Increased Bioavailability of Mercury in the Lagoons of Lomé, Togo: The Possible Role of Dredging

Surface sediments of the lagoons of Lomé, Togo, were analyzed for mercury, methylmercury, and trace elements. Concentrations were greater than typical for natural lagoon sediments, and with greater variability within the Eastern lagoon compared to the Western one. The Eastern lagoon is larger and has been dredged in the past, while the Western lagoon, which also receives major waste inputs, has not been dredged and shows less tidal flushing. Accordingly, one naturally believes that the Eastern lagoon is cleaner and probably safe to use due to its natural resources, including fishes to eat. Unexpectedly, we describe here that mercury methylation was greater in the Eastern lagoon, indicating increased bioavailability of mercury, as probably facilitated by past dredging that decreased solid-phase retention of inorganic mercury. Urbanization has historically been more developed in the southern part of the lagoons, which is still reflected in contamination levels of sediment despite dredging, probably because sources of contamination are still more important there today. Such urban contamination emphasizes the need to regulate waste discharges and possible airborne contamination in growing cities of developing countries, and implements environmental and public health monitoring, especially in relation to misbelieves systematically associated with the cleansing effect of dredging activity.     

Estimation of the environmental risk posed by landfills using chemical, microbiological and ecotoxicological testing of leachates

The leachates from 22 municipal solid waste (MSW) landfill sites in Southern Poland were characterized by evaluation of chemical, microbiological and ecotoxicological parameters. Chemical analyses were mainly focused on the identification of the priority hazardous substances according to Directive on Priority Substances, 2008/105/EC (a daughter directive of the WFD) in leachates. As showed, only five substances (Cd, Hg, hexachlorobutadiene, pentachlorobenzene and PAHs) were detected in the leachates. The compounds tested were absent or present at very low concentrations. Among them, only PAHs were found in all samples in the range from 0.057 to 77.2 μg L⁻¹. The leachates were contaminated with bacteria, including aerobic, psychrophilic and mesophilic bacteria, coliform and fecal coliforms, and spore-forming-bacteria, including Clostridium perfringens, and with filamentous fungi. From the analysis of specific microorganism groups (indicators of environmental pollution by pathogenic or opportunistic pathogenic organisms) it can be concluded that the landfill leachates showed sanitary and epidemiological hazard. In the ecotoxicological study, a battery of tests comprised of 5 bioassays, i.e. Microtox®, Spirotox, Rotoxkit F™, Thamnotoxkit F™ and Daphtoxkit F™ magna was applied. The leachate samples were classified as toxic in 13.6%, highly toxic in 54.6% and very highly toxic in 31.8%. The Spirotox test was the most sensitive bioassay used. The percentage of class weight score was very high - above 60%; these samples could definitely be considered seriously hazardous and acutely toxic to the fauna and microflora.No correlations were found between the toxicity values and chemical parameters. The toxicity of leachate samples cannot be explained by low levels of the priority pollutants. It seems that other kinds of xenobiotics present in the samples at subacute levels gave the high aggregate toxic effect.The chemical, ecotoxicological and microbiological parameters of the landfill leachates should be analyzed together to assess the environmental risk posed by landfill emissions.     

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.     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

Dietary patterns and blood levels of PCDDs, PCDFs, and dioxin-like PCBs in 1656 Japanese individuals

The association between dietary patterns and blood dioxin levels has not been fully investigated. The present study population consisted of 755 men and 901 women (aged 15-73 years) living in 90 different areas of 30 prefectures of Japan. Dietary habits were assessed by inquiring about the consumption frequency of 28 foods, food groups and beverages. In addition, the blood levels of 29 polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzo-furans (PCDFs), and dioxin-like polychlorinated biphenyl (DL-PCBs) congeners were determined by high-resolution gas chromatography/mass spectrometry. The median total toxicity equivalent (TEQ) in the blood, which was calculated on the basis of the toxicity equivalency factors of WHO (2005), was 16 pg TEQ g⁻¹ lipid. Principal component analysis identified five dietary patterns: Healthy diet (high intake of vegetables and fruits); Meat/High fat intake (high intake of meat, meat products, and eggs); Seafood and Alcohol (high intake of fish, shellfish, and alcoholic beverages); Miscellaneous; and Milk products and Alcohol intake (high intake of milk, Milk products, and alcoholic beverages). After adjusting for sex, age, body mass index, and smoking habits, the Seafood and Alcohol pattern scores were significantly related to higher blood levels of total TEQ and PCDDs/PCDFs/DL-PCBs, and the Milk products and Alcohol pattern scores were correlated with higher blood levels of DL-PCBs. More detailed analysis showed that the intake frequencies for alcoholic beverages and seafood were independently and positively associated with total TEQ and the TEQ of PCDFs and DL-PCBs. The association between alcoholic beverage intake and PCDDs was also significant. Analysis of dietary patterns may be useful for identifying the dietary characteristics of individuals with a high dioxin body burden.     

Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

Seasonal change of PCDDs/PCDFs/DL-PCBs in the water of Ayase River, Japan: pollution sources and their contributions to TEQ

In Japan, Ayase River is one of the most polluted rivers by PCDDs, PCDFs and dioxin-like PCBs, which are referred to as dioxins in this paper. The water samples of the river were collected once per month for a year, and dioxins were analyzed to examine the dioxin sources and their contributions to toxic equivalent (TEQ). The WHO-2006 TEQs ranged from 0.26 to 7.0 pg-TEQ L⁻¹ and the average was 2.7 pg-TEQ L⁻¹; eight of 12 samples exceeded the environmental quality standard in Japan (1.0 pg-TEQ L⁻¹). The TEQ value was high during the irrigation period from May to August. The most part of the dioxins in the river water existed in suspended solids (SS) and it seemed that the river received water with highly-dioxin-contaminated SS in the irrigation period. The homologue profiles of the water samples suggested that the dioxins were influenced by pentachlorophenol (PCP) and chlornitrofen (CNP) formulations which were widely used as herbicides for the paddy fields in Japan. According to TEQ apportionment estimated by using indicative congeners, the TEQ was mainly contributed by PCP. Moreover, it was also shown that the TEQ contributions of PCP and CNP formulations increased along with the increase of the total TEQ and the TEQ contribution was dominated by these herbicides during the irrigation period. Therefore, it was concluded that the herbicides-originated dioxins run off from the paddy fields into the river during the irrigation period and increased the dioxins level in the river water. The result from the principal component analysis was consistent with these conclusions.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

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.