Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange--an on-site approach

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators (diethylenetetraaminepentaacetic acid (DTPA), ethylendiaminetetraacetic acid (EDTA)) and metal exchange with strongly competitive cations (Cu(II) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake (Venner Moor, Münsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC (dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES (inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species (Fe, Mn, Zn) could be characterized. Conditional exchange constants Kex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn > > Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu(II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.     

Influence of organic loading on an anaerobic sequencing biofilm batch reactor (ASBBR) as a function of cycle period and wastewater concentration

The effect of organic loading on the performance of a mechanically stirred anaerobic sequencing biofilm batch reactor (ASBBR) has been investigated, by varying influent concentration and cycle period. For microbial immobilization 1-cm polyurethane foam cubes were used. An agitation rate of 500 rpm and temperature of 30+/-2 degrees C were employed. Organic loading rates (OLR) of 1.5-6.0gCODl(-1)d(-1) were applied to the 6.3-l reactor treating 2.0 l synthetic wastewater in 8 and 12-h batches and at concentrations of 500-2000mgCODl(-1), making it possible to analyze the effect of these two operation variables for the same organic loading range. Microbial immobilization on inert support maintained approximately 60 gTVS in the reactor. Filtered sample organic COD removal efficiencies ranged from 73 to 88% for organic loading up to 5.4gCODl(-1)d(-1). For higher organic loading (influent concentration of 2000mgCODl(-1) and 8-h cycle) the system presented total volatile acids accumulation, which reduced organics removal efficiency down to 55%. In this way, ASBBR with immobilized biomass was shown to be efficient for organic removal at organic loading rates of up to 5.4gCODl(-1)d(-1) and to be more stable to organic loading variations for 12-h cycles. This reactor might be an alternative to intermittent systems as it possesses greater operational flexibility. It might also be an alternative to batch systems suspended with microorganisms since it eliminates both the uncertainties regarding granulation and the time necessary for biomass sedimentation, hence reducing the total cycle period.     

Fed-batch and batch operating mode analysis of a stirred anaerobic sequencing reactor with self-immobilized biomass treating low-strength wastewater

This work presents an analysis of a stirred anaerobic sequencing discontinuous reactor with different substrate feeding strategies resulting in batch, fed-batch/batch and fed-batch operating modes. The reactor, containing granulated biomass, was fed with approximately 2.0L of synthetic domestic wastewater with Chemical Oxygen Demand of nearly 500 mg/L per cycle and operated at 30 degrees C and 50 rpm. Three feeding strategies with a total cycle time of 6 h, including 30-min settling, were adopted: batch mode with a fill cycle of 6 min, a fed-batch/batch mode with fill cycles of 60, 120 and 240 min and fed-batch mode with a fill cycle of 320 min. The system attained average non-filtered and filtered substrate removal efficiency of 78 and 84%, respectively, for all operating conditions, presenting good stability, solid retention and no granule break-up. A first order kinetic model with a residual organic matter concentration was proposed to analyze the influence of the feeding strategy on the performance during a cycle and bicarbonate alkalinity and total volatile acids concentration profiles were also quantified in order to verify the transient stability behavior.     

Landform Classification for Land Use Planning in Developed Areas: An Example in Segovia Province (Central Spain)

Landform-based physiographic maps, also called land systems inventories, have been widely and successfully used in undeveloped/rural areas in several locations, such as Australia, the western United States, Canada, and the British ex-colonies. This paper presents a case study of their application in a developed semi-urban/suburban area (Segovia, Spain) for land use planning purposes. The paper focuses in the information transfer process, showing how land use decision-makers, such as governments, planners, town managers, etc., can use the information developed from these maps to assist them. The paper also addresses several issues important to the development and use of this information, such as the goals of modern physiography, the types of landform-based mapping products, the problem of data management in developed areas, and the distinctions among data, interpretations, and decisions.     

Solidification/stabilisation of arsenic bearing fly ash from the metallurgical industry. Immobilisation mechanism of arsenic

When a fly ash waste material from a copper refining process containing large amounts of As2O3 is solidified using cement and lime, the arsenic concentration in the leachate can be lowered to ca. 5 mg/l in a saturated solution of Ca(OH)2. It is shown that the decrease of the concentration in the leachate, mainly of As(III), is due to the formation of insoluble CaHAsO3 in the leachate in the presence of Ca(OH)2. This method is compared with a method whereby use is made of oxidation of the waste before solidification to oxidise As(III) to As(V) using H2O2. The arsenic concentration in the leachate of the extraction test of an oxidised S/S sample was lowered to ca. 0.5 mg/l, a factor of 10 below the one for a non-oxidised sample. It is shown that the decrease of the concentration in the leachate mainly of As(V) is due to the formation of insoluble Ca3(AsO4)2 in the presence of Ca(OH)2. Extensive use was made of the speciation program MINTEQA2, to clarify the immobilisation of arsenic.     

Preferential bromide and pesticide movement to tile drains under different cropping practices

Subsurface drainage systems are useful tools to study chemical leaching in soils. Our objective was to compare the breakthrough behavior of bromide, atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamid] to tile drains under two fall tillage practices (conventional tillage [CT] with a moldboard plow, and reduced tillage [RT] with a chisel plow) in field plots cultivated with corn (Zea mays L.). Leachate volume were greater in RT than in CT, with no statistical differences. Soil analysis showed that bromide migrated deeper in the soil profile than both herbicides, with little tillage effect. All chemicals were detected in drainage water at the same time and followed an event-driven behavior. Tillage had no effect on atrazine and metolachlor found in drainage water, while bromide concentration peaks were higher in RT than in CT in 1999. Concentration peaks were recorded earlier for atrazine and metolachlor than for bromide. Plots of cumulative relative chemical mass (cumulative mass divided by total mass measured in drainage) as a function of cumulative drainage were mostly linear for bromide, while they were S-shaped for both herbicides. Drainage that corresponded to 50% of relative cumulative mass ranged from 40 to 55% for bromide and from 5 to 28% for both herbicides. Rapid chemical movement to tile drains suggested that preferential flow was important in both CT and RT, and that these tillage practices had little influence on this phenomena.     

Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

Study of a predictive methodology for quantification and mapping of the radon-222 exhalation rate

We propose a new methodology for predicting areas with a strong potential for radon (222Rn) exhalation at the soil surface. This methodology is based on the Rn exhalation rate quantification, starting from a precise characterisation of the main local geological and pedological parameters that control the radon source and its transport to the soil/atmosphere interface. It combines a cross mapping analysis of these parameters into a geographic information system with a model of the Rn vertical transport by diffusion in the soil. The rock and soil chemical and physical properties define the entry parameters of this code (named TRACHGEO) which calculates the radon flux density at the surface. This methodology is validated from in situ measurements of radon levels at the soil/atmosphere interface and in dwellings. We apply this approach to an area located in western France and characterised by a basement displaying a heterogeneous radon source potential, as previously demonstrated by lelsch et al. (J. Environ. Radioactivity 53(1) (2001) 75). The new results obtained show that spatial heterogeneity of pedological characteristics in addition to basement geochemistry--must be taken into account to improve the mapping resolution. The TRACHGEO forecasts explain the Rn exhalation variability on a larger scale and in general correlate well with in situ observations. Moreover, the radon-prone sectors identified by this approach generally correspond to the location of the dwellings showing the highest radon concentrations.     

Distribution of long-lived radionuclides of the 238U series in the sediments of a small river in a uranium mineralized region of Spain

A study is presented on the distribution and mobilization of the natural U isotopes (238U and 234U), 230Th, and 226Ra in the sediments of a small river crossing an uranium mineralized zone where a disused uranium mine is located. Due to the preferential directions for surface run-off waters and to the mine's situation, one sampling point along the river bed was identified as a point of accumulation of radionuclides. The average values of the activity concentrations (Bq/kg) in this sediment sample were 5,025, 5,055, 5,915 and 1,694 for 238U, 234U, 230Th and 226Ra, respectively, while the respective average values of the activity concentrations (Bq/kg) for the sediment sample considered to give the background level were 125, 124, 131 and 370. Isotopic ratios between the descendants of 238U served to clarify some paths of distribution, involving the soils nearest to the sampling points and the location of these points with respect to the disused mine. The differences in behaviour found between the uranium, thorium and radium isotopes were associated to the mobility of these radionuclides in the fluvial system studied. Correlations between the radionuclide activity concentration ratios and stable element concentrations in the sediment samples were also investigated.     

Uranium transport around the reactor zone at Bangombé and Okélobondo (Oklo): examples of hydrogeological and geochemical model integration and data evaluation

The sites at Bangombé and Okélobondo (Oklo) in Gabon provide a unique opportunity to study the behaviour of products from natural nuclear reactions in the vicinity of reactor zones which were active around two billion years ago. The Commission of the European Communities initiated the Oklo Natural Analogue Programme. One of the principal aims was to study indications of present time migration of elements from the reactor zones under ambient conditions. The hydrogeological and hydrochemical data from the Oklo sites were modelled in order to better understand the geochemical behaviour of radionuclides in the natural system, by using independent models and by comparing the modelling outcome. Two modelling approaches were used: M3 code (hydrochemical mixing and mass balance model), developed by the Swedish Nuclear Fuel and Waste Management Company (SKB) and HYTEC (reactive transport model) developed by Ecole des Mines de Paris. Two different reactor zones were studied: Bangombé, a shallow site, the reactor being at 11 m depth, and OK84 at Okélobondo, situated at about 450 m depth, more comparable with a real repository location. This allowed the validation of modelling tools in two different sedimentary environments: one shallow, with a more homogeneous layering situated in an area of meteoric alteration, and the other offering the opportunity to study radionuclide migration from the reaction zone over a distance of 450 m through very heterogeneous sedimentary layers. The modeling results indicate that the chemical reactions retarding radionuclide transport are very different at the two sites. At Bangombé, the decomposition of organic material consumes oxygen and at Okélobondo the oxygen is consumed by inorganic reactions resulting, in both cases, in uranium retardation. Both modelling approaches (statistic with M3 code and deterministic with HYTEC code) could describe this situation. The goal of this exercise is to test codes which can help to describe and understand the processes taking place at the sites, validate the models with in situ data, and thus build confidence in the tools used for future site characterization. Ultimately, this allows identifying and selecting processes and parameters that can be used as input into repository performance assessment calculations and modelling exercises.