Hydrology, suspended sediment dynamics and nutrient loading in Lake Takkobu, a degrading lake ecosystem in Kushiro Mire, northern Japan

Suspended sediment and nutrient loadings from agricultural watersheds have lead to habitat degradation in Lake Takkobu. To examine their relationships with land-use activities, we monitored sediment, nutrient and water discharges into the lake for a 1-year sampling period. The Takkobu River contributed the largest portion of the annual water discharge into the lake, compared with the other tributaries. During dry conditions, lake water flowed into the Kushiro River, and conversely during flooding, Kushiro River water flowed into the lake. Inflows from the Kushiro River had a high proportion of inorganic matter, with high concentrations of total nitrogen and total phosphorus, attributed to agricultural land-use development and stream channelization practiced since the 1960s in the Kushiro Mire. Nutrient loadings from these two rivers were significantly higher during flooding than in dry conditions. However, there was no clear correlation between river discharge and nutrient concentrations. Since land-use activities in the Kushiro River and Takkobu River watersheds were concentrated near rivers, nutrients easily entered the drainage system under low flow conditions. In contrast, water discharged from small, forest-dominated watersheds contained a low proportion of inorganic matter, and low nutrient concentrations. The suspended sediment delivered to the lake during the sample period was estimated as approximately 607 tons, while the total nitrogen and total phosphorus inflows were about 10,466 and 1,433 kg, respectively. Suspended sediment input into the lake was 65%, and total nitrogen and total phosphorus were 40% and 48%, respectively, being delivered by the Kushiro River.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans from food salt samples processed by heat treatment in Korea

Eight samples of processed food salt collected from five plants in Korea were analyzed for 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) using liquid-liquid extraction, clean-up procedures, and high resolution gas chromatography-high resolution mass spectrometry. The study included the analyses of two kinds of salt product sample: bamboo-salt and parched salt. The levels of toxic PCDD/Fs found in the salt product samples were extremely low: the results revealed TEQ levels ranging between the sub pg TEQ/g and sub fg TEQ/g. The differences in the TEQ values of toxic PCDD/F were observed between the salt product samples, which were treated with different frequency of baking using four different fuels (firewood, pine wood, pine resin, and indirect heating by gas) at temperatures from 300 to 2000 degrees C. In bamboo-salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.57-66 pg/g and 5.7x10(-5)-0.64 pg TEQ/g, respectively. PCDD/Fs levels in bamboo-salts baked by firewood were found to be higher than those baked by pinewood or pine resin. In parched salt samples, the concentrations and TEQ values of toxic PCDD/Fs ranged between 0.97-3.7 pg/g and 0.0097-0.017 pg TEQ/g, respectively. The data was discussed regarding the concentration and the distribution pattern of congeners.     

Treatment of 2,4-dichlorophenol polluted soil with free and immobilized laccase

Enzyme treatment is currently considered for remediation of terrestrial systems polluted with organic compounds. In this study, two soils from Pennsylvania with 2.8 or 7.4% organic matter contents (Soils 1 and 2, respectively) were amended with 14C-labeled 2,4-dichlorophenol (2,4-DCP) and incubated with a laccase from Trametes villosa (free or immobilized on montmorillonite). 2,4-DCP was either transformed to methanol-soluble polymeric products (11-32%) or covalently bound to soil organic matter (53-85%); unaltered 2,4-DCP could be recovered from soil by methanol extraction (0-38%) at the completion of a 14-d incubation period. In Soil 1, both free and immobilized laccase removed 100% of 2,4-DCP without regard for moisture conditions. In Soil 2, immobilized laccase removed more 2,4-DCP (about 95%, regardless of moisture conditions) than free enzyme (55, 75, and 90% at 30, 55, and 100% of maximum water-holding capacity, respectively). Binding of 2,4-DCP in the humin fraction was nearly the same for free and immobilized laccase. More 2,4-DCP, however, was bound to humic and fulvic acids in the presence of immobilized laccase than in the presence of free laccase. In general, immobilized laccase performed better than free laccase. However, for practical applications, the higher activity of immobilized laccase is offset by a 23% loss in enzyme activity during immobilization, which approximates the 30% increase in free laccase needed to achieve the same level of remediation. Furthermore, immobilized laccase is more costly than free T. villosa laccase.     

Assessment of groundwater contamination using geographic information systems

In this study two sites were selected in order to investigate groundwater contamination and spatial relationships among groundwater quality, topography, geology, landuse and pollution sources. One site is the Asan area, an agricultural district where pollution sources are scattered and which is mainly underlain by granite of Cretaceous age. The other site is the Gurogu area of Seoul city, an industrial district where an industrial complex and residential areas are located and which is mainly underlain by gneiss of Precambrian age. Groundwater samples collected from these districts were analysed for chemical constituents. An attribute value files of chemical constituents of groundwater and the spatial data layers were constructed and pollution properties were investigated to establish out spatial relationships between the groundwater constituents and pollution sources using geographic information systems (GIS).Relatively high contents of Si and HCO₃ ^– in the groundwater from the Asan area reflect the effect of water–rock interaction whereas high contents of Cl^–, NO₃ ^– and Ca²⁺ in the groundwater from the Gurogu area are due to the pollution of various sources. The significant seasonal variation of SiO₂, HCO₂ ^– and Ca²⁺ contents, and that of Ca²⁺ content were observed in the Asan and the Gurogu areas, respectively. Seasonal variation of pollutants such as Cl^–, NO₃ ^– and SO₄ ^2– was not observed in either area. Pollution over the critical level of the Korean drinking water standard has been investigated from 15 sampling sites out of 40 in the Asan area, and 33 sampling sites out of 51 in the Gurogu area. Pollution by NO₃ ^–, Cl^–, Fe²⁺, Mn²⁺, SO₄ ^2– and Zn²⁺ in the groundwater from the industrial district (Gurogu area) and that of NO₃ , SO₄ ^2– and Zn²⁺ in the groundwater from the agricultural district (Asan area) were observed. The principal pollutant in both areas is NO₃ ^–. Deep groundwater from the Asan area is not yet contaminated with NO₃ ^– except for one site, but most of the shallow groundwater site occurring near the potential point sources is seriously contaminated. From the result of buffering analysis, it seems clear that factories and stock farms are the principal pollution sources in the Asan area. The groundwater from the Gurogu area has already been seriously polluted considering the fact of NO₃ ^– contamination of deep groundwater. Chlorine pollution of shallow groundwater in the Gurogu area was also observed. Spatial relationship between pollution level and its source was clarified in this study by using GIS, which will be applicable to the effective management of groundwater quality.     

Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

Removal of insoluble chloride from bottom ash for recycling

In order to recycle bottom ash and use it as raw material for cement production, the removal of insoluble chloride was investigated by testing various washing techniques. The present work is also focused on investigating the properties of insoluble chlorides and determining the conditions for dissolving these compounds in order to reduce the chlorine content to the required level, i.e., less than 0.1 wt%. Within this framework, the effect of washing with water and CO2 bubbling was investigated, because the main insoluble chloride found in bottom ash, i.e., Friedel's salt, can be dissolved by CO2. Then, in order to better understand the removal of Cl, Friedel's salt was artificially synthesized by hydration and then the effect of CO2 bubbling was investigated. If all chlorides in the ash are converted into Friedel's salt by hydration, all chlorides can then be dissolved by CO2 bubbling. In addition, the effect of pH on removing the remaining insoluble chlorides was investigated by washing the ash with sulfuric acid solution. It was found that the most effective technique to reduce the Cl content to less than 1000 ppm was washing with sulfuric acid solution, while keeping the pH value at less than 4. By using this method, Friedel's salt and other insoluble chlorides were dissolved.     

Dynamics of nitrogen,phosphorus, algal biomass,and suspended solids in an artificial lentic ecosystem and significant implications of regional hydrology on trophic status

Chemical and biological parameters were analyzed to examine how regional hydrological fluctuations influence water quality of a artificial lentic ecosystem over a two-year period The intensity of seasonal monsoon rain accounted for most of annual inflow and discharge and influenced flow pathway (interflow vs. overflow), resulting in a modification of chemical and biological conditions. Sharp contrasting interannual hydrology of intense vs. weak monsoon occurred during the study. The intense monsoon disrupted thermal stratification and resulted in ionic dilution, high TP and high inorganic solids (NVSS) in the headwater reach. The variation of NVSS accounted 75% of TP variation (slope = 4.14, p < 0.01, n = 48). Regression analysis of residual chlorophyll-a (Chl) versus flushing rate indicated that short hydraulic retention time and high mineral turbidity affected algal growth in the headwater reach during summer monsoon. In contrast, severe drought during weak monsoon produced strong thermal stratification, low inorganic solids, high total dissolved solids (TDS), and low TP in the entire system. In addition, Chl concentrations were controlled by phosphorus. Based on the physical, chemical and biological parameters, riverine conditions, dominated during the intense monsoon, but lacustrine conditions were evident during the weak monsoon. The interannual dynamics suggest that monsoon seasonality is considered the main forcing factor regulating overall functions and processes of the waterbody and this characteristic has an important implication to eutrophication of the system.     

Comparison of some homogeneity tests in analysis of over-dispersed binomial data

This paper compares the procedures based on the extended quasi-likelihood, pseudo-likelihood and quasi-likelihood approaches for testing homogeneity of several proportions for over-dispersed binomial data. The type I error of the Wald tests using the model-based and robust variance estimates, the score test, and the extended quasi-likelihood ratio test (deviance reduction test) were examined by simulation. The extended quasi-likelihood method performs less well when mean responses are close to 1 or 0. The model-based Wald test based on the quasi-likelihood performs the best in maintaining the nominal level. The score test performs less well when the intracluster correlations are large or heterogeneous. In summary: (i) both the quasilikelihood and pseudo-likelihood methods appear to be acceptable but care must be taken when overfitting a variance function with small sample sizes; (ii) the extended quasi-likelihood approach is the least favourable method because its nominal level is much too high; and (iii) the robust variance estimator performs poorly, particularly when the sample size is small.     

Effects of in-situ ozonation on indigenous microorganisms in diesel contaminated soil: survival and regrowth

Soil column experiments were conducted to investigate the effects of chemical oxidation on the survival of indigenous microbes (i.e., heterotrophic microbes, phenanthrene-degrading microbes, and alkane-degrading microbes) for field soil contaminated with diesel fuel. Rapid decreases of total petroleum hydrocarbons (TPH) and aromatics of diesel fuel were observed within the first 60 min of ozone injection; after 60 min, TPH and aromatics decreased asymptotically with ozonation time. The three types of indigenous microbes treated were very sensitive to ozone in the soil column experiment, hence the microbial population decreased exponentially with ozonation time. The numbers of heterotrophic, alkane-degrading, and phenanthrene-degrading bacteria were reduced from 10(8) to 10(4), 10(7) to 10(3), and 10(6) CFU g soil(-1) to below detection limit after 900 min of ozonation, respectively. Except for the soil sample ozonated for 900 min, incubation of ozone-treated soil samples that were not limited by oxygen diffusion showed further removal of TPH. The soil samples that were ozonated for 180 min exhibited the lowest concentration of TPH and the highest regrowth rate of the heterotrophic and alkane-degrading populations after the 9 weeks of incubation.     

Use of autotrophic sulfur-oxidizers to remove nitrate from bank filtrate in a permeable reactive barrier system

This study was conducted to evaluate the potential applicability of an in situ biological reactive barrier system to treat nitrate-contaminated bank filtrate. The reactive barrier consisted of sulfur granules as an electron donor and autotrophic sulfur-oxidizing bacteria as a biological component. Limestone was also used to provide alkalinity. The results showed that the autotrophic sulfur oxidizers were successfully colonized on the surfaces of the sulfur particles and removed nitrate from synthetic bank filtrate. The sulfur-oxidizing activity continuously increased with time and then was maintained or slightly decreased after five days of column operation. Maximum nitrate removal efficiency and sulfur oxidation rate were observed at near neutral pH. Over 90% of the initial nitrate dissolved in synthetic bank filtrate was removed in all columns tested with some nitrite accumulation. However, nitrite accumulation was observed mainly during the initial operation period, and the concentration markedly diminished with time. The nitrite concentration in effluent was less than 2 mg-N/l after 12 days of column operation. When influent nitrate concentrations were 30, 40, and 60 mg-N/l and sulfur content in column was 75%, half-order autotrophic denitrification reaction rate constants were 31.73 x 10(-3), 33.3 x 10(-3), and 36.4 x 10(-3) mg(1/2)/l(1/2)min, respectively. Our data on the nitrate distribution profile along the column suggest that an appropriate wall thickness of a reactive barrier for autotrophic denitrification may be 30 cm when influent nitrate concentration is less than 60 mg-N/l.