Assessment of Uncertainty in Long-Term Mass Balances for Acidification Assessments: A MAGIC Model Exercise

Long-term (1860–2010) catchment mass balance calculations rely on models and assumptions which are sources of uncertainty in acidification assessments. In this article, we report on an application of MAGIC to model acidification at the four Swedish IM forested catchments that have been subject to differing degrees of acidification stress. Uncertainties in the modeled mass balances were mainly associated with the deposition scenario and assumptions about sulfate adsorption and soil mass. Estimated base cation (BC) release rates (weathering) varied in a relatively narrow range of 47–62 or 42–47 meq m⁻² year⁻¹, depending on assumptions made about soil cation exchange capacity and base saturation. By varying aluminum solubility or introducing a dynamic weathering feedback that allowed BC release to increase at more acidic pHs, a systematic effect on predicted changes in acid neutralizing capacity (ΔANC ca. 10–41 μeq l⁻¹) and pH (ca. ΔpH = 0.1–0.6) at all sites was observed. More robust projections of future changes in pH and ANC are dependent on reducing uncertainties in BC release rates, the timing, and extent of natural acidification through BC uptake by plants, temporal changes in soil element pools, and fluxes of Al between compartments.     

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.     

Photoinduced reduction of divalent mercury in ice by organic matter

Reduction of divalent mercury and subsequent emission to the atmosphere has been identified as loss process from surface snow, but its mechanism and importance are still unclear. The amount of mercury that stays in the snow pack until spring is of significance, because during snow melt it may be released to the aquatic environment and enter the food web. Better knowledge of its fate in snow might further assist the interpretation of ice core data as paleo-archive. Experiments were performed under well-controlled laboratory conditions in a coated wall flow tube at atmospheric pressure and irradiated with light between 300 nm and 420 nm. Our results show that the presence of benzophenone and of oxalic acid significantly enhances the release of mercury from the ice film during irradiation, whereas humic acid is less potent to promote the reduction. Further it was found that oxygen or chloride, and acidic conditions lowered the photolytically induced mercury release in the presence of benzophenone, while the release got larger with increasing temperatures.     

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.     

Spatial distribution of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs) in an e-waste dismantling region in Southeast China: Use of apple snail (Ampullariidae) as a bioindicator

Fengjiang is a large e-waste dismantling site located in southeast China. In this paper, apple snail and soil samples were collected from this e-waste dismantling site and 25 vicinal towns to investigate the contamination status, spatial distributions and congener patterns of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs). Total PCB concentrations in apple snails (3.78-1812 ng g⁻¹ dry weight (dw)) were significant higher than that in soil samples (0.48-90.1 ng g⁻¹ dw). PBDE (excluding BDE 209) concentrations in apple snail and soil samples ranged from 0.09 to 27.7 ng g⁻¹ dw and 0.06 to 31.2 ng g⁻¹ dw, respectively. Concentrations of PCBs and PBDEs in snails and soils correlated negatively with the distance from Fengjiang. Both the concentrations and profiles of the pollutants were significantly correlated (p < 0.05) between the snail and soil samples, indicating the suitability of apple snail as a reliable bioindicator for PCBs and PBDEs contamination in this region. Relatively high concentrations of PCBs and PBDEs at locations far from e-waste dismantling sites implied that these pollutants have been transported to surrounding regions.     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

Influence of constant and fluctuating temperature on biodegradation rates of fish biodiesel blends contaminating Alaskan sand

Bioremediation of sandy soil contaminated with fish-biodiesel, conventional diesel, and blends of both was studied in microcosm experiments at different temperatures, simulating the subarctic environment. While distinct lag, exponential, and stationary phases were observed at 20 °C, degradation at 6 °C was slow and the lag phase continued throughout the 4-week experiment. A three-phase 1st order kinetic model successfully described respiration at 20 °C, a one-phase model was sufficient at 6 °C. For temperatures fluctuating between ∼6 and ∼20 °C, higher than expected microbial activity persisted at 6 °C for several days, due to the presence of active cultures, even though the soil temperature closely followed the air temperature. At 20 °C, respiration peaked already after 1 week, and 18-51% of the initially added fuel was mineralized within 4 weeks, whereby degradation was higher at higher biodiesel percentages. Biodiesel addition accelerated mineralization of blends with regular diesel beyond expectations. In blends with 20% biodiesel, the degradation rate constant was twice as high as for conventional diesel. These synergistic effects are likely due to an active microbial population. Addition of biodiesel to conventional diesel could reduce the impact of diesel spills.