Phosphorus characterization in sediments impacted by septic effluent at four sites in central Canada

Characterization of phosphorus (P) enriched solids was undertaken in the sediments below four mature septic system infiltration beds, where previous monitoring of phosphate (PO₄) concentrations in the groundwater had indicated that substantial retention of P was occurring in the vadose zone. At each site, zones of sediment P enrichment were identified by an acid extraction procedure. Acid extractable sediment P concentrations were found to be 2–5 times higher than background values, within narrow discrete zones generally 10–30 cm in thickness, located within one meter of the infiltration pipes. Back scattered electron images of the P enriched zones indicated that the P solids occurred as distinct authigenic grains (up to 300 μm diameter) and as grain coatings. Microprobe analyses indicated predominantly Fe–P in calcareous sediments (Cambridge and Langton) and Al–Fe–P in non-calcareous sediments (Muskoka and Harp Lake). Porewater analyses indicated that the zones of P accumulation were closely associated with zones of redox change characterized by the conversion of effluent NH₄⁺ to NO₃⁻. The data suggests that a substantial amount of the septic derived P is being attenuated by mineral precipitation reactions that occur rapidly after the effluent encounters subsurface sediments. Reductive dissolution of ferric (oxy)hydroxide minerals as a consequence of reducing environments near the infiltrations pipes, the release of Fe²⁺ in solution and subsequent conversion of Fe²⁺ to Fe³⁺ may promote the precipitation of ferric or ferrosoferric PO₄ minerals. In sediments with limited buffering capacity (calcite deficient), the decrease in pH resulting from effluent oxidation may cause Al (oxy)hydroxide dissolution and subsequent precipitation of Al–P rich phases. These precipitation reactions appear to have the capacity to immobilize a substantial amount of septic derived P (25–99% at these sites) for a considerable period of time.     

Modelling the geochemical fate and transport of wastewater-derived phosphorus in contrasting groundwater systems

A 1D reactive transport model (RTM) is used to obtain a mechanistic understanding of the fate of phosphorus (P) in the saturated zone of two contrasting aquifer systems. We use the field data from two oxic, electron donor-poor, wastewater-impacted, sandy Canadian aquifers, (Cambridge and Muskoka sites) as an example of a calcareous and non-calcareous groundwater system, respectively, to validate our reaction network. After approximately 10 years of wastewater infiltration, P is effectively attenuated within the first 10 m down-gradient of the source mainly through fast sorption onto calcite and Fe oxides. Slow, kinetic sorption contributes further to P removal, while precipitation of phosphate minerals (strengite, hydroxyapatite) is quantitatively unimportant in the saturated zone. Nitrogen (N) dynamics are also considered, but nitrate behaves essentially as a conservative tracer in both systems. The model-predicted advancement of the P plume upon continued wastewater discharge at the calcareous site is in line with field observations. Model results suggest that, upon removal of the wastewater source, the P plume at both sites will persist for at least 20 years, owing to desorption of P from aquifer solids and the slow rate of P mineral precipitation. Sensitivity analyses for the non-calcareous scenario (Muskoka) illustrate the importance of the sorption capacity of the aquifer solids for P in modulating groundwater N:P ratios in oxic groundwater. The model simulations predict the breakthrough of groundwater with high P concentrations and low N:P ratios after 17 years at 20 m from the source for an aquifer with low sorption capacity (<0.02% w/w Fe(OH)(3)). In this type of system, denitrification plays a minor role in lowering the N:P ratios because it is limited by the availability of labile dissolved organic matter.     

An in situ study of the effect of nitrate on the reduction of trichloroethylene by granular iron

The effect of nitrate on the reduction of TCE by commercial granular iron was investigated in column experiments designed to allow for the in situ monitoring of the iron surface film with Raman spectroscopy. Three column experiments were conducted; one with an influent solution of 100 mg/l nitrate+1.5 mg/l TCE, and two control columns, one saturated directly with 100 mg/l nitrate solution, the other pre-treated with Millipore water prior to the introduction of a 100 mg/l nitrate solution. In the presence of nitrate, TCE adsorbed onto the iron, but there was little TCE reduction to end-products ethene and ethane. The iron used (Connelly, GPM, Chicago) is a product typical of those used in permeable granular iron walls. The material is covered by an air-formed high-temperature oxidation film, consisting of an inner layer of Fe(3)O(4), and an outer, passive layer of Fe(2)O(3). In the control column pre-treated with Millipore water, the passive Fe(2)O(3) layer was removed upon contact with the water in a manner consistent with an autoreduction reaction. In the TCE+nitrate column and the direct nitrate saturation column, nitrate interfered with the removal of the passive layer and maintained conditions such that high valency protective corrosion species, including Fe(2)O(3) and FeOOH, were stable at the iron surface. The lack of TCE reduction is explained by the presence of these species, as they inhibit both mechanisms proposed for TCE reduction by iron, including catalytic hydrogenation, and direct electron transfer.     

城市富营养化水体底泥净化磷效果

以城市富营养化水体底泥和上覆水为材料,研究了扰动状态下底泥对外源磷的净化效果。结果表明,扰动状态下,200 g湿底泥从上覆水中共吸收外源磷19.92 mg,而静止状态下,200 g湿底泥仅吸收了13.61 mg。然而,厌氧状态下,前者内源磷释放量仅占吸收磷量的43%,而后者则高达63.4%。说明底泥扰动不仅强化了底泥对外源磷的吸收,而且也强化了内源磷的固定能力。这与扰动状态下外源磷在不同形态磷间的数量分布有关。底泥扰动和静止状态下,难释放态磷(HCl-P、闭蓄态Fe/Al-P)的增加量分别占底泥吸收外源磷量的36%和21%。     

Labile organic carbon regulates phosphorus release from eroded soil transported into anaerobic coastal systems

Coastal eutrophication is expected to increase due to expanding and intensifying agriculture which causes a large amount of soil-associated P to be transported into aquatic systems. We performed anaerobic long-term incubations on field soil to mimic the conditions that eroded soil encounters in brackish sediments. The release of P from soil increased with the amount of labile organic C (acetate) addition and decreased with the soil/solution ratio. We deduce that in less-productive brackish systems, microbial Fe reduction allows for the maintenance of the coupled cycling of Fe and P and restricts the amount of P entering the oxic water. In more eutrophic systems, the formation of Fe sulfides as a result of SO₄ reduction inactivates Fe, and leads to a higher release of P, thus generating an adverse feedback effect. The dependence of the fate of soil-bound Fe and P on the trophic status of the receiving water should be recognized in eutrophication management.     

Humic acids enhance the microbially mediated release of sedimentary ferrous iron

Iron (Fe) is an essential element for many organisms, but high concentrations of iron can be toxic. The complex relation between iron, arsenic (As), bacteria, and organic matter in sediments and groundwater is still an issue of environmental concern. The present study addresses the effects of humic acids and microorganisms on the mobilization of iron in sediments from an arsenic-affected area, and the microbial diversity was analyzed. The results showed that the addition of 50, 100, and 500 mg/L humic acids enhanced ferrous iron (Fe(II)) release in a time-dependent and dose-dependent fashion under anaerobic conditions. A significant increase in the soluble Fe(II) concentrations occurred in the aqueous phases of the samples during the first 2 weeks, and aqueous Fe(II) reached its maximum concentrations after 8 weeks at the following Fe(II) concentrations: 28.95?±?1.16 mg/L (original non-sterilized sediments), 32.50?±?0.71 mg/L (50 mg/L humic acid-amended, non-sterilized sediments), 37.50?±?1.85 mg/L (100 mg/L humic acid-amended, non-sterilized sediments), and 39.00?±?0.43 mg/L (500 mg/L humic acid-amended, non-sterilized sediments). These results suggest that humic acids can further enhance the microbially mediated release of sedimentary iron under anaerobic conditions. By contrast, very insignificant amounts of iron release were observed from sterilized sediments (the abiotic controls), even with the supplementation of humic acids under anaerobic incubation. In addition, the As(III) release was increased from 50?±?10 μg/L (original non-sterilized sediments) to 110?±?45 μg/L (100 mg/L humic acid-amended, non-sterilized sediments) after 8 weeks of anaerobic incubation. Furthermore, a microbial community analysis indicated that the predominant class was changed from Alphaproteobacteria to Deltaproteobacteria, and clearly increased populations of Geobacter sp., Paludibacter sp., and Methylophaga sp. were found after adding humic acids along with the increased release of iron and arsenic. Our findings provide evidence that humic acids can enhance the microbially mediated release of sedimentary ferrous iron in an arsenic-affected area. It is thus suggested that the control of anthropogenic humic acid use and entry into the environment is important for preventing the subsequent iron contamination in groundwater.     

The solid-phase controls on the mobility of heavy metals at the Copper Cliff tailings area, Sudbury, Ontario, Canada

The Copper Cliff Tailings Disposal Area, located near Sudbury, Ontario, covers an area of approximately 2200 ha and constitutes more than 10% of the total area of all mine tailings in Canada. The area has been utilized since 1936, receiving sulphide-containing tailings from the Inco Sudbury operations. Field measurements of pore-gas oxygen and carbon dioxide in the vadose zone indicate that sulphide oxidation has progressed to depths of 1.6 m to 1.7 m within the tailings. The oxidation of sulphide minerals within the vadose zone, and the accompanying dissolution of carbonate and aluminosilicate minerals within these tailings releases SO₄, Fe(II) and other metals to the pore water. In the vadose and saturated zones, concentrations of Fe and Ni exceed 10100 mg/l and 2210 mg/l, respectively. These high concentrations of dissolved metals are attenuated by a series of precipitation, coprecipitation and adsorption reactions. The precipitation of secondary sulphate and hydroxide phases also create hardpan layers at or near the oxidation front. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary-phase precipitation is occurring at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of jarosite, gypsum and goethite within the shallow tailings, suggesting that these phases are controlling the dissolved concentrations of Fe, SO₄ and Ca. Extraction experiments conducted on the tailings solids indicate that the constituents contained in the water-soluble fraction of the shallow, weathered tailings are derived from the original pore water and the dissolution of highly soluble phases such as gypsum. The acid-leachable fraction of the weathered tailings accounts for up to 25% of the heavy metals, and the reducible fraction may contain up to 100% of the heavy metals within the shallow, weathered tailings. Based on the pore water profiles and the geochemistry of the tailings solids, a relative mobility scale of Fe=Mn=Ni=Co>Cd Zn>Cr=Pb>Cu can be determined.     

Geochemistry of a septic-system plume in a coastal barrier bar, Point Pelee, Ontario, Canada

The major ion and trace metal geochemistry of a septic system plume in a shallow sand aquifer was characterized to assess geochemical processes controlling the transport of nutrients and their release to a nearby wetland. The plume was generated from a 16-year-old tile bed, and is more than 60 m long, 40 m wide and 7 m thick. The groundwater pH at the site is near neutral, but up to 0.4 units lower in the plume core as a result of H⁺ generated from NH₃ and DOC oxidation in the unsaturated zone. The plume can be divided into distinct redox zones, which show differences in nutrient mobility. Proximal to the tile bed, there is a shallow suboxic zone, with intermediate Eh values (>400 mV), low concentrations of dissolved oxygen (<1.0 mg/l), and elevated concentrations of Mn (1–3 mg/l) and nutrients (10–80 mg/l NO₃–N, 1–15 mg/l NH₃–N, 0.1–1.5 mg/l PO₄–P, 6–13 mg/l dissolved organic carbon). At the base of the aquifer, there is a reduced zone (Eh<200 mV) with elevated concentrations of Fe (1–14 mg/l), PO₄ and NH₃, but negligible concentrations of NO₃ (<0.01 mg/l N). Distal from the tile bed, the shallow groundwater is suboxic to oxic, and has elevated concentrations of NO₃ and NH_3, but negligible PO₄. In the lower reduced zone, elevated concentrations of PO₄ occur up to 60 m away. The release of groundwater containing even very low concentrations of PO₄ (<0.02 mg/l P) can lead to the development of eutrophic conditions in surface water bodies. Geochemical calculations indicate that, in the Mn-rich zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, rhodochrosite, calcite and ferrihydrite. In the reduced zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, vivianite, calcite and siderite. Formation of these phases, or related phases, are likely limiting the concentrations of dissolved PO₄, Fe and Mn and controlling the geochemical evolution of the plume.     

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13 %. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (?1.072 and ?24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.     

Distribution of metals in a polluted aquifer: A comparison of aquifer suspended material to fine sediments of the adjacent environment

Metal concentrations were determined for groundwater suspended matter from a site in the coastal aquifer of Israel which has been irrigated with secondary sewage effluents since the 1960's. Suspended matter was collected from the aquifer saturated zone by pumping and by a multi-layer sampler. Fine sediments were collected from both the unsaturated and saturated zones of the contaminated aquifer, as well as from an adjacent uncontaminated environment. Ag, Cu, Fe, Mn and Zn were leached from the samples in three sequential chemical extractions which are taken to represent the carbonate, organic and oxide phases. Comparison of the aquifer samples to those of the adjacent environment showed that Fe and Mn are primarily enriched in non-mobile fine sediments and not in suspended matter, whereas the concentrations of Zu, Cu and Ag show up to an order of magnitude enrichment in the mobile suspended matter in groundwater. The enrichment of these metals in the suspended matter indicates that metals from sewage effluents and agricultural activities have reached the groundwater.     

Variations of alkaline phosphatase activity and P fractions in sediments of a shallow Chinese eutrophic lake (Lake Taihu)

The distribution of alkaline phosphatase activity (APA) and P fractions in sediment cores and the relationship between them were studied in a shallow Chinese freshwater lake (Lake Taihu). Sediment cores were collected from four sites, characterized by different degrees of eutrophication in June 2004. Sediment P was fractionated into Fe/Al-P, Ca-P, organic P (OP), inorganic P (IP) and total P (TP). The former two species made the largest contribution to the sediment P pool. Results show that trophic status and hydrological conditions have great impact on the APA of the sediments. The order of the APA in sediments was conjectured to be: macrophyte dominated lake>transitional lake>algal dominated lake. APA profiles follow a similar downcore decreasing trend. There was a positive relationship between the APA and the TP, IP. The multiple linear regression equation of the APA and P fractions is: APA=-97+0.768TP-0.985Fe/Al-P.     

Effects of oxygen on the release and distribution of phosphorus in the sediments under the light condition

Effects of oxygen on the release and distribution of phosphorus (P) in the sediments in the presence of light were investigated, using sediment cores and overlying water from Lake Taihu, in China. The results show that P can be released from sediments to the overlying water in both anoxic and aerobic conditions. But more P was released in the anoxic condition. The transformation of P between various fractions in the sediments was observed during the release experiments. Concentrations of Ca-bound P and organic P in the sediments decreased in both conditions, but Fe/Al-bound P increased in the aerobic condition. The decrease of total P and P fractions in the sediments is consistent with the accumulative increase in quantity (AIQ) of total P (TP) in the overlying water, but is contrary with the AIQ of dissolved inorganic P. This is due to the uptake of algae by the dissolved inorganic P. Total nitrogen in the sediments in the anoxic condition was lower than that in the aerobic condition, and pH in the overlying water increased in the anoxic condition.     

Influence of hydrology on heavy metal speciation and mobility in a Pb-Zn mine tailing

Among the inorganic toxicants of greatest concern in mine tailings, Pb, Zn, Cu, Cd and As figure prominently due to their abundance and potential toxicity. Here we report on their biolability and solid-phase speciation in two sediment cores subject to variable hydrological regimes at an abandoned pyritic mine tailing. The oxic conditions of well-drained sediments induced pyrite oxidation and the subsequent liberation of H+, SO4(2-) and considerable quantities of Fe(III), which precipitated as goethite. Solubility of Pb, Zn, Cu and Cd was closely coupled to pH and goethite presence. Metal lability was particularly low in zones of neutralization, formed by the accumulation of calcite, first carried then deposited by percolating waters in both saturated and unsaturated cores. We conclude that differential hydrology induces variable heavy metal speciation and biolability in Pb-Zn mine tailings, and suggest that site-specific risk assessments must account for past and present hydrological regimes.     

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.     

Effects of water characteristics on nitrate reduction by the Fe0/CO2 process

In this study, CO2 was bubbled into Fe0-contained solution to create an acidic environment favorable to reduction of aqueous nitrate under various water qualities. Results showed that nitrate of 30 mg l(-1) could be removed from solutions almost completely within 30 min under the conditions of 2 g Fe0 l(-1) and CO2 bubbling flow rate of 200 ml min(-1). It was observed from the Fe0/CO2 system that one mole of nitrate reduced by Fe0 led to the formation of 6.6 mol of ferrous ions. The removal of nitrate increases with increasing Fe0 dosage, however, the removal makes no difference as the Fe0 is applied at a relatively higher dosage. In the system with various water qualities, nitrate removal was inhibited significantly in the presence of humic acid. Calcium ions strongly retard nitrate removal, whereas chloride ions promote the reduction of nitrate in a significant way. Sodium ions impose only slight inhibitive effect on nitrate removal. Water molecule in the studied system can be of significance due to its competitive capability of electrons released from Fe0.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges-Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 microg/L to 191 microg/L with a mean concentration of 33 microg/L. Groundwater is mainly Ca-HCO(3) type with high concentrations of dissolved As, Fe, and Mn, but low level of SO(4). The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 microg/L. Deeper aquifer (>100 m depth) has a mean arsenic concentration of 18 microg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Assessment of metal and nutrient concentrations in river water and sediment collected from the cities in the Pearl River Delta,South China

The effects of anthropogenic activities, industrialization and urbanization on the accumulation of heavy metals and nutrients in sediments and water of rivers in the Pearl River Delta region were examined. Most sediments were seriously contaminated with Cd, Pb, and Zn in accordance with the classification by Hong Kong Environmental Protection Department. Total phosphorus (P) and nitrogen (N) concentrations in sediments ranged from 0.02% to 0.12% and 0.06% to 0.64%, respectively. High carbon (C), N, P and sulphur (S) levels at Yuen Long Creek were related to the discharge of industrial effluents along the river. The enrichment of P and ammoniacal-nitrogen (NH4+-N) in water were obvious. For most sites, the P concentration exceeded 0.1 mg/l, which is the recommended concentration in flowing water to encourage excessive growth of aquatic plants. Nine out of the 16 sites studied had NH4+-N concentration over 2 mg/l. The rivers in the south of Deep Bay (Hong Kong) had high nutrient exports compared with the rivers in the east region and western oceanic water. The concentrations of nitrate-nitrogen NO3--N in surface water were under the maximum contaminant level in public drinking water supplies (10 mg/l) except for one site. Although the concentrations of heavy metals in overlying water were low, their accumulations were significant. High contents of nickel (Ni) and zinc (Zn) in water were found at certain locations, suggesting the occurrence of some local contamination. These preliminary results indicated that river and sediment transported pollutants is likely one of the factors for the water quality degradation of Deep Bay water.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 µg/L to 191 µg/L with a mean concentration of 33 µg/L. Groundwater is mainly Ca–HCO₃ type with high concentrations of dissolved As, Fe, and Mn, but low level of SO₄. The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 µg/L. Deeper aquifer (> 100 m depth) has a mean arsenic concentration of 18 µg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Groundwater chemistry of the Okélobondo uraninite deposit area (Oklo, Gabon): two-dimensional reactive transport modelling

The stability of uranium-bearing minerals in natural environments is of interest to evaluate the feasibility of radioactive waste repositories. The uraninite bodies, UO2(s), in the Oklo district (Gabon) are the result of a natural fission process, which took place 1970 Ma ago. These deposits can be regarded as natural analogues for spent fuel. One of the uraninite bodies, the Okélobondo deposit, is located at a depth of 300 m. Groundwater samples from boreholes located at shallow depths (100-200 m) show neutral to basic pH, anoxic conditions (Eh = 0.10 to -0.05 V) and are saturated with respect to uraninite. In contrast, deeper samples collected in the vicinity of the ore body are oxidising (Eh = 0.32-0.47 V), slightly basic (pH = 7.0-8.5) and undersaturated with respect to uraninite. These oxidising conditions at depth, if present under repository conditions, may affect the stability of uranium oxide. In order to improve our understanding of the observed site geochemistry, the available information on the lithology and groundwater flow was integrated in a reactive transport model. The chemical composition and the pH-Eh values of the water sampled above and in the western side of the Okélobondo deposit can be explained by the interaction of meteoric recharge with pelites, dolomites and sandstones. The dissolution of Fe(II)-silicates and the oxidation of the Fe(II)-aqueous species maintained the pH-Eh distribution along the Fe(2+)-Fe(OH)3(am) equilibrium, with the result that uraninite does not dissolve. This may explain the lower uranium content in the water samples from pelites and dolomites above the Okélobondo deposit. The high Mn/Fe ratio and the high pH-Eh values of the water sampled at depth, close to the Okélobondo deposit, suggest a control by the Mn(2+)-MnOOH(s) equilibrium. This control is attributed to the dissolution of a large rhodochrosite, MnCO3(s), and manganite, MnOOH(s) deposit in the recharge area on the eastern side.     

Use of abiotic oxidative-reductive technologies for remediation of munition contaminated soil in a bioslurry reactor

The possibility to clean-up TNT contaminated soil, 400 mg TNT kg-1, surrounding Nebraska Ordnance Plant's (US), below the USEPA goal of 17.2 mg TNT kg-1 using Fenton oxidation (Fe2+ + H2O2), Fe0 reduction, combined Fe0/H2O2 and CaO2 was explored at pilot scale. Treatments were performed in a 60 l airlift reactor, which was a prototype of larger commercial unit. All the treatments reduced TNT soil concentration below the required clean-up goal and in shorter time with respect to bench scale. Using 2% (w/w) Fe0, TNT soil concentration reduced below the required standard just within 4 h. No significant TNT destruction improvement was observed when 2% Fe0 (w/w soil) was combined with four sequential additions of 0.25% H2O2. Laboratory experiments with 14C-TNT indicated that most of the 14C, approximately 80%, was unextractable residue. A time greater than 24 h was required either with Fenton reagent, 8 x (80 mg Fe2+ L-1 + 0.125% H2O2) or 0.2% (w/w) CaO2. The optimal performance of Fenton reagent was obtained when the reagent was added in eight increments rather than in a single or double dose and less cumulative amount of H2O2 (0.75%) was required with respect to bench scale (1%).