几种印染助剂对壳聚糖稳定纳米铁去除酸性品红的影响

以氯化铁为铁源,硼氢化钠为还原剂,壳聚糖为稳定剂,采用液相还原法制备壳聚糖稳定纳米铁（CS-nZⅥ）;研究了印染废水中常见助剂NaNO₃、Na₂SO₄、NaH₂PO₄、K₂Cr₂O₇、EDTA二钠盐存在下,超声波辅助CS-nZⅥ对酸性品红（AF）降解的影响。结果表明,反应15 min,0.01 g CS-nZⅥ对25 mL、100 mg/L AF的去除率高达99.9%;各种助剂的存在使得纳米铁表面不同程度失活,阻碍反应的进行,使得AF的去除率下降。NaNO₃、K₂Cr₂O₇、EDTA二钠盐与纳米铁发生反应,与AF存在明显的竞争作用。重复利用实验表明,CS-nZⅥ重复利用7次仍具有一定的反应活性。此外,CS-nZⅥ对加标（50 mg/L）实际废水中AF的去除率达到99%以上,表明CS-nZⅥ是一种潜在的环境修复材料。     

A2O工艺中雌激素的行为变化和去除机理

研究了厌氧-缺氧-好氧(A2O)活性污泥工艺对生活污水中天然雌激素雌酮(Estrone,E1)、17β-雌二醇(17β-Estradiol,E2)以及17α-乙炔基雌二醇(17α-Ethynylestradiol,EE2)的去除性能。在对COD、N和P具有良好去除效果的前提下,对E1、E2和EE2的去除率可分别达到92.7%、100%和62.7%。通过对各反应单元内3种雌激素的物料平衡分析,表明A2O工艺对雌激素的去除主要发生在厌氧段和好氧段。以失活污泥作为对照组,好氧硝化过程中雌激素去除的小试实验发现,好氧过程中E1、E2的去除主要依靠生物降解作用,而EE2的去除则主要依赖于活性污泥对其的吸附作用。     

改性蚁酸木质素的制备与应用

采用加拿大一枝黄花茎杆为原料提取蚁酸木质素,通过氧化或接枝复合的方法对蚁酸木质素进行改性,对改性产物进行了FTIR和SEM表征。实验结果表明：接枝复合改性产物中存在-CONH的接枝复合链,氧化改性产物基本保持了蚁酸木质素原来的吸收峰;采用接枝复合改性产物处理初始质量浓度为50 mg/L的亚甲基蓝废水,在废水pH 7、吸附时间4 h、改性产物加入量22 mg/mL的条件下,亚甲基蓝去除率为90.94%;采用氧化改性产物处理相同亚甲基蓝废水,在废水pH 10、吸附时间12 h、改性产物加入量22 mg/mL的条件下,亚甲基蓝去除率为81.93%。     

Abnormal glucose regulation in pyrethroid pesticide factory workers

The purpose of this study was to investigate associations between pyrethroids occupational exposures, and risk of abnormal glucose regulation. Data from total of 3080 subjects in two pesticide factories were used. This was a population-based case-controlled study in China. In total, 18.3% of subjects with impaired glucose regulation (IGR) and 6.5% of subjects with diabetes, and the prevalence of abnormal glucose regulation was 24.8%, 86 subjects had known type 2 diabetes and 114 had newly diagnosed diabetes. The prevalence of subjects with abnormal glucose regulation increased from 21.3% in the controls to 29.3% in the exposures (χ² = 33.182, P < 0.001). Multivariate logistic regression was used to control potential confounders and calculate odd ratios as the estimate of effect. An indication of increased risk for abnormal glucose regulation was noted for exposure to pyrethroids (OR = 1.482, 95%CI = 1.238-1.774). Abnormal glucose regulation is common in subjects exposed to pyrethroids. The present investigation indicates the adverse health effects of pyrethroids are underestimated.     

Detection of dicofol and related pesticides in human breast milk from China, Korea and Japan

Previously, we demonstrated that the concentrations of DDTs were greater in breast milk collected from Chinese mothers than from Japanese and Korean mothers. To investigate dicofol as a possible source of the DDTs in human breast milk, we collected breast milk samples from 2007 to 2009 in China (Beijing), Korea (Seoul, Busan) and Japan (Sendai, Takarazuka and Takayama). Using these breast milk samples, we quantified the concentrations of dichlorobenzophenone, a pyrolysis product of dicofol (simply referred to as dicofol hereafter), dichlorodiphenyltrichloroethane and its metabolites (DDTs) using GC-MS. Overall, 12 of 14 pooled breast milk samples from 210 mothers contained detectable levels of dicofol (>0.1 ng g⁻¹ lipid). The geometric mean concentration of dicofol in the Japanese breast milk samples was 0.3 ng g⁻¹ lipid and significantly lower than that in Chinese (9.6 ng g⁻¹ lipid) or Korean breast milk samples (1.9 ng g⁻¹ lipid) (p < 0.05 for each). Furthermore, the ΣDDT levels in breast milk from China were 10-fold higher than those from Korea and Japan. The present results strongly suggest the presence of extensive emission sources of both dicofol and DDTs in China. However, exposure to dicofol cannot explain the large exposure of Chinese mothers to DDTs because of the trace levels of dicofol in the ΣDDTs. In the present study, dicofol was confirmed to be detectable in human breast milk. This is the first report to identify dicofol in human samples.     

Residues and dynamics of pymetrozine in rice field ecosystem

The fate of pymetrozine was studied in rice field ecosystem, and a simple and reliable analytical method for determination of pymetrozine in soil, rice straw, paddy water and brown rice was developed. Pymetrozine residues were extracted from samples, cleaned up by solid phase extraction (SPE) and then determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS). The average recovery was 81.2-88.1% from soil, 83.4-88.6% from rice straw, 87.3-94.1% from paddy water and 82.9-85.3% from brown rice. The relative standard deviation (RSD) was less than 15%. The limits of detection (LODs) of pymetrozine calculated as a sample concentration were 0.0003 mg kg⁻¹ (mg L⁻¹) for soil and paddy water, 0.001 mg kg⁻¹ for brown rice and rice straw. The results of kinetics study of pymetrozine residue showed that pymetrozine degradation in water, soil, and rice straw coincided with C = 0.194e^−0.986t, C = 0.044e^−0.099t, and C = 0.988e^−0.780t, respectively; the half-lives were about 0.70 d, 7.0 d and 0.89 d, respectively. The degradation rate of pymetrozine in water was the fastest, followed by rice straw. The highest final pymetrozine residues in brown rice were 0.01 mg kg⁻¹, which was lower than the EU’s upper limit of 0.02 mg kg⁻¹ in rice. Therefore, a dosage of 300-600 g a.i.hm⁻² was recommended, which could be considered as safe to human beings and animals.     

Temperature-dependent sorption of polycyclic aromatic hydrocarbons on natural and treated sediments

In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient K_d increasing 2-5 times as the temperature decreases 30 °C. The increase of K_d value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of K_d in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔH_S) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔH_S, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.     

Polybrominated diphenyl ethers (PBDEs) and mercury in fish from lakes of the Tibetan Plateau

High mountains may act as cold traps for globally transported persistent organic pollutants (POPs) and mercury (Hg). In the present study, 60 fish samples were collected from eight alpine lakes across the Tibetan Plateau. Concentrations of polybrominated diphenyl ethers (PBDEs), total mercury (HgT) and methyl mercury (MeHg) were quantified in the fish muscle tissues to improve the understanding of pollution status and factors regulating the transport and fate of these contaminants on the Plateau. The results showed that lake-averaged ∑₁₄PBDEs concentration was between 0.09 ng g⁻¹ dw and 4.32 ng g⁻¹ dw, which was lower than those reported for European mountains. The total mercury concentration in individual fish ranged from 243 to 2384 ng g⁻¹ dw, and that of MeHg from 131 to 1610 ng g⁻¹ dw, which is much higher than those reported in other mountain fish. The spatial variation of PBDEs and mercury in the Plateau is largely controlled by the specific meteorological patterns.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

Biodegradation and bio-sorption of antibiotics and non-steroidal anti-inflammatory drugs using immobilized cell process

In the present study, the removal mechanisms of four antibiotics (sulfamethoxazole, sulfadimethoxine, sulfamethazine, and trimethoprim) and four non-steroidal anti-inflammatory drugs (acetaminophen, ibuprofen, ketoprofen, and naproxen) in immobilized cell process were investigated using batch reactors. This work principally explores the individual or collective roles of biodegradation and bio-sorption as removal routes of the target pharmaceuticals and the results were validated by various experimental and analytical tools. Biodegradation and bio-sorption were found as dominant mechanisms for the drug removal, while volatilization and hydrolysis were negligible for all target pharmaceuticals. The target pharmaceuticals responded to the two observed removal mechanisms in different ways, typically: (1) strong biodegradability and bio-sorption by acetaminophen, (2) strong biodegradability and weak bio-sorption by sulfamethoxazole, sulfadimethoxine, ibuprofen and naproxen, (3) low biodegradability and weak bio-sorption by sulfamethazine and ketoprofen, and (4) low biodegradability and medium bio-sorption by trimethoprim. In the sorption/desorption experiment, acetaminophen, sulfamethoxazole and sulfadimethoxine were characterized by strong sorption and weak desorption. A phenomenon of moderate sorption and well desorption was observed for sulfamethazine, trimethoprim and naproxen. Both ibuprofen and ketoprofen were weakly sorbed and strongly desorbed.