固相萃取-液相色谱/质谱法测定水中硝基苯酚类化合物

建立了固相萃取-液相色谱/质谱测定水中硝基苯酚类化合物的方法。在最优条件下,7种硝基苯酚类化合物的分离度较好,目标物在0.02~3.00 mg/L范围内线性良好,相关系数均0.998,检出限为0.007~0.026μg/L,加标回收率为71.1%~95.9%,精密度为7.36%~18.6%。该方法操作简便、准确,具有较好的实用性。     

加速溶剂萃取-液相色谱测定土壤中酞酸酯类化合物

建立了加速溶剂萃取-液相色谱法测定土壤中14种酞酸酯类化合物的方法。结果表明,该方法对14种酞酸酯分离度较好,加标回收率为67.1%~128%,精密度RSD(n=6)为5.2%~15.0%,方法检出限为0.021~0.034 mg/kg。该方法操作简便、准确,具有较好的实用性。     

基质固相分散-快速溶剂萃取-GC/MS法同时测定土壤中有机氯农药和多环芳烃

建立了基质固相分散-ASE提取-GC/MS法同时测定土壤中8种有机氯农药和16种多环芳烃的方法。对方法的线性、检出限、精密度、回收率及土壤质控样品进行了分析,结果表明,8种有机氯农药和16种多环芳烃线性良好,相关系数为0.997 5～0.999 8,方法检出限为0.39～1.57μg/kg,空白加标样品的相对标准偏差小于20%,实际土壤样品加标回收率为60.6%～125%,土壤质控样品结果均在范围内。该方法能够满足土壤中8种有机氯农药和16种多环芳烃的检测要求。     

碱提取-丙基化衍生法同时测定土壤中的甲基汞和乙基汞

建立了碱提取-丙基化衍生方式同时测定土壤中甲基汞和乙基汞的方法。优化了仪器分析条件,研究了碱提取温度、提取时间、缓冲溶液加入量和衍生化试剂加入量对测定结果的影响。应用本方法对5种实际土壤样品进行测定,甲基汞和乙基汞的方法检出限分别为0.5 μg/kg和0.3 μg/kg,相对标准偏差分别为1.3%~17%和0.94%~16%,平均回收率分别为88.2%~110%和66.1%~110%。该法适用于批量土壤样品中甲基汞和乙基汞的分析测定。     

Tenax萃取技术用于养殖底泥中有机氯农药的生物有效性研究

本研究以经济底栖生物菲律宾蛤仔和河蚬为受试生物,分别对不同浓度梯度的海洋和淡水底泥中9种代表性有机氯农药(OCPs)进行累积实验;同时采用Tenax连续萃取法研究2类底泥中OCPs的脱附动力学,提供简单、快速评价养殖底泥中OCPs生物有效性的方法,并将Tenax萃取结果与2种底栖生物的累积结果进行比较。结果表明,菲律宾蛤仔和河蚬对OCPs的生物-底泥富集因子(BSAF)分别为0.31~1.89和0.12~2.12,且底泥中有机碳标化的OCPs浓度与生物体内脂肪标化的OCPs浓度之间的相关性较差。Tenax脱附动力学的结果表明,2类底泥中OCPs的快速脱附比例(F_(rap))均在50%左右,其快速、慢速和极慢速脱附速率常数数量级分别为10~(~(-1))、10~(-2)和10~(-4)。Tenax快速脱附组分与2种底栖生物累积结果之间具有良好的相关性(r~2=0.75,P0.0001),表明Tenax萃取技术可以预测OCPs在底栖生物体内的累积量,并且该方法克服了大型底栖生物累积实验结果重复性较差等缺点。另外通过与基于热力学平衡的方法对比发现,Tenax萃取技术更适用于滤食性或可消化底泥的底栖生物对底泥污染物的富集;同时Tenax 6 h和24 h单点萃取技术可以作为简单快速评价底泥疏水性有机污染物(HOCs)生物有效性的替代方法,进一步为养殖领域的底泥污染状况以及相关水产品的质量安全和食用风险提供生物有效性评价依据。     

Eco-friendly approach for leaching out heavy metals from sewage sludge

Sewage sludge contains rich organic matter and nutrients essential for the growth of plants but the presence of toxic heavy metals restricts its land application. To overcome this, the study aims an eco-friendly approach for leaching out heavy metals. Sewage sludge from sewage treatment plant, Chennai, India was characterised. The analysis of total heavy metal concentration was done by digesting in nitric acid and different forms were extracted by community bureau of reference sequential method. Heavy metals: As, Cd, Cr, Cr, Ni, Pb and Zn were determined using inductively coupled plasma optical emission spectrometry Perkin Elmer Optima 5300 DV. The experimental set-up for heavy metal leaching was held for five consecutive days at different concentrations of humic acid (0.1%, 0.5% and 1%) at varied pH (5–9). Results revealed that at the end of fifth day at pH 8, 1% humic acid is capable of leaching out 75.5% cadmium, 66.0% nickel, 52.0% lead, 51.2% zinc, 31.2% copper and 8.5% cadmium from sewage sludge. Statistically positive correlation (0.7088) existed between the percentage of heavy metals leached out and the sum of soluble and reducible fractions. Thus, from ecological point of view, humic acid can be used to leach out heavy metals from sewage sludge serving the need in restoration of soil fertility upon land application.     

土壤气相抽提法去除红壤中挥发性有机污染物的影响因素研究

土壤气相抽提技术(SVE)是一种安全、经济、高效的土壤治理技术,广泛应用于不饱和土壤中挥发性有机污染物的去除.本实验以我国南方典型土壤红壤(粘性较大的土壤)为实验土样,选用最常见的挥发性有机物苯作为污染物,采用一维土柱通风模拟SVE过程,研究了通风流量、土壤含水率以及间歇操作对苯污染红壤去污过程的影响.结果表明,在各土柱垂向气相中苯浓度变化趋势一致,通风初期浓度迅速降低后进入长时间的拖尾阶段,拖尾阶段初期进行间歇操作可降低能耗达到较经济的治理效果.通风流量与土壤含水率是影响净化时间和修复效果的重要因素,两者均存在最佳值.当通风流量为600 mL/min,含水率为17.2%时本实验净化时间降低为36 h,去除率为99.9%,达到了最佳的治理效果.     

Removal of carotene-like colored compounds by liquid-liquid extraction during polycyclic aromatic hydrocarbons analysis of plant tissue

Plants contain a wide variety of chemicals, some of which may have similar chromatographic behavior to polycyclic aromatic hydrocarbons (PAHs). During solid phase extraction (SPE) with Si-gel for instance, the co-elution of carotene-like colored compounds with PAHs has been observed. In this paper, liquid–liquid extraction was applied for the separation and subsequent analysis of PAHs from plant extracts. PAHs containing 2–6 rings, which include naphthalene, phenanthrene, pyrene, benzo[a]pyrene and benzo[ghi]perylene, were used as representative target chemicals. Carotene-like compounds extracted from Komatsuna (Brassica campestris) shoot by acetone followed by Si-gel treatment were incorporated as undesired components in the model matrix. Results showed the feasibility of employing either acetonitrile or 2% (w/v) KOH–methanol as solvents for high PAHs recovery and low extraction of colored fraction. For acetonitrile, 86.9–93.5% of each PAH could be recovered after three extraction cycles (relative standard deviation, RSD < 1.6%) with only about 10% co-extraction of colored fraction. For 2% KOH–methanol, PAHs recoveries ranging from 79.3% to 83.1% after five cycles (RSD < 1.5%) were achieved while the percent extraction of colored fraction was also low at 10%. The relatively higher selectivity of the solvents for PAHs over the colored fraction as well as the solubility of the matrix solution in the solvent may have contributed to these results. On this basis, liquid–liquid extraction is very useful for the pre-treatment of plant extracts for PAHs analysis.     

Determination of zinc speciation in basic oxygen furnace flying dust by chemical extractions and X-ray spectroscopy

There is a growing concern regarding the environmental and public health risks associated with airborne particulate matter (PM). The basic oxygen furnace is one of the most important atmospheric dust sources of the steel manufacturing process. It emits dust enriched in heavy metal such as Zn, which is assumed to contribute to the toxic potential of atmospheric PM. Dust collected before and after the filtration system was analyzed to determine Zn speciation. To this end, a variety of analytical tools were used and a sequential extraction protocol has been specifically developed for iron and steel dust. The Zn speciation results obtained by EXAFS and sequential extraction were in excellent agreement. Before filtration, the speciation of Zn in BOF was 43% ZnFe₂O₄, 23% ZnCO₃ and 16% ZnO. The same species were detected after filtration with different proportions. BOF dust after filtration contains more soluble Zn phases which may play a role in the toxic effects of the emissions.     

Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices

BACKGROUND, AIM AND SCOPE: Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). EDCs comprise many classes of organic compounds. The development or optimization of analytical protocols for the simultaneous determination of EDCs in environmental samples is an analytical challenge because these compounds exhibit different physicochemical characteristics, they occur in the aquatic environment in relatively low concentrations and, furthermore, environmental samples are considered as complex matrices. The aim of this study is the development of analytical methods for the simultaneous determination of phenolic and steroid EDCs in aqueous and solid samples. The target compounds are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, the estrogens (estriol, estrone, 17beta-estradiol, 17alpha-estradiol) and the synthetic steroids (mestranol and 17alpha-ethynylestradiol). MATERIALS AND METHODS: Solid phase extraction employing Oasis HLB cartridges and different elution solvents was used for the recovery studies of the target compounds from various types of water samples (ultrapure water, artificial seawater, river water and seawater). Ultrasonic assisted extraction was applied for the recovery of the target EDCs from the solid samples. The recoveries were assessed using various solvents for the extraction and the elution of EDCs from different SPE cartridges used for clean up. Gas chromatography-mass spectrometry after derivatization with N,O-bis(trimethylsilyl)-trifluoroacetamide was employed for the determination of these compounds. RESULTS AND DISCUSSION: The recovery rates of three elution solvents (methanol, acetone and ethylacetate) for the extraction of target EDCs from artificial seawater were assessed after preconcentration on SPE cartridges. Acetone showed better recoveries and was further tested for its extraction efficiency in different water types (river water, seawater). Ultrasonic assisted extraction was used for the recovery of target EDCs from solid matrices. Acetone, methanol, mixture of acetone-methanol (1:1) and ethylacetate were used as extraction solvents. Ethylacetate and the mixture of acetone-methanol (1:1) exhibited better extraction efficiencies. An additional clean up step was necessary for sediment samples. Different SPE cartridges were employed for clean up of the extracts (Oasis HLB, C18, Florisil, silica, combination of silica and alumina). Florisil cartridges were finally used. The proposed methods were further validated on the determination of target EDCs in field collected samples (river water, seawater, wastewater, total suspended solids and sediments) from the major area of Thessaloniki, Greece. CONCLUSIONS: Efficient and accurate integrated methods for the simultaneous determination of alkylphenols (nonylphenol, octylphenol), their ethoxylate oligomers (mono- and di-ethoxylate of nonylphenol and octylphenol), bisphenol A and steroids (estriol, estrone, 17beta-estradiol, 17alpha-estradiol, mestranol and 17alpha-ethynylestradiol) in aqueous and solid samples were developed. The proposed methods were applied for the determination of the target compounds in representative environmental samples in the area of Thessaloniki, Northern Greece. RECOMMENDATIONS AND PERSPECTIVES: This study confirms the occurrence of selected EDCs in inland and marine waters in the area of Thessaloniki, Northern Greece. Since there is no previous data on the occurrence of the target EDCs in the major area, an extended survey is in progress to evaluate the occurrence and fate of these compounds.