Transport of hydrocarbons from an emplaced fuel source experiment in the vadose zone at Airbase Vaerløse, Denmark.

An emplaced hydrocarbon source field experiment was conducted in the relatively homogeneous sandy geology of the vadose zone at Airbase Vaerløse, Denmark. The source (10.2 l of NAPL) consisted of 13 hydrocarbons (n-, iso- and cyclo-alkanes and aromates) and CFC-113 as a tracer. Monitoring in the 107 soil gas probes placed out to 20 m from the centre of the source showed spreading of all the compounds in the pore air and all compounds were measured in the pore air within a few hours after source emplacement. Seven of the fourteen compounds were depleted from the source within the 1 year of monitoring. The organic vapours in the pore air migrated radially from the source. The CFC-113 concentrations seemed to be higher in the deeper soil gas probes compared with the hydrocarbons, indicating a high loss of CFC-113 to the atmosphere and the lack of degradation of CFC-113. For the first days after source emplacement, the transport of CFC-113, hexane and toluene was successfully simulated using a radial gas-phase diffusion model for the unsaturated zone. Groundwater pollution caused by the vadose zone hydrocarbon vapours was only detected in the upper 30 cm of the underlying groundwater and only during the first 3 months of the experiment. Only the most water-soluble compounds were detected in the groundwater and concentrations decreased sharply with depth (approximately one order of magnitude within 10 cm depth) to non-detect at 30 cm depth. The groundwater table varied more than 1 m within the measurement period. However that did not influence the direction of the groundwater flow. Approximately 7 months after source emplacement the groundwater table rose more than 1 m within 1 month. That did not cause additional pollution of the groundwater.

Product formation from thiophene by a mixed bacterial culture. Influence of benzene as growth substrate.

The influence of benzene as a growth substrate on the cometabolic conversion of thiophene was investigated in batch systems with microorganisms originating from an creosote contaminated site. Benzene was shown to stimulate the conversion of thiophene with a first-order rate, during the initial phase of transformation. The microorganisms were able to transform thiophene in the absence of benzene at a zero-order rate. Thiophene was converted to five oxidation products, regardless of the presence of benzene. Benzene had no influence on the distribution of these oxidation products. The main oxidation product, a thiophene sulphoxide dimer, represented 78+/-12% of the transformed thiophene, while the second most important product, also a thiophene sulphoxide dimer, represented 20+/-2% of the converted thiophene.

Population changes in a biofilm reactor for phosphorus removal as evidenced by the use of FISH.

Induction of denitrification was investigated for a lab-scale phosphate removing biofilm reactor where oxygen was replaced with nitrate as the electron acceptor. Acetate was used as the carbon source. The original biofilm (acclimatised with oxygen) was taken from a well-established large-scale reactor. During the first run, a decrease in the denitrifying bio-P activity was observed after 1 month following a change in the anaerobic phase length. This was initially interpreted as a shift in the microbial population caused by the changed operation. In the second run, biomass samples were regularly collected and analysed by fluorescent in situ hybridisation (FISH) and confocal laser scanning microscopy (CLSM). Concurrently, samples were taken from the original reactor with oxygen as electron acceptor in order to investigate natural microbial fluctuations. A similar decrease in the activity as in the first run was seen after one month, although the phase lengths had not been varied. Hence, the decrease after 1 month in the first and second run should be seen as a start-up phenomenon. FISH could detect a noticeable shift in the microbial population mainly within the first 2 weeks of operation. Almost all bacteria belonging to the alpha subclass disappeared and characteristic clusters of the beta and gamma subclasses were lost. Small clusters of gram-positive bacteria with a high DNA G + C content (GPBHGC) were gradually replaced by filamentous GPBHGC. Most of the bacteria in the denitrifying, phosphate removing biofilm belonged to the beta subclass of Proteobacteria. The applied set of gene probes had been selected based on existing literature on biological phosphate removing organisms and included a recently published probe for a Rhodocyclus-like clone. However, none of the specific probes hybridised to the dominant bacterial groups in the reactors investigated. No noticeable changes were detected in the aerobic bench-scale reactor during this period, indicating that the observed changes in the lab-scale reactor were caused by the changed environment.

Attenuation of methane and volatile organic compounds in landfill soil covers.

The potential for natural attenuation of volatile organic compounds (VOCs) in landfill covers was investigated in soil microcosms incubated with methane and air, simulating the gas composition in landfill soil covers. Soil was sampled at Skellingsted Landfill at a location emitting methane. In total, 26 VOCs were investigated, including chlorinated methanes, ethanes, ethenes, fluorinated hydrocarbons, and aromatic hydrocarbons. The soil showed a high capacity for methane oxidation resulting in very high oxidation rates of between 24 and 112 microg CH4 g(-1) h(-1). All lower chlorinated compounds were shown degradable, and the degradation occurred in parallel with the oxidation of methane. In general, the degradation rates of the chlorinated aliphatics were inversely related to the chlorine to carbon ratios. For example, in batch experiments with chlorinated ethylenes, the highest rates were observed for vinyl chloride (VC) and lowest rates for trichloroethylene (TCE), while tetrachloroethylene (PCE) was not degraded. Maximal oxidation rates for the halogenated aliphatic compounds varied between 0.03 and 1.7 microg g(-1) h(-1). Fully halogenated hydrocarbons (PCE, tetrachloromethane [TeCM], chlorofluorocarbon [CFC]-11, CFC-12, and CFC-113) were not degraded in the presence of methane and oxygen. Aromatic hydrocarbons were rapidly degraded giving high maximal oxidation rates (0.17-1.4 microg g(-1) h(-1)). The capacity for methane oxidation was related to the depth of oxygen penetration. The methane oxidizers were very active in oxidizing methane and the selected trace components down to a depth of 50 cm below the surface. Maximal oxidation activity occurred in a zone between 15 and 20 cm below the surface, as this depth allowed sufficient supply of both methane and oxygen. Mass balance calculations using the maximal oxidation rates obtained demonstrated that landfill soil covers have a significant potential for not only methane oxidation but also cometabolic degradation of selected volatile organics, thereby reducing emissions to the atmosphere.

Method for determination of methane potentials of solid organic waste.

A laboratory procedure is described for measuring methane potentials of organic solid waste. Triplicate reactors with 10 grams of volatile solids were incubated at 55 degrees C with 400 ml of inoculum from a thermophilic biogas plant and the methane production was followed over a 50-day period by regular measurements of methane on a gas chromatograph. The procedure involves blanks as well as cellulose controls. Methane potentials have been measured for source-separated organic household waste and for individual waste materials. The procedure has been evaluated regarding practicality, workload, detection limit, repeatability and reproducibility as well as quality control procedures. For the source-separated organic household waste a methane potential of 495 ml CH4/g VS was found. For fat and oil a lag-phase of several days was seen. The protein sample was clearly inhibited and the maximal methane potential was therefore not achieved. For paper bags, starch and glucose 63, 84 and 94% of the theoretical methane potential was achieved respectively. A detection limit of 72.5 ml CH4/g VS was calculated from the results. This is acceptable, since the methane potential of the tested waste materials was in the range of 200-500 ml CH4/g VS. The determination of methane potentials is a biological method subject to relatively large variation due to the use of non-standardized inoculum and waste heterogeneity. Therefore, procedures for addressing repeatability and reproducibility are suggested.

Persistence of methyl tertiary butyl ether (MTBE) against metabolism by Danish vegetation.

BACKGROUND: Methyl tertiary butyl ether (MTBE) is the second most highly produced industrial chemical in the US and a frequent groundwater pollutant. At the same time, MTBE is quite persistent to biotic and abiotic decomposition. The goal of this study was to find plant species that could degrade MTBE and might be used in phytoremediation. METHODS: Excised roots and leaves (0.3 g) from more than 24 Danish plant species out of 15 families were kept in glass vessels with 25 ml spiked aqueous solution for 2 to 4 days. MTBE concentrations were 1 to 5 mg/L. Samples were taken directly from the solution with a needle and injected to a purge and trap unit. MTBE and the main metabolite, TBA, were measured by GC/FID. RESULTS AND DISCUSSION: Solutions with roots of poplar (Populus robusta) and a willow hybrid (Salix viminalis x schwerinii) produced TBA in trace amounts, probably stemming from bacteria. Significant MTBE reduction (> 10%) was not observed in any of the tests. Leaves from none of the species (trees, grasses and herbs) reduced the concentration of MTBE in the solution and no TBA, nor any other known metabolite of MTBE, was detected. CONCLUSION: It was not possible to find plants capable of efficiently degrading MTBE. This gives rise to the conclusion that plants probably cannot degrade MTBE at all, or only very slowly. RECOMMENDATIONS AND OUTLOOK: For phytoremediation projects, this has, as consequence, that the volatilization by plants (except with genetically engineered plants) is the only relevant removal process for MTBE. For risk assessment of MTBE, degradation by the plant empire is not a relevant sink process.

Uptake of tributyltin into willow trees.

BACKGROUND: Organotins have been used world-wide as antifoulants in ship paints. Repeatedly, severe effects on aquatic species have resulted. The use of organotins for this purpose was ruled out, and dumping of contaminated harbor sludge into the sea was prohibited. Land-based dumping is seen as an alternative. OBJECTIVE: This study investigates sorption, uptake and translocation of tributyltin (TBT) to willow trees in order to evaluate phytoremediation as treatment option. The study considers the influence of pH on the plant uptake of organotins. EXPERIMENTAL SET-UP: Chemicals investigated were the weak base tributyltin chloride (TBTCl) and the neutral tributyltin hydride (TBTH). Organotins were extracted from solution and plant material with toluene, and analyzed as tin by AAS with graphite oven. The pH in solution varied from pH 4 to pH 7. The sorption to living and dead roots, stems and leaves was measured in shaking experiments. The uptake into intact trees was measured at nominal levels of 1 and 10 mg TBT/l for TBTH and TBTCl at low and high pH. RESULTS: The sorption to roots and leaves dropped for dead tissue, but did not vary much with pH. The sorption to stems increased for dead stems and with pH. The solubility of TBTCl in water was below 10 mg/l and lowest at pH 4. Concentrations of TBTCl and TBTH in solutions with trees dropped rapidly to low values. Highest TBT contents in trees were found in roots and lower stems. The concentrations followed the concentrations in solution. The pH had only a small effect on the plant uptake of TBTCl, and no effect on the uptake of TBTH. No effective translocation to higher stems or leaves was found. DISCUSSION: An ion trap mechanism that accumulates the weak base TBTCl in the xylem sap of plants and leads to upward translocation could not be detected. Neither TBTCl at low or high pH, nor the neutral lipophilic chemical TBTH, were translocated effectively to leaves. The TBT+ cation sorbed strongly to plant tissue. The exact mechanism for the strong sorption of the cation is unknown, but similar effects have been observed for algae, liposomes and isolated biomembranes. CONCLUSIONS: Both the uptake of the neutral TBTH and the uptake of the neutral molecule form of TBTCl into willows was as is to be expected from theory. The cation TBT+ showed an unexpected behavior which has been observed before. No ion trap occurs, and the phytoextraction of TBT is not feasible. OUTLOOK: Planting trees, or other appropriate vegetation, could have a beneficial remediation effect by aeration of the TBT-contaminated soil or sludge. In a follow-up paper, the toxicity of TBT to willow trees will be described.

Particles in swimming pool filters--does pH determine the DBP formation?

The formation was investigated for different groups of disinfection byproducts (DBPs) during chlorination of filter particles from swimming pools at different pH-values and the toxicity was estimated. Specifically, the formation of the DBP group trihalomethanes (THMs), which is regulated in many countries, and the non-regulated haloacetic acids (HAAs) and haloacetonitriles (HANs) were investigated at 6.0≤pH≤8.0, under controlled chlorination conditions. The investigated particles were collected from a hot tub with a drum micro filter. In two series of experiments with either constant initial active or initial free chlorine concentrations the particles were chlorinated at different pH-values in the relevant range for swimming pools. THM and HAA formations were reduced by decreasing pH while HAN formation increased with decreasing pH. Based on the organic content the relative DBP formation from the particles was higher than previously reported for body fluid analogue and filling water. The genotoxicity and cytotoxicity estimated from formation of DBPs from the treated particle suspension increased with decreasing pH. Among the quantified DBP groups the HANs were responsible for the majority of the toxicity from the measured DBPs.

Effect of pH on the formation of disinfection byproducts in swimming pool water--is less THM better?

This study investigated the formation and predicted toxicity of different groups of disinfection byproducts (DBPs) from human exudates in relation to chlorination of pool water at different pH values. Specifically, the formation of the DBP groups trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs) and trichloramine (NCl(3)), resulting from the chlorination of body fluid analog, were investigated at 6.0 ≤ pH ≤ 8.0. Either the initial concentration of active chorine or free chlorine was kept constant in the tested pH range. THM formation was reduced by decreasing pH but HAN, and NCl(3) formation increased at decreasing pH whereas the formation of HAAs remained constant. Under our experimental conditions, the formation of NCl(3) (suspected asthma inducing compound) at pH = 6.0 was an order of magnitude higher than at pH = 7.5. Furthermore, the effect of the presence of bromide on DBP formation was investigated and found to follow the same pH dependency as without bromide present, with the overall DBP formation increasing, except for HAAs. Estimation of genotoxicity and cytotoxicity of the chlorinated human exudates showed that among the quantified DBP groups, HAN formation were responsible for the majority of the toxicity from the measured DBPs in both absence and presence of bromide.

Attenuation of fluorocarbons released from foam insulation in landfills.

Chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) have been used as blowing agents (BAs) for foam insulation in home appliances and building materials, which after the end of their useful life are disposed of in landfills. The objective of this project was to evaluate the potential for degradation of BAs in landfills, and to develop a landfill model, which could simulate the fate of BAs in landfills. The investigation was performed by use of anaerobic microcosm studies using different types of organic waste and anaerobic digested sludge as inoculum. The BAs studied were CFC-11, CFC-12, HCFC-141b, HFC-134a, and HFC-245fa. Experiments considering the fate of some of the expected degradations products of CFC-11 and CFC-12 were included like HCFC-21, HCFC-22, HCFC-31, HCFC-32, and HFC-41. Degradation of all studied CFCs and HCFCs was observed regardless the type of waste used. In general, the degradation followed first-order kinetics. CFC-11 was rapidly degraded from 590 microg L(-1) to less than 5 microg L(-1) within 15-20 days. The degradation pattern indicated a sequential production of HCFC-21, HCFC-31, and HFC-41. However, the production of degradation products did not correlate with a stoichiometric removal of CFC-11 indicating that other degradation products were produced. HCFC-21 and HCFC-31 were further degraded whereas no further degradation of HFC-41 was observed. The degradation rate coefficient was directly correlated with the number of chlorine atoms attached to the carbon. The highest degradation rate coefficient was obtained for CFC-11, whereas lower rates were seen for HCFC-21 and HCFC-31. Equivalent results were obtained for CFC-12. HCFC-141b was also degraded with rates comparable to HCFC-21 and CFC-12. Anaerobic degradation of the studied HFCs was not observed in any of the experiments within a run time of up to 200 days. The obtained degradation rate coefficients were used as input for an extended version of an existing landfill fate model incorporating a time dependent BA release from co-disposed foam insulation waste. Predictions with the model indicate that the emission of foam released BAs may be strongly attenuated by microbial degradation reactions. Sensitivity analysis suggests that there is a need for determination of degradation rates under more field realistic scenarios.

Availability and quality of solid waste and wastewater in Southern Thailand and its potential use as fertiliser.

Recycling nutrients to agriculture with waste in Southern Thailand has been assessed in three model-areas: Kuan Lang, Prik and Phattalung. Samples of biodegradable solid waste and gray wastewater were collected and characteris ed physically and chemically. At present nutrients in the biodegradable solid waste and wastewater are lost, but especially kitchen waste and grey household wastewater constitute a large fertiliser potential. The average daily per capita generation rate of household kitchen waste is 228 g wet matter, 0.65 g N, 0.16 g P 0.34 g K, 0.05 g S, 0.39 g Ca, 0.06 g Mg, 6.9 mg Zn, 0.29 mg Cu, 0.05 mg Ni, 0.02 mg Pb, 0.09 mg Cd and 0.006 mg Hg. The average daily per capita generation rate of grey household wastewater is 102 L, 2.4 g N, 2.4 g P, 4.2 g K, 2.0 g S, 2.2 g Ca, 0.82 g Mg, 42 mg Zn, 0.91 mg Cu, 1.6 mg Ni, 0.46 mg Pb, 0.20 mg Cd and < 0.06 mg Hg. The waste products generally contain higher amounts of K, Ca, Mg, Zn, Cu and Pb (relative to phosphorous) than conventional chemical fertiliser, while N, S, Ni, Hg and Cd is at the same level.

Technical, economic and environmental feasibility of recycling nutrients in waste in Southern Thailand.

Technical, economic and environmental criteria were used to evaluate the feasibility of recycling plant nutrients in kitchen waste, human excreta and sullage from households in Phattalung (urban), Kuan Lang (peri urban) and Prik (rural) in Southern Thailand. The difference in situation and context of the three areas called for individual solutions, and for each area three sanitation systems were evaluated. However, in all three areas recycling human excreta and kitchen waste via composting latrines was found to be more environmental feasible than human excreta managed in septic tanks or sub surface trickle irrigation and kitchen waste disposed of at landfill sites or treated at composting plants. Sullage should in Kuan Lang and Prik be used directly on garden crops, but in Phattalung be treated in waste stabilisation ponds before discharge, to be environmentally feasible. The economic feasibility results varied among the three areas and among the involved stakeholders: farmers and Kuan Lang administration benefited from recycling waste, at the expense of other private users, Phattalung municipality and Prik municipality. The main cause of these conflicting interests was lack of cost recovery and public participation, which should therefore serve as the fundament of any future environmental and economic feasible sanitation system.