Model approach for estimating potato pesticide bioconcentration factor

We presented a model that estimates the bioconcentration factor (BCF) of pesticides in potatoes supposing that the pesticide in the soil solution is absorbed by the potato by passive diffusion, following Fick's second law. The pesticides in the model are nonionic organic substances, traditionally used in potato crops that degrade in the soil according to a first-order kinetic equation. This presents an expression that relates BCF with the pesticide elimination rate by the potato, with the pesticide accumulation rate within the potato, with the rate of growth of the potato and with the pesticide degradation rate in the soil. BCF was estimated supposing steady state equilibrium of the quotient between the pesticide concentration in the potato and the pesticide concentration in the soil solution. It is suggested that a negative correlation exists between the pesticide BCF and the soil sorption partition coefficient. The model was built based on the work of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108], in which an expression to calculate the diffusivity of persistent organic substances in potatoes is presented. The model consists in adding to the expression of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108] the hypothesis that the pesticide degrades in the soil. The value of BCF suggests which pesticides should be monitored in potatoes.     

Fungal bioremediation of the creosote-contaminated soil: influence of Pleurotus ostreatus and Irpex lacteus on polycyclic aromatic hydrocarbons removal and soil microbial community composition in the laboratory-scale study

The aim of this study was to determine the efficacy of selected basidiomycetes in the removing of polycyclic aromatic hydrocarbons (PAH) from the creosote-contaminated soil. Fungi Pleurotus ostreatus and Irpex lacteus were supplemented with creosote-contaminated (50-200 mg kg(-1) PAH) soil originating from a wood-preserving plant and incubated at 15 °C for 120 d. Either fungus degraded PAH with 4-6 aromatic rings more efficiently than the microbial community present initially in the soil. PAH removal was higher in P. ostreatus treatments (55-67%) than in I. lacteus treatments (27-36%) in general. P. ostreatus (respectively, I. lacteus) removed 86-96% (47-59%) of 2-rings PAH, 63-72% (33-45%) of 3-rings PAH, 32-49% (9-14%) of 4-rings PAH and 31-38% (11-13%) of 5-6-rings PAH. MIS (Microbial Identification System) Sherlock analysis of the bacterial community determined the presence of dominant Gram-negative bacteria (G-) Pseudomonas in the inoculated soil before the application of fungi. Complex soil microbial community was characterized by phospholipid fatty acids analysis followed by GC-MS/MS. Either fungus induced the decrease of bacterial biomass (G- bacteria in particular), but the soil microbial community was influenced by P. ostreatus in a different way than by I. lacteus. The bacterial community was stressed more by the presence of I. lacteus than P. ostreatus (as proved by the ratio of the fungal/bacterial markers and by the ratio of trans/cis mono-unsaturated fatty acids). Moreover, P. ostreatus stimulated the growth of Gram-positive bacteria (G+), especially actinobacteria and these results indicate the potential of the positive synergistic interaction of this fungus and actinobacteria in creosote biodegradation.     

Ecorisk evaluation and treatability potential of soils contaminated with petroleum hydrocarbon-based fuels

We used a series of toxicity tests to monitor oil degradation in the Kuwaiti oil lakes. Three soils from different locations with a history of hydrocarbon contamination were treated in bench-scale microcosms with controlled nutrient amendments, moisture content, and temperature that had promoted mineralization of total hydrocarbon and oil and grease in a preliminary study. Two hundred days of bioremediation treatment lowered hydrocarbon concentration to below 2 and 5 mg g(-1) for soils A and B, respectively, while in soil C hydrocarbon concentration remained at 12 mg g(-1). Although 85% of the total petroleum hydrocarbons (TPHs) in soil A were reduced 50d after treatment, results of the seed germination and Microtox tests suggested an initial increase in toxicity, indicating that toxic intermediary metabolites may have formed during biodegradation. Also, the significant decrease of TPHs and corresponding high toxicity levels were noted in soil B 200d after bioremediation. Clearly, toxicity values, and not just hydrocarbon concentration, are a key factor in assessing the effectiveness of bioremediation techniques. Field chemistry data showed a significant reduction in hydrocarbon levels after the biological treatment. We concluded that the toxicity assessment of the contaminated soil with a battery of toxicity bioassays could provide meaningful information regarding a characterization procedure in ecological risk assessment.     

Increased thyroid volume, prevalence of thyroid antibodies and impaired fasting glucose in young adults from organochlorine cocktail polluted area: outcome of transgenerational transmission?

In 137 females (F) and 94 males (M) aged 21-35 years from organochlorines (OCs) polluted area (POLL) increased thyroid volume (ThV), prevalence of antibodies to thyroperoxidase (TPOab), thyrotropin receptor (TRab) and of impaired fasting glucose (IFG) was found compared to 116 F and 107 M from background pollution area (BCGR). In F and M from POLL also strikingly increased level of PCBs, DDE and HCB was found. Such findings were compared to the generation of their parents aged 41-55 years consisting of 320F/213M from POLL and 406F/231M from BCGR. However, in spite of strikingly lower level of those OCs in young adults from POLL, they showed about the same prevalence of adverse health signs as the old generation. From such reason 44 young F and 40 young M with lowest PCBs level from POLL were selected to obtain nearly the same PCB level as found in all young F and M from BCGR. In such PCB adjusted groups the prevalence of TPOab, TRab, IFG and increased ThV was still significantly higher than that in all young subjects from BCGR. At the same time, also the level of DDE and HCB in such PCBs adjusted groups was considerably lower. It was concluded that such adverse effects in young adults from POLL possibly did not result from their actual OCs levels, but very likely from their exposure to high OCs levels of their mothers during their prenatal and perinatal life. Thus, the data may be compatible with present views on transgenerational transmission of endocrine disruptors action.     

Dioxins in adipose tissue of women in Southern Spain

Seventeen polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were quantified in adipose tissue samples of non-occupationally exposed women living in Southern Spain. Geometric mean levels of sum of congeners and WHO(PCDD/F)-TEQ(2005) were 410 and 17.9pgg(-1) fat, respectively. Among PCDDs, octachlorodibenzo-p-dioxin (OCDD) showed the highest concentration with a mean value of 265pgg(-1) fat, followed by 1,2,3,6,7,8-HxCDD (49.3pgg(-1) fat) and 1,2,3,4,6,7,8-HpCDD (45.2pgg(-1) fat). These three congeners were responsible for around 90% of the sum of all PCDD/F congeners in adipose tissue. The geometric mean 2,3,7,8-TCDD value was 1.87pgg(-1) fat. 2,3,4,7,8-PeCDF (8.43pgg(-1) fat) showed the highest concentration among the PCDFs, followed by 1,2,3,4,7,8-HxCDF (4.17pgg(-1) fat) and 1,2,3,6,7,8-HxCDF (3.28pgg(-1) fat), and these three congeners were responsible for 4% of the sum of all studied PCDD/F congeners in adipose tissue and 76% of the sum of ten PCDFs. 1,2,3,7,8,9-HxCDF was the only congener not quantified in any sample, while 1,2,3,4,7,8,9-HpCDF, 1,2,3,7,8-PeCDF, OCDF and 2,3,7,8-TCDF were found in 5, 16, 16 and 19 samples, respectively. All other congeners were quantifiable in all 20 samples. Congeners contributing most to the WHO(PCDD/F)-TEQ(2005) were 1,2,3,7,8-PeCDD (31.6%), 1,2,3,6,7,8-HxCDD (28.3%) and 2,3,4,7,8-PeCDF (14.6%). The body burden of log-transformed WHO(PCDD/F)-TEQ(2005) levels increased with age (B=0.02; 95% CI=0.01, 0.03; p=0.02). Although these adipose tissue PCDD/F levels are similar to previously published findings in Spain and other European countries, further research is needed to determine trends in the exposure of women to these chemical residues.     

Monitoring PCDD/Fs, PCBs and metals in the ambient air of an industrial area of Catalonia, Spain

In 2005 and 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and metals (As, Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sn, Tl and V) were measured in air samples collected in an industrial area of Sant Adrià del Besòs (Barcelona, Catalonia, Spain) where a municipal solid waste incinerator (MSWI) is placed, and in a background/control area. In general terms, concentrations of all environmental pollutants were higher at the industrial site. No significant seasonal/temporal variations were observed in any of the areas. No Pearson correlation was found between the PCDD/F concentrations and the environmental conditions of the two sampling periods considered. Principal component analyses (PCA) were performed to get information on the relationship among samples, pollutants, and emission sources. The results indicate that the MSWI of S. Adrià de Besòs is not a significant emission source of the above compounds for the area under its direct influence. Moreover, a notable difference in the PCDD/F congener profiles was found between ambient air and stack gas emissions, indicating that the current levels of PCDD/Fs are more related to other potential emissions sources rather than to those from the MSWI.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

Non-Fickian dispersion in a single fracture

Solute transport in fractured rocks is of major interest in many applications, from the petroleum industry to ground water management. This work focuses on the dispersion process in a transparent replica of a real single fracture. The fracture exhibits strong changes in heterogeneity, with the first half very heterogeneous and the second half fairly homogeneous. Three models have been used to interpret the tracer experiments: the classical advection-dispersion equation (ADE), the continuous time random walk (CTRW), and the stratified model. The main goals were to test these models and to study possible correlations between fitting parameters and heterogeneities. As expected, the solution derived from the ADE equation appears to be unable to model long-time tailing behavior. On the other hand, the results confirm the CTRW robustness and the coefficient beta seems well correlated to heterogeneities. Finally, the stratified model is also able to describe non-Fickian dispersion. The parameters defined by this model are correlated to the heterogeneities of the fracture.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.