TiO2 dosage, irradiation time and light intensity to increase DPAA removal efficiency. Soil:water ratio was found to have a more significant effect on DPAA removal efficiency than other properties. The optimum conditions to treat 4 g soil with a DPAA concentration of 20 mg kg(-1) were found to be a 1:10 soil: water ratio, 40 mW cm(-2) light intensity, 5% TiO2 in soil, and a 3-hour irradiation time, with a removal efficiency of up to 82.7%. Furthermore, this method (except for a change in irradiation time from 3 to 1.5h) was validated in nine different soils and the removal efficiencies ranged from 57.0 to 78.6%. Removal efficiencies were found to be negatively correlated with soil electrical conductivity, organic matter content, pH and total phosphorus content. Finally, coupled with electron spin resonance (ESR) measurement, these soil properties affected the generation of OH• by TiO2 in soil slurry. This study suggests that TiO2 photocatalytic oxidation is a promising treatment for removing DPAA from soil.

Mechanochemical destruction of DDTs with Fe-Zn bimetal in a high-energy planetary ball mill

Mechanochemical destruction has been proposed as a promising, non-combustion technology for the disposal of toxic, halogenated, organic pollutants. In the study presented, additives including Fe, Zn, Fe-Zn bimetal, CaO and Fe2O3 were tested for their effectiveness to remove DDTs by MC. The results showed that Fe-Zn bimetal was the most efficient additive, with 98% of DDTs removed after 4h. The Fe-Zn mass ratio was optimized to avoid possible spontaneous combustion of the ground sample during subsample collection. Inorganic water-soluble chloride in the ground sample increased by 91% after 4h of grinding, which indicated dechlorination during destruction of DDTs. In addition, relationships were established between the rate constant and the rotation speed or the charge ratio. Discrete Element Method (DEM) modeling was used to simulate the motion of the grinding ball and calculate both total impact energy and normal impact energy. The latter expressed a stronger, linear correlation with the rate constant. Therefore, normal impact energy is proposed to be the main driving force in the MC destruction of DDTs.