Modeling in-situ uranium(VI) bioreduction by sulfate-reducing bacteria

We present a travel-time based reactive transport model to simulate an in-situ bioremediation experiment for demonstrating enhanced bioreduction of uranium(VI). The model considers aquatic equilibrium chemistry of uranium and other groundwater constituents, uranium sorption and precipitation, and the microbial reduction of nitrate, sulfate and U(VI). Kinetic sorption/desorption of U(VI) is characterized by mass transfer between stagnant micro-pores and mobile flow zones. The model describes the succession of terminal electron accepting processes and the growth and decay of sulfate-reducing bacteria, concurrent with the enzymatic reduction of aqueous U(VI) species. The effective U(VI) reduction rate and sorption site distributions are determined by fitting the model simulation to an in-situ experiment at Oak Ridge, TN. Results show that (1) the presence of nitrate inhibits U(VI) reduction at the site; (2) the fitted effective rate of in-situ U(VI) reduction is much smaller than the values reported for laboratory experiments; (3) U(VI) sorption/desorption, which affects U(VI) bioavailability at the site, is strongly controlled by kinetics; (4) both pH and bicarbonate concentration significantly influence the sorption/desorption of U(VI), which therefore cannot be characterized by empirical isotherms; and (5) calcium-uranyl-carbonate complexes significantly influence the model performance of U(VI) reduction.     

Occurrence of alkylphenolic substances in a Great Lakes coastal marsh, Cootes Paradise, ON, Canada

Occurrence and fate of alkylphenols (APs), known endocrine disruptors, were investigated in a Great Lakes coastal wetland, Cootes Paradise, ON. The wetland, which receives discharges from a Wastewater Treatment Plant (WTP) and several Combined Sewer Overflows (CSOs), is an important spawning ground for fish and crucial habitat for other fauna. Elevated concentrations of nonylphenol ethoxylates (NPEs) and their degradation product nonylphenol (NP) were found in water and sediment samples near the sources. Since transfer of APs through the food chain is of concern, we compared their concentrations in invertebrates from clean and contaminated sites. The results reveal transfer of alkylphenolics from sediments to biota and their accumulation in the invertebrate tissue, particularly the highly hydrophobic 4-NP, whose concentrations ranged from 1.9 to 6.3 microg g(-1). To our knowledge, this is the first study to evaluate AP concentrations in tissue of benthic invertebrates under real environmental conditions.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

Transport of Sr2+ and SrEDTA2- in partially-saturated and heterogeneous sediments

Strontium-90 has migrated deep into the unsaturated subsurface beneath leaking storage tanks in the Waste Management Areas (WMA) at the U.S. Department of Energy's (DOE) Hanford Reservation. Faster than expected transport of contaminants in the vadose zone is typically attributed to either physical hydrologic processes such as development of preferential flow pathways, or to geochemical processes such as the formation of stable, anionic complexes with organic chelates, e.g., ethylenediaminetetraacetic acid (EDTA). The goal of this paper is to determine whether hydrological processes in the Hanford sediments can influence the geochemistry of the system and hence control transport of Sr(2+) and SrEDTA(2-). The study used batch isotherms, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core. Isotherms and repacked column experiments suggested that the SrEDTA(2-) complex was unstable in the presence of Hanford sediments, resulting in dissociation and transport of Sr(2+) as a divalent cation. A decrease in sorption with increasing solid:solution ratio for Sr(2+) and SrEDTA(2-) suggested mineral dissolution resulted in competition for sorption sites and the formation of stable aqueous complexes. This was confirmed by detection of MgEDTA(2-), MnEDTA(2-), PbEDTA(2-), and unidentified Sr and Ca complexes. Displacement of Sr(2+) through a partially-saturated undisturbed core resulted in less retardation and more irreversible sorption than was observed in the saturated repacked columns, and model results suggested a significant reservoir (49%) of immobile water was present during transport through the heterogeneous layered sediments. The undisturbed core was subsequently disassembled along distinct bedding planes and subjected to sequential extractions. Strontium was unequally distributed between carbonates (49%), ion exchange sites (37%), and the oxide (14%) fraction. An inverse relationship between mass wetness and Sr suggested that sandy sediments of low water content constituted the immobile flow regime. Our results suggested that the sequestration of Sr(2+) in partially-saturated, heterogeneous sediments was most likely due to the formation of immobile water in drier regions having low hydraulic conductivities.     

Sonochemical substrate selectivity and reaction pathway of systematically substituted azo compounds

The sonochemical degradation of the systematically substituted azo compound 2,7-dihydroxy-1-phenylazonaphthaline-3,6-disulfonic acid was investigated using a frequency of 850 kHz and an acoustic input power of 61 W. All derivatives were degraded completely within 6h by the ultrasonic treatment. Trifluoromethyl substituted azo compounds exhibited 2-3-fold higher degradation rates in comparison to the reference hydrogen substituted azo compound (k=0.54 h(-1)). In contrast to enzymatic processes (azoreductase or laccase), the ultrasonic treatment for these ortho-, meta-, and para-substituted azo compound showed 1.5-50-fold higher degradation rates. Additionally the ultrasound treatment was characterized by shorter reaction times. As a result of the detection and identification of specific intermediates using LC-MS a reaction pathway of the sonochemical degradation of the analysed azo compound is proposed indicating the formation of cyclohexadienone and naphthalene quinone derivatives.     

Bacteria transport and deposition under unsaturated conditions: the role of the matrix grain size and the bacteria surface protein

Unsaturated (80% water saturated) packed column experiments were conducted to investigate the influence of grain size distribution and bacteria surface macromolecules on bacteria (Rhodococcus rhodochrous) transport and deposition mechanisms. Three sizes of silica sands were used in these transport experiments, and their median grain sizes were 607, 567, and 330 microm. The amount of retained bacteria increased with decreasing sand size, and most of the deposited bacteria were found adjacent to the column inlet. The deposition profiles were not consistent with predictions based on classical filtration theory. The experimental data could be accurately characterized using a mathematical model that accounted for first-order attachment, detachment, and time and depth-dependent straining processes. Visual observations of the bacteria deposition as well as mathematical modelling indicated that straining was the dominant mechanism of deposition in these sands (78-99.6% of the deposited bacteria), which may have been enhanced due to the tendency of this bacterium to form aggregates. An additional unsaturated experiment was conducted to better deduce the role of bacteria surface macromolecules on attachment and straining processes. In this case, the bacteria surface was treated using a proteolitic enzyme. This technique was assessed by examining the Fourier-transform infrared spectrum and hydrophobicity of untreated and enzyme treated cells. Both of these analytical procedures demonstrated that this enzymatic treatment removed the surface proteins and/or associated macromolecules. Transport and modelling studies conducted with the enzyme treated bacteria, revealed a decrease in attachment, but that straining was not significantly affected by this treatment.     

Estimates of ambient background concentrations of trace metals in soils for risk assessment

Site-specific or soil type-specific ambient background concentrations (ABCs) of trace metals in soils are needed for risk assessment. We investigated three different methods for estimating ABCs in soils using a dataset of 5691 soil samples from England and Wales. The concentrations of Co, Cr and Ni were strongly associated with Al and Fe, and multiple regressions explained 62-85% of their variation, and Al and Fe can therefore be used to predict ABCs for these metals. Soil texture had a major influence on the concentrations of Cd, Co, Cr, Cu, Ni and Zn, and the medians were 3-5 fold higher in clayey than in sandy soils. This was used to predict texture-specific ABCs. Lead concentration was higher in acidic peaty soils than in other soils. A probability graph method was used to estimate ABC for Pb in a population of relatively uncontaminated soils. Potential applications of ABCs are discussed.     

Dynamic equilibrium of radiocesium with stable cesium within the soil-mushroom system in Turkish pine forest

Mushrooms and soils collected from pine forests in Izmir, Turkey were measured for radiocesium and stable Cs in 2002. The ranges of (137)Cs and stable Cs concentrations in mushrooms were 9.84+/-1.67 to 401+/-3.85Bqkg(-1) dry weight and 0.040+/-0.004 to 11.3+/-1.09mgkg(-1) dry weight, respectively. The concentrations of (137)Cs and stable Cs in soils were 0.29+/-0.18 to 161+/-1.12Bqkg(-1) dry weight and 0.14+/-0.004 to 1.44+/-0.045mgkg(-1) dry weight, respectively. Even though different species were included, the concentration ratios of (137)Cs to stable Cs were fairly constant for samples collected at the same forest site, and were in the same order of magnitude as the (137)Cs to stable Cs ratios for the organic soil layers. The soil-to-mushroom transfer factors of (137)Cs and stable Cs were in the range of 0.19-3.15 and 0.17-12.3, respectively. The transfer factors of (137)Cs were significantly correlated to those of stable Cs.     

Percentile estimation using variable censored data

Much progress has been made in recent years to address the estimation of summary statistics, using data that are subject to censoring of results that fall below the limit of detection (LOD) for the measuring instrument. Truncated data methods (e.g., Tobit regression) and multiple-imputation are two approaches for analyzing data results that are below the LOD. To apply these methods requires an assumption about the underlying distribution of the data. Because the log-normal distribution has been shown to fit many data sets obtained from environmental measurements, the common practice is to assume that measurements of environmental factors can be described by log-normal distributions. This article describes methods for obtaining estimates of percentiles and their associated confidence intervals when the results are log-normal and a fraction of the results are below the LOD. We present limited simulations to demonstrate the bias of the proposed estimates and the coverage probability of their associated confidence intervals. Estimation methods are used to generate summary statistics for 2,3,7,8-tetrachloro dibenzo-p-dioxin (2,3,7,8-TCDD) using data from a 2001 background exposure study in which PCDDs/PCDFs/cPCBs in human blood serum were measured in a Louisiana population. Because the congener measurements used in this study were subject to variable LODs, we also present simulation results to demonstrate the effect of variable LODs on the multiple-imputation process.     

Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.