Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

Hydroxytyrosol, the phenolic compound of olive oil protects human PBMC against oxidative stress and DNA damage mediated by 2,3,7,8-TCDD

The protective effect of hydroxytyrosol (HT), a strong antioxidant compound from extra virgin olive oil, against TCDD induced toxicity was investigated in human peripheral blood mononuclear cells (PBMC). PBMC (1 × 10⁶ cells mL⁻¹) were divided into four groups and were incubated in a CO₂ incubator (5% CO₂) for 12 h with vehicle, TCDD (10 nM), TCDD + HT (10 nM + 100 μM) and HT alone (100 μM) respectively. To clarify the role of HT against TCDD induced cytotoxicity, oxidative stress and the levels of antioxidant enzymes were assessed. Incubation of PBMC with TCDD significantly decreased cell viability, catalase (CAT) and glutathione peroxidase (GPx) and increased the levels of superoxide dismutase (SOD), glutathione reductase (GR) and oxidative stress markers such as lipid peroxidation products (LPO), protein carbonyl content (PCC) and reactive oxygen species (ROS). Whereas, HT had an effective antioxidant property as observed by the increased cell viability, normalization of antioxidant enzymes and decreased levels of LPO, PCC and ROS in PBMC co-treated with HT and TCDD. Apoptosis detection and comet assay results shows that HT, by acting as an antioxidant, prevents the damage to DNA induced by TCDD. In addition light microscopic and histopathological observations revealed that the cells are apoptotic and degenerated during TCDD treatment, whereas cells showed intact morphology during co-treatment with HT. On the whole, the results reveal that HT exerts a promising antioxidant potential in protecting the PBMC against TCDD induced oxidative stress, which might be due to the presence of catechol moiety in its structure.     

An occupational exposure assessment of polychlorinated dibenzo-p-dioxin and dibenzofurans in firefighters

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are unintentional byproducts of combustion and industrial processes. Firefighters face the risk of occupational exposure to PCDD/Fs. Congener-specific analyses of 17 PCDD/Fs were performed on 20 serum samples collected from firefighters and fire scene investigators, and four soot samples that had deposited on the surfaces of the fire helmets and were collected after the firefighters had fought fires. The PCDD/F concentrations on the helmets that were contaminated by being worn at the fire scenes were 63-285 times higher than those on a clean helmet. The median serum PCDD/F concentration of the 16 firefighters (12 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was not different from those of the males from the general Taiwanese population (9.4 pg WHO₂₀₀₅-TEQ g⁻¹ lipid). However, the median PCDD/F level in the four fire scene investigators (15 pg WHO₂₀₀₅-TEQ g⁻¹ lipid) was higher than those in the male from the general Taiwanese population (Mann-Whitney U test, p < 0.01). Furthermore, the serum samples from the firefighters and fire scene investigators, and the soot samples from the fire scenes presented similarly distinctive PCDD/F profiles that had elevated proportions for 10 PCDF congeners. Limited data indicated that the fire scene investigators were occupationally exposed to PCDD/Fs at the fire scenes. We suggested that the firefighters were not occupationally exposed to PCDD/Fs at the fire scenes due to appropriate protection. However, the fire scene investigators may have had more occupational exposure to PCDD/Fs due to poor protection, and further research must be performed to confirm this.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

PCDD/F enviromental impact from municipal solid waste bio-drying plant

The present work indentifies some environmental and health impacts of a municipal solid waste bio-drying plant taking into account the PCDD/F release into the atmosphere, its concentration at ground level and its deposition. Four scenarios are presented for the process air treatment and management: biofilter or regenerative thermal oxidation treatment, at two different heights. A Gaussian dispersion model, AERMOD, was used in order to model the dispersion and deposition of the PCDD/F emissions into the atmosphere. Considerations on health risk, from different exposure pathways are presented using an original approach. The case of biofilter at ground level resulted the most critical, depending on the low dispersion of the pollutants. Suggestions on technical solutions for the optimization of the impact are presented.     

Tracing the sources of refractory dissolved organic matter in a large artificial lake using multiple analytical tools

Structural and chemical characteristics of refractory dissolved organic matter (RDOM) from seven different sources (algae, leaf litter, reed, compost, field soil, paddy water, treated sewage) were examined using multiple analytical tools, and they were compared with those of RDOM in a large artificial lake (Lake Paldang, Korea). Treated sewage, paddy water, and field soil were distinguished from the other sources investigated by their relatively low specific UV absorbance (SUVA) values and more pronounced fulvic-like versus humic-like fluorescence of the RDOM samples. Microbial derived RDOM from algae and treated sewage showed relatively low apparent molecular weight and a higher fraction of hydrophilic bases relative to the total hydrophilic fraction. For the biopolymer types, the presence of polyhydroxy aromatics with the high abundance of proteins was observed only for vascular plant-based RDOM (i.e., leaf litter and reed). Molecular weight values exhibited positive correlations with the SUVA and the hydrophobic content among the different RDOM, suggesting that hydrophobic and condensed aromatic structures may be the main components of high molecular weight RDOM. Principal component analysis revealed that approximately 77% of the variance in the RDOM characteristics might be explained by the source difference (i.e., terrestrial and microbial derived) and a tendency of further microbial transformation. Combined results demonstrated that the properties of the lake RDOM were largely affected by the upstream sources of field soil, paddy water, and treated sewage, which are characterized by low molecular weight UV-absorbing and non-aromatic structures with relatively high resistance to further degradation.     

淀粉-g-丙烯酸/凹凸棒土复合物制备及其吸附废水中NH_4~＋-N性能

采用反相乳液聚合法以凹凸棒土为原料,合成了新型NH4＋-N吸附剂淀粉-g-丙烯酸/凹凸棒土,并进行了氨氮吸附对比实验。结果表明：凹凸棒土氨氮单位吸附量为4.243 mg/g;淀粉-g-丙烯酸/凹凸棒土氨氮单位吸附量为5.301 mg/g,吸附能力比未改性的凹凸棒土提高了25%。淀粉-g-丙烯酸/凹凸棒土的氨氮吸附过程比凹凸棒土更符合Freundlich等温吸附模型。随着pH、温度的升高,凹凸棒土和淀粉-g-丙烯酸/凹凸棒土对NH4＋-N吸附量逐渐增大。     

壳聚糖的物理/化学改性及其对含酚废水的处理

将壳聚糖物理改性为球形颗粒,然后在微波辐射下,球形壳聚糖与柠檬醛接枝反应,再与NaBH4还原反应,制备一种新型环保材料--物化改性壳聚糖.采用红外光谱仪(IR)、X衍射仪(XRD)、电子显微镜(SEM)和比表面测定及孔径分析仪(BET)结构表征改性壳聚糖.通过含酚制药废水的动态小柱吸附实验,研究了时间、柱高和出水流速等...     

V/Ce共掺杂TiO2光催化降解甲醛的实验研究

采用溶胶凝胶法制备了不掺杂、V 掺杂、Ce掺杂、V/Ce共掺杂纳米TiO₂光催化剂,并将其分别负载于瓷砖上,利用X射线衍射分析（XRD）和扫描电镜分析（SEM）技术对薄膜样品的结构和形貌进行了表征。通过对甲醛的降解实验评价光催化剂的光催化活性。实验结果表明,光催化剂的负载量、共掺杂离子的掺杂量、掺杂配比、煅烧温度影响纳米TiO₂的光催化活性。V/Ce共掺杂TiO₂光催化剂产生了协同效应,其光催化活性优于纯TiO₂和单掺杂TiO₂样品。     

湿式空气氧化法处理TNT红水的影响因素

使用湿式空气氧化技术与生物技术联合处理TNT精制阶段所产生的红水,研究了湿式空气氧化过程中反应温度、反应时间、初始压强和pH值对流出物的COD值与流出物可生化性的影响规律。研究结果表明,随着反应温度和反应初始压强的升高、反应时间的延长、催化剂投加量的增加和反应pH值的降低,出水COD值均有所下降。在温度为300℃、初始压强为14MPa、反应时间为2h、pH值为5,3、铁盐催化剂添加量为2g的条件下,出水COD值为498mg／L,COD去除率可达到99．27％。在温度为300℃、初始压强为11MPa、反应时间为1h、pH值为3、添加1g铁盐催化剂的条件下：反应流出物的BOD5／COD值为0．301,此时可生化性已经得到很好改善。通过生物方法对反应流出物后续处理发现,湿式空气氧化技术处理TNT红水在反应温度300℃以上,反应流出物均可生物降解。