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.     

沉积物和土壤孔隙水中甲基汞的一种新型平衡被动采样装置的研制

在这项研究中,我们探索了利用疏水性有机化学品（HOCs）开发的策略对甲基汞（MeHg）进行平衡被动采样的概念。被动取样应允许基于平衡分配到取样器中的基础上预测沉积物孔隙水（MeHgCL）中MeHg的化学不稳定部分的浓度,而无需模拟通过取样器材料的扩散速率。我们的目标是确定具有模拟甲基汞在动物和沉积物中分配的潜力的取样器材料,并在适合于原位取样器的时间框架内提供可逆吸附。测试的候选材料包括一系列嵌有合适的甲基汞吸收剂的聚合物。最有潜力的是琼脂糖包埋的活性炭（AC）、琼脂糖包埋的巯基自组装膜（SMS）和半胱氨酸功能化聚对苯二甲酸乙二醇酯（PET）,对MeHgOH和MeHg与溶解有机物（Suwannee河腐殖酸）的络合作用,测井采样器的水分配系数（Kpw）为2.8～5。沉积物中采样器的平衡时间约为1～2周。琼脂糖包埋AC对MeHg积累机制的研究表明,样品受MeHg与AC颗粒相互作用的动力学影响,而不受凝胶扩散的限制。AC显示Hg和MeHg的相对快速解吸,表明该吸附剂能够进行可逆的平衡测量。在沉积物:水的微观结构中,用等温线校准的被动取样器测得的孔隙水浓度与直接测得的浓度在2倍（未经修正的沉积物）或4倍（经修正的AC沉积物）内一致。这项工作为甲基汞的被动采样提供了一种潜在的新途径。     

Quantification of activated carbon contents in soils and sediments using chemothermal and wet oxidation methods

Activated carbon (AC) strongly sorbs organic pollutants and can be used for remediation of soils and sediments. A method for AC quantification is essential to monitor AC (re)distribution. Since AC is black carbon (BC), two methods for BC quantification were tested for AC mixed in different soils and sediments: i) chemothermal oxidation (CTO) at a range of temperatures and ii) wet-chemical oxidation with a potassium dichromate/sulfuric acid solution. For three soils, the amount of AC was accurately determined by CTO at 375 °C. For two sediments, however, much of the AC disappeared during combustion at 375 °C, which could probably be explained by catalytic effects by sediment constituents. CTO at lower temperatures (325-350 °C) was a feasible alternative for one of the sediments. Wet oxidation effectively functioned for AC quantification in sediments, with almost complete AC recovery (81-92%) and low remaining amounts of native organic carbon (5-16%).     

Study of the biouptake of labeled single-walled carbon nanotubes using fluorescence-based method

Single-wall carbon nanotubes (CNT) are one of the most attractive engineered nanomaterials due to their unique electrical, mechanical and thermal properties, and potential use in a variety of commercial products. Due to their small size, CNT could become easily airborne and reach the various environmental compartments and eventually the food chain and humans. However, the environmental fate processes and health impacts of CNT are not clear. This study investigated a method for the quantitative measurement of carbon nanotube (CNT) in natural media such soil and benthic organism tissues. Fluorescence dye Nile blue was used for noncovalent labeling of CNT to enable their fluorescence detection. Labeled nanotubes were successfully detected in soil samples as well as in worm tissue. We were also able to detect the presence of labeled carbon nanotubes in worms exposed for 1 week to CNT-laden soil, which indicates CNT may transfer through environmental food web. The method allows for laboratory measurements of CNT mass transfer and partitioning into various environmental systems.     

Chemopreventive role of Indigofera aspalathoides against 20-methylcholanthrene-induced carcinogenesis in mouse

This investigation was undertaken to evaluate the chemopreventive effect of hydroalcoholic extract of Indigofera aspalathoides (HAIA) against 20-methylcholanthrene (20-MC)-induced carcinogenesis in mice. Tumor was induced by single subcutaneous administration of 20-MC (200 µg per mouse) in Swiss albino mice. After 24 h of 20-MC administration, HAIA was administered at the doses of 250 and 500 mg kg^?1 body weight orally for 90 consecutive days. Mice of all groups were observed for 15 weeks to record tumor incidence (fibrosarcoma) and survival time. After 15 weeks the mice were sacrificed for the estimation of hematological profiles like hemoglobin (Hb), white blood cell (WBC), red blood cell (RBC), and liver biochemical parameters, namely lipid peroxidation, reduced glutathione (GSH), glutathione-S-transferase (GST), superoxide dismutase (SOD), and catalase (CAT). HAIA treatment markedly reduced tumor incidence and prolonged the life span of sarcoma-bearing mice as compared to 20-MC control mice. Hematological profiles were significantly (p < 0.001) restored to normal levels in HAIA-treated mice as compared to 20-MC control mice. HAIA treatment significantly (p < 0.001) modulated the aforesaid liver biochemical parameters as compared to 20-MC control. The results concluded that I. aspalathoides demonstrated a remarkable chemopreventive effect in chemical-induced carcinogenesis in mouse. The potential chemopreventive action may be due to its antioxidant and detoxifying properties.     

Investigating differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans in soil and soil components using selective supercritical fluid extraction

Supercritical fluid extraction (SFE) with pure carbon dioxide was performed at increasingly strong conditions to investigate differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in two impacted soils, in their sieved size fractions, and in small (a few mg) samples of industry-related waste products separated from impacted soil. The binding strengths of PCDD/Fs were shown to be different in the two soils, and in their different soil particle size fractions. As might be expected based on surface area considerations, one soil showed the strongest binding in the smallest (<5 μm) sieved fraction. However, the other soil showed the strongest binding in the larger sized fractions, possibly indicating that process-related particles could be controlling PCDD/F binding. Selective SFE of various types of particles including black carbon and charcoal (separated from soil), and from a suspected process anode residue did show different PCDD/F binding behavior ranging from quite weak binding (charcoal) to very strong binding (anode particles). Shifts to the stronger SFE fractions in the soils after activated carbon treatment agreed well with the decreases previously found in the uptake of PCDD/Fs by earthworms, as well as decreases in their freely-dissolved aqueous concentrations in soil/water slurries. These results show that, as previously demonstrated for PAHs and PCBs, selective SFE can be a useful tool to investigate differences in PCDD/F binding behaviors in impacted soils and sediments and their component parts, as well as a rapid tool for estimating the effectiveness of activated carbon treatments on decreasing the bioavailability of PCDD/Fs in soils and sediments.     

Influence of activated carbon amendment on the accumulation and elimination of PCBs in the earthworm Eisenia fetida

In this study we investigated the use of activated carbon (AC) as a soil amendment for reducing bioavailability of polychlorinated biphenyls (PCBs) to the earthworm Eisenia fetida. Artificial soil was contaminated with PCBs and used in bioaccumulation experiments fresh or after aging for 19 months. PCB bioaccumulation in earthworms was reduced by 68% when AC was placed as a layer without mixing and by 94% when AC was manually mixed into the soil. Aging of the same AC mixed soil for 19 months resulted in an overall reduction of 99% in PCB biouptake. AC-treated aged soil also showed two orders of magnitude lower equilibrium aqueous concentrations of PCBs compared to untreated aged soils. The findings from this study indicate that application of engineered sorbents like AC to PCB impacted soils may greatly reduce PCB uptake at the base of the terrestrial food chain.