The evolution of microbial communities with increasing carbon tetrachloride concentrations was studied in two anaerobic columns containing sand and two different clay soils, one of which contained high levels of iron. Microbial communities were characterized through analysis of column effluents with denaturing gradient gel electrophoresis and quantitative polymerase chain reaction for archaea and eubacteria as inlet carbon tetrachloride concentrations were increased from 0.8 to 29 μM. Inhibition of microbial activity was observed in both columns, and was associated with the accumulation of chloroform at concentrations of 0.2 to 0.4 μM as inlet CT concentrations were increased to 2.4-3.0 μM in the low-iron clay column and approximately 16 μM in the iron rich clay column. Inhibition was indicated by decreasing rates of methanol and carbon tetrachloride degradation, decreases in effluent levels of DNA, and shifts in microbial communities of the columns. Even with the inhibition observed, in the iron-rich clay column CT degradation continued to the end of the study with inlet CT concentrations of 29 μM, in contrast to the low-iron clay column in which minimal CT degradation occurred once CT inlet concentrations exceeded 3 μM. The greater capacity for CT degradation in the column containing the iron-rich clay was hypothesized to be the result of reaction with biogenic ferrous iron produced by biological dissimilatory iron reduction.

Column experiments were conducted using ideal natural sands and stainless-steel beads to examine the complete dissolution behavior of an organic immiscible liquid. Trichloroethene was used as the representative organic liquid. The elution curves exhibited multi-step behavior, with multiple extended periods of relatively constant contaminant flux. These secondary steady-state stages occurred at concentrations several orders-of-magnitude below aqueous solubility for the well-sorted sands. In contrast, the secondary steady-state stages occurred within 1 log of aqueous solubility for the poorly sorted sand. The non-ideal behavior is hypothesized to result from constraints to hydraulic accessibility of the organic liquid to flowing water, which may be expected to be mediated by the pore-scale configuration of the flow field and the fluid phases.

Little is known about the transport of microorganisms through freeze-fractured clay soils. Normally consolidated clay (NCC) and compacted clay (CC) columns (representing a natural clay barrier and a compacted barrier, respectively) were exposed to six consecutive freeze-thaw cycles and permeated for 21 days with an Escherichia coli cell suspension (approximately 1 × 10⁷ colony forming units (CFU)/mL) containing a 2.1-mM bromide tracer. An unfractured sand column was also examined for comparison with the clay columns. While no E. coli was detected in the effluent of both untreated NCC and CC control clay columns, a relatively low density of E. coli (between 228 and 270 CFU/mL compared to 1 × 10⁷ CFU/mL in the influent) was first detected in the effluent of the freeze-fractured NCC and CC columns at 0.29 and 0.31 pore volumes (or at 5.4 and 4.1 h), respectively. It took 11 min for a full breakthrough of E. coli through the sand column, but only about 0.1% of the influent E. coli density was detected in the effluents of the freeze-fractured NCC and CC columns at day 21. These observations show that despite the high bacterial retention capacity of the freeze-fractured clay columns, the fractures were large enough for the E. coli to flow through. Based on batch sorption tests and the permeation data, it is estimated that 18%, 7%, and 84% of the freeze-fractured NCC, CC, and sand columns would be exposed to the influent, respectively, under a full E. coli breakthrough condition. Our data show that the high bacterial retention capacity of clay barriers can be compromised by freeze-thaw conditions.

The elemental composition and bioaccessibility of trace metals have been determined in a variety of geosolids (soils, road dusts and house dusts) from an arid, coastal region (Dhahran, Saudi Arabia). Concentrations of many elements reflected those of the local geology, ascertained by analysis of desert sand. Several trace metals (e.g. Cu, Sb, Zn, Pb, Tl and Sn) were moderately enriched in both road and house dusts, reflecting external and internal (household) anthropogenic sources. For a given trace metal, bioaccessibilities, assessed using a physiologically based extraction test, were broadly similar across the range of geosolids. Median values for a simulated gastric phase ranged from less than 10% (Ba, Cu, Cr, Ni and V) to more than 50% (As, Cd, Sb, Sn and Tl), and for a subsequently simulated intestinal phase from less than 15% (Ba, Cr, Cu, Ni, V and Zn) to more than 50% (As, Cd, Sb, Tl and U). Results suggest that the levels and bioaccessibilities of trace metals in dusts from arid environments are controlled by the dilution of anthropogenic particulates by variable (but significant) proportions of fine, baseline sand.

A method that utilizes solid-phase microextraction (SPME) coupled with gas chromatography (GC) and chemical ionization tandem mass spectrometry (MS/MS) was developed for analyzing a group of emerging pollutants, N-nitrosamines, in water. The developed analytical method requires a water sample of less than 5 ml and only 1.5 h for complete analysis. The method detection limits for N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine, and N-nitrosodi-n-propylamine were in the range of 3.2 to 3.5 ng/l; for N-nitrosomorpholine, it was 15.2 ng/l. The method was successfully employed to measure the N-nitrosamine concentration at trace levels of nanogram per liter in four water treatment plants (WTPs) and one water distribution system. In the WTPs, only NDMA was detected in the treatment processes. Within the treatment train, NDMA was observed after chlorination. The level of NDMA significantly declined after slow sand filtration due presumably to microbial degradation. The NDMA concentration collected from consumer tap water was about 40% higher on average than that in the finished water. The excellent performance of the SPME/GC/MS/MS method in various water matrices as well as the shorter analysis time and smaller sample volume compared to currently used extraction techniques makes it an alternative means for the analysis of N-nitrosamine in drinking water, wastewater, and laboratory research with small reactors.

Background, aim, and scope The Lower Mississippi River is a major transportation route for commercial goods and petroleum products produced and refined locally. Oil spills caused by vessel accidents and equipment failure at refineries are a serious threat to the drinking water supply of Southern Louisiana, as well as to the many natural, economic, and social resources supported by the river. Providing accurate trajectory modeling to contingency planners is critical to protecting the local environment. The majority of trajectory model results, assuming a uniform shoreline, show 60-70% of spilled oil can be retained. This study examines the impact of detailed shoreline mapping that captures spatial and temporal changes in shoreline type on oil spill trajectory modeling. Materials and methods Detailed shoreline maps based on recent remote sensing imagery were generated to identify spatial changes in shoreline. A hydrodynamic model of the 78 mile reach from Convent, Louisiana to West Pointe a la Hache was developed to obtain the stage levels and velocity fields of four river discharges. Based on river stage level, another layer was added to the shoreline maps, so that shoreline type was accurately represented at each river discharge, a feature not included in previous mapping. An oil spill trajectory model was then used to investigate the effect of implementing different re-floatation half-lives that correlate to the shoreline maps developed for this study at four river discharges. Results Detailed shoreline mapping showed the Lower Mississippi River has four major shoreline types each with different oil re-floatation half-lives: muddy clay, sand, low vegetation, and high vegetation. As flow rate changed, the shoreline spatial variability also changed, from 84% mud/sand and 16% vegetation at low flow rates to 4% mud and 96% vegetation at higher flow rates. At flow rates with large variability in shoreline type, the distribution of oil attached to the shore was significantly different from results of simulations that used a constant shoreline type and re-floatation half-life. Discussion At low flow rates, simulations with the detailed delineation of shoreline type predicted that ~30% of the oil would be beached/retained because the oil was able to travel further down the reach and interact with the shoreline in multiple locations. Simulations at the low flow rates with the existing shoreline mapping predicted approximately 65% of the oil would be retained as did all the simulations at the highest flow rates. At high flow rates, the oil interacted mostly with vegetation and results were very similar to those obtained with a single re-floatation half-life of 1 year. In addition to shoreline type, river geometry and the hydrodynamics were major factors influencing the distribution of oil along the river reach. Conclusions Shoreline re-floatation half-lives have a major impact on simulating the distribution of oil along the shore after a spill, especially in areas with a high variability of shoreline type as in the lower Mississippi River. Assigning the correct re-floatation half-life and retention capacity is only possible when shoreline types have been correctly identified. The maps developed for this study provided an important level of detail and incorporated the change in shoreline type with flow rate, resulting in more detailed trajectory modeling of the study reach. Recommendations and perspectives Shoreline maps should include as much detail about shoreline type as possible. When developing shoreline maps or environmental sensitivity assessments, the focus should include specific characteristics of the study area; using standardized maps or methods of assessment may leave out detail that could negatively impact modeling efforts. Finally, shoreline sensitivity to oiling is an important area of research that will benefit from an improved understanding of oil retention by vegetation.

Background, aim and scope Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa's residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha⁻¹ of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications. Methods The sponge-trapping and KCl-extraction method was used for determining NH₃ volatilisation from surface-applied DAP in samples of BRS collected from each of Alcoa's three Western Australia Refineries (Kwinana, Pinjarra, Wagerup) under various pH conditions (pH 4, 7, 9 and 11). Following cessation of volatilisation, the residual N was extracted from BRS using 2 M KCl and concentrations of NH ₄ ⁺ -N and NO ₃ ⁻ -N were determined by flow injection analysis. Results The quantities of NH₃ volatilised increased dramatically as the pH increased from 4 to 11. Much of the N lost as NH₃ (up to 95.2%) occurred within a short period (24 h to 7 days), particularly for the pH 9 and 11 treatments. Concentrations of residual NH ₄ ⁺ -N recovered in DAP-treated BRS at the end of the experiment decreased with increasing pH. This finding was consistent with increasing loss of N via volatilisation as pH increased. The concentration of NO ₃ ⁻ -N was very low due to no nitrification in BRS. Discussion The pH was a key driver for NH₃ volatilisation from DAP-treated BRS and primarily controlled N dynamics in BRS. Results indicate that NH₄ not adsorbed by BRS was highly susceptible to volatilisation. The likely lack of nitrifying bacteria did not allow conversion of ammonium to nitrate, thereby further exacerbating the potential for loss via volatilisation Conclusions It was demonstrated that the pH is the key factor controlling the loss of inorganic N from BRS. Although volatilisation was considerably lower at pH 4, achieving this pH reduction in the field is not possible at present. Findings from this study highlight the need to better understand which forms of N fertiliser are most suitable for use in highly alkaline BRS. Recommendation and perspectives Although pH reduction is the most likely means of stopping NH₃ volatilisation in BRS, it is economically and operationally unfeasible to add sufficient acidity for adequately lowering pH in the BRS for revegetation. More attention on forms of fertilisers more suitable to highly alkaline, microbially inert soil conditions appears to be warranted.

Background, aim and scope The production of alumina involves its extraction from bauxite ore using sodium hydroxide under high temperature and pressure. This process yields a large amount of residue wastes, which are difficult to revegetate due to their inherent hostile properties—high alkalinity and sodicity, poor water retention and low nutrient availability. Although phosphorus (P) is a key element limiting successful ecosystem restoration, little information is available on the availability and dynamics of P in rehabilitated bauxite-processing residue sand (BRS). The major aim of this experiment was to quantify P availability and behaviour as affected by pH, source of BRS and di-ammonium phosphate (DAP) application rate. Materials and methods This incubation experiment was undertaken using three sources of BRS, three DAP application rates (low, without addition of DAP; medium, 15.07 mg P and 13.63 mg N of DAP per jar, 100 g BRS; and high, 30.15 mg P and 27.26 mg N per jar, 100 g BRS), and four BRS pH treatments (4, 7, 9 and 11 (original)). The moisture content was adjusted to 55% water holding capacity and each BRS sample was incubated at 25°C for a period of 119 days. After this period, Colwell P and 0.1 M H₂SO₄ extractable P in BRS were determined. In addition, P sequential fractionation was carried out and the concentration of P in each pool was measured. Results and discussion A significant proportion (37% recovered in Colwell P and 48% in 0.1 M H₂SO₄ extraction) of P added as DAP in BRS are available for plant use. The pH did not significantly affect 0.1 M H₂SO₄ extractable P, while concentrations of Colwell P in the higher initial pH treatments (pH 7, 9 and 11) were greater than in the pH 4 treatments. The labile fractions (sum of NH₄Cl (AP), bicarbonate and first sodium hydroxide extractable P (N(I)P)) consisted of 58-64% and 70-72% of total P in the medium and high DAP rate treatments, respectively. This indicates that most P added as DAP remained labile or moderately labile in BRS, either in solution, or in adsorbed forms on the surface of more crystalline P compounds, sesquioxides and carbonate, or associated with amorphous and some crystalline Al and Fe hydrous oxides. In addition, differences in the hydrochloric acid extractable P and the residual-P fractions among the treatments with and without DAP addition were relative small comparing with other P pools (e.g., NaOH extractable P pools), further indicating the limited capacity of BRS for fixing P added in Ca-P and other most recalcitrant forms. Conclusions P availability in the original BRS without addition of DAP was very low, mostly in recalcitrant form. It has been clearly demonstrated that significant proportions of P added as DAP could remain labile or moderately labile for plant use during the rehabilitation of bauxite-processing residue disposal areas. There was limited capacity of BRS for fixing P in more recalcitrant forms (e.g., Ca-P and residual-P). Concentrations of most P pools in BRS increased with the DAP application rate. The impact of the pH treatment on P availability varied with the type of P pools and the DAP rate. Recommendation and perspectives It is recommended that the development of appropriate techniques for more accurate estimation of P availability in BRS and the quantification of the potential leaching loss of P in BRS are needed for the accurate understanding of P availability and dynamics in BRS. In addition, application of organic matters (e.g., biosolids and biochar, etc.) to BRS may be considered for improving P availability and buffering capacity.

Background, aim, and scope Transport of bacteria through natural porous media is an issue of increasing concern arising in several very important environmental processes. These include the percolation of bacteria from fecal waste to drinking water reservoirs, thus leading to a risk for human health, or the bioremediation of contaminated soils in which the bacteria are expected to travel long distances underground in order to reach contaminated areas and degrade chemicals originating from accidental spills. An understanding of bacterial retention and transport mechanisms in porous media would be of great help in the development of models able to predict the distance covered by bacterial suspensions in these situations. Materials and methods Experiments were carried out preparing columns filled of soil and sand, introducing bacteria culture (Escherichia coli, Pseudomona putida, and Listeria innocua) solutions by the top of the column. Breakthrough curves were obtained to see the transport of the bacteria in the column. Results The transport of different bacteria in the two soils aimed at establishing the relative importance of straining in different conditions. This has enabled us to obtain certain parameters, such as the sticking coefficients derived from the filtration theory or bacterial recoveries after multi-step elution, which aid our understanding of how bacteria are retained by mechanisms different to those usually included in the physico-chemical filtration theory. Discussion Several indicators may be used to determine the degree of relevance of straining as a mechanism acting during bacterial transport through porous media. Usually, in natural media, neither straining nor physico-chemical filtration is the sole mechanism contributing to bacterial retention. The retention of bacteria by straining mechanisms can be assessed by means of elution profiles under varying conditions. The inversion of flow in our experiments gave rise to secondary elution peaks, probably originating from bacteria retained in narrow pores Conclusions According to experimental observations, straining was shown to contribute highly to bacterial retention in all the soils tested, in particular in the soils with a broader grain size distribution and more irregular shape. In both media, an increase in ionic strength did not lead to significant differences in bacterial retention, possibly due to the lack of relevance of ionic repulsion as a barrier to physico-chemical attachment of particles Recommendation and perspectives The study of bacteria transport in natural soil is an important step in the development of decontamination processes. The importance of the straining in the transport process has been revealed in the work carried out in this paper.