Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in aqueous solutions and in organic solvents

Aqueous solutions of selected polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were prepared using a generator column and exposed to UV (300 nm) light in the laboratory and to sunlight in an outdoor environment. In the laboratory, additional exposures were also carried out using 60% acetonitrile/water solutions. At 300 nm di- and tetra PCDDs had higher first-order photodegradation rate constants in 60% acetonitrile/water than in pure water. The solvent effect was reversed for PCDFs. These results may be a reflection of the higher polarity of PCDFs compared to PCDDs. In both the indoor and outdoor exposures photodegradation rates decreased with increasing concentrations of chlorination. However, OCDF exposed to 300 nm light in 60% acetonitrile/water and to sunlight in pure water photodegraded more rapidly than tetra CDF. Photolysis rates in sunlight were considerably slower (t(1/2) of 6.4-23 h) than photolysis rates at 300 nm in the laboratory (t(1/2) of 4.3-680 min), reflecting the lower intensity of sunlight in the 300 nm region of the UV/Vis spectrum. The extent of dechlorination of the PCDDs/PCDFs was less than 20% and reductive dechlorination does not appear to be a major process in the photodegradation of PCDDs/PCDFs in aqueous solutions.     

Source apportionment of fine particles in Washington, DC, utilizing temperature-resolved carbon fractions

Integrated ambient particulate matter < or =2.5 microm in aerodynamic diameter (PM2.5) samples were collected at a centrally located urban monitoring site in Washington, DC, on Wednesdays and Saturdays using Interagency Monitoring of Protected Visual Environments samplers. Particulate carbon was analyzed using the thermal optical reflectance method that divides carbon into four organic carbon fractions, pyrolyzed organic carbon, and three elemental carbon fractions. A total of 35 variables measured in 718 samples collected between August 1988 and December 1997 were analyzed. The data were analyzed using Positive Matrix Factorization and 10 sources were identified: sulfate (SO4(2-))-rich secondary aerosol I (43%), gasoline vehicle (21%), SO4(2-)-rich secondary aerosol II (11%), nitrate-rich secondary aerosol (9%), SO4(2-)-rich secondary aerosol III (6%), incinerator (4%), aged sea salt (2%), airborne soil (2%), diesel emissions (2%), and oil combustion (2%). In contrast to a previous study that included only total organic carbon and elemental carbon fractions, motor vehicles were separated into fractions identified as gasoline vehicle and diesel emissions containing carbon fractions whose abundances were different between the two sources. This study indicates that the temperature-resolved carbon fraction data can be utilized to enhance source apportionment, especially with respect to the separation of diesel emissions from gasoline vehicle sources. Conditional probability functions using surface wind data and deduced source contributions aid in the identifications of local sources.     

Digested sewage sludge solidification by converter slag for landfill cover

A new technology for solidification of digested sewage sludge referred to as converter slag solidification (CSS) has been developed using converter slag as the solidifying agent and quick lime as the solidifying aid. The CSS technology was investigated by analyzing the physicochemical properties of solidified sludge and determining its microstructural characteristics. The feasibility of using solidified sludge as a landfill cover material was considered in the context of the economical recycling of waste. Sludge solidified using the CSS technology exhibited geotechnical properties that are appropriate for replacing currently used cover soil. Microscopic analyses using XRD, SEM and EDS revealed that the main hydrated product of solidification was CSH (CaO . SiO2 . nH2O), which may play an important role in the effective setting process. Negligible leaching of heavy metals from the solidified sludge was observed. The solidification process of the hydrated sludge, slag and quicklime eliminated the coliform bacteria. Recycled sewage sludge solidified using CCS technology could be used as an effective landfill cover.     

Heavy metal removal by activated sludge: influence of Nocardia amarae.

The goal of this research was to examine the metal binding capacity of Nocardia amarae cells and to assess the influence of Nocardia cells on the overall metal binding capacity of activated sludge. Metal sorption capacities of the pure Nocardia cells and activated sludge biomass containing various levels of added Nocardia pure cultures were determined by a series of batch experiments. Batch sorption isotherms for nickel (Ni), copper (Cu), and cadmium (Cd) showed that the pure culture of N. amarae exhibited significantly higher metal sorption capacity than the activated sludge biomass obtained from Wilmington Wastewater Treatment Plant (Wilmington, DE). Surface area of biomass estimated by a dye technique showed that pure N. amarae cells growing at stationary phase have substantially more specific surface area than that of activated sludge from Wilmington Treatment Plant. A two-fold difference in specific surface area indicated that the higher metal sorption capacity of Nocardia cells may be due to the higher specific surface area. The metal sorption capacity of activated sludge increased proportionally with the amount of Nocardia cells present in the mixed liquor. This increase was attributed to the greater specific surface area of the mixed liquor samples containing greater amounts of Nocardia cells.     

Effect of dissolved humic matters on the leachability of PCDD/F from fly ash--laboratory experiment using Aldrich humic acid

The effect of dissolved humic matters (DHM) on the leachability of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) in fly ash was studied theoretically and in laboratorial condition to verify the previous results for pilot and field experiment of incineration residues landfill. In theoretical review, it was shown that DHM could influence the actual solubility and leachability of PCDD/F. The higher concentration of DHM showed the higher leachability of PCDD/F. In the leaching test, three different DHM concentrations and pHs of solutions were adopted to fly ash samples imaging the various characteristics of municipal solid waste leachate. It was proved experimentally that the leachability of PCDD/F increased with increasing DHM concentration in all pH conditions. The highest leachability was shown at the highest pH. Isomer distribution patterns of PCDD/F in all leachates were similar in all pH conditions. It backed up the distribution theory of PCDD/F between DHM and water.     

Effects of host plant exposure to cadmium on mycorrhizal infection and soluble carbohydrate levels of Pinus sylvestris seedlings

In a Cd-contaminated environment, not only mature trees but also their seeds and young seedlings can be exposed to Cd. Cadmium taken up by young seedlings may influence mycorrhizal infection, which might in turn influence resistance to Cd toxicity. In order to eliminate soil-mediated responses of mycorrhizal infection to Cd, Pinus sylvestris seedlings were exposed to Cd prior to fungal inoculation and replanted to clean substrates with fungal inoculum. Cadmium pretreatment reduced the proportion of living mycorrhizal short roots of seedlings inoculated with Paxillus involutus. However, no such effect was observed for seedlings inoculated with Suillus bovinus and Rhizopogon subcaerulescens. Therefore, infection by P. involutus appeared to be affected by Cd taken up by seedlings. Overall stem length and biomass of the seedlings were reduced by Cd pretreatment. Infection by S. bovinus and R. subcaerulescens increased stem length and biomass of the seedlings. Root soluble carbohydrate concentrations were lower in mycorrhizal seedlings than non-mycorrhizal seedlings.     

A preliminary risk assessment of trace elements accumulated in fish to the Indo-Pacific Humpback dolphin (Sousa chinensis) in the northwestern waters of Hong Kong

In order to assess the potential risks associated with consumption of contaminated prey items to the Indo-Pacific Humpback dolphin (Sousa chinensis), fish species (Collichthys lucida, Pseudosciaena crocea, Johnius sp., Thryssa sp., Mugil sp. and Trichiurus sp.) representing the main food items of the dolphin were collected from the northwestern waters of Hong Kong, including the Sha Chau and Lung Kwu Chau Marine Park, which form the main habitat of the dolphin in Hong Kong. Within these waters, there are several potential sources of pollution including significant inputs from the Pearl River catchment, several major sewage outfalls and a series of mud pits that receive contaminated dredged sediments. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V, and Zn) in the fish tissue were analyzed by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of the risks of adverse effects on the dolphin due to consumption of tainted fish was undertaken using two toxic reference benchmarks, namely the reference dose (RfD) and toxicity reference value (TRV). The risk quotient (RQ) calculated for each element showed that the risks from consumption of fish were generally low and within safe limits. The risks associated with arsenic, cadmium and mercury were, however, elevated. The highest calculated RQ was associated with total arsenic; however, the majority of arsenic in marine organisms tends to be in the non-toxic organic form, and the actual risk to the dolphin due to this metalloid is likely to be lower.     

HPLC pigment analysis of marine phytoplankton during a red tide occurrence in Tolo Harbour,Hong Kong

A red tide was detected in the inner parts of Tolo Harbour, Hong Kong, in November 2000. Water samples were collected from a fixed station at the centre of the red tide patch for microscopic analysis of phytoplankton community composition and high performance liquid chromatography (HPLC) analysis of phytoplankton pigments. At the peak of the red tide on 24 November 2000, phytoplankton was dominated by the dinoflagellate Scrippsiella trochoidea. The red tide began to decline at the end of November and, by 1 December 2000, the phytoplankton was dominated by diatoms. Chlorophylls and carotenoids in water samples were analysed using HPLC pigment separation technique. Dinoflagellates were indicated by the signature pigment peridinin. Significant correlation (r=0.999) was found between the peridinin concentration and dinoflagellate density. A decrease in peridinin and an increase in fucoxanthin, a major carotenoid in diatoms, marked the shift in phytoplankton composition at the end of the red tide. HPLC analysis also revealed the occurrence of minor phytoplankton groups that are difficult to identify by light microscopy. Red tide monitoring and study of red tide dynamics in Hong Kong have been based on cell counting and spectrophotometric or fluorometric measurement of chlorophyll a. HPLC pigment analysis provides an effective alternative for investigating phytoplankton dynamics during red tide and other algal blooms.     

Formation and emission status of PCDDs/PCDFs in municipal solid waste incinerators in Korea

This study was carried out to examine the formation and the emission status of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) in the flue gases of commercial-scale municipal solid waste (MSW) incinerators, and thus to provide the engineering data for the reduction of PCDDs/PCDFs emitted from MSW incinerators. The formation concentrations of the PCDDs/PCDFs generated at the outlet of waste heat boilers (WHB) were in the range of 1.18-29.61 ng-TEQ/N m3 (average 5.75 ng-TEQ/N m3), while the emission concentrations at the stacks were in the range of 0.026-4.548 ng-TEQ/N m3 (average 0.924 ng-TEQ/N m3). Two major 2,3,7,8-substituted congeners were 2,3,4,7,8-PeCDF and 2,3,4,6,7,8-HxCDF, and their concentrations were up to 50% and 64% of total TEQ values at the outlet of WHB and the stack, respectively. From the results of multi-regression analysis, the formation concentration of PCDDs/PCDFs could be predicted as follows with the correlation factor of r2 = 0.962: PCDDs/PCDFs (ng-TEQ/N m3) = 3.036 (Cl) + 0.094 (T1) - 0.472 (Combustibles) + 0.059 (CO) - 0.039 (THC) - 3.366 (H) + 22.157, where T1 (degrees C) is the temperature at the outlet of the WHB. Cl, Combustibles and H are given as percentages and the others are in parts per million.     

Levels of PCDDs and PCDFs in two kinds of fast foods in Korea

We initiated an attempt to gather preliminary Korean fast food data on the concentrations, whole weight and international toxic equivalent (TEQ), in two kinds of fast foods, hamburger and fried chicken. The levels of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) in hamburgers are detected to be lower than in fried chickens. Total TEQ level of PCDDs in fried chicken is 47.45 times higher than in hamburger. In case of PCDFs, it is 48.61 times. Even though these are compared to the only one brand and three samples each, we think that these high levels of PCDDs/PCDFs in fried chicken are very important data because of the potentially increasing daily intake. If we continue to survey for PCDDs/PCDFs in fast foods more even, especially fried chicken, these data will be useful to calculate the estimated daily intake of TEQ levels of PCDDs/PCDFs in Korea.