Steady-state models for the prediction of P retention coefficient (R) in lakes were evaluated using data from 93 natural lakes and 119 reservoirs situated in the temperate zone. Most of the already existing models predicted R relatively successfully in lakes while it was seriously under-estimated in reservoirs. A statistical analysis indicated the main causes of differences in R between lakes and reservoirs: (a) distinct relationships between P sedimentation coefficient, depth, and water residence time; (b) existence of significant inflow-outflow P concentration gradients in reservoirs. Two new models of different complexity were developed for estimating R in reservoirs: [graphic removed] , where τ is water residence time (year), was derived from the Vollenweider/Larsen and Mercier model by adding a calibrated parameter accounting for spatial P non-homogeneity in the water body, and is applicable for reservoirs but not lakes, and [graphic removed] , where [Pin] is volume-weighted P concentration in all inputs to the water body (μg l-¹), was obtained by re-calibrating the OECD general equation, and is generally applicable for both lakes and reservoirs. These optimised models yield unbiased estimates over a large range of reservoir types.

We estimated the total inorganic fluxes of nitrogen (N), sulfur (S), chloride (Cl-, sodium (Na⁺, calcium (Ca²⁺, magnesium (Mg²⁺, potassium (K⁺ and hydronium (H⁺. The resistance deposition algorithm that is programmed as part of the CALMET/CALPUFF modeling system was used to generate spatially-distributed deposition velocities, which were then combined with measurements of urban and rural concentrations of gas and particle species to obtain dry deposition rates. Wet deposition rates for each species were determined from rainfall concentrations and amounts available from the National Acid Deposition Program (NADP) monitoring network databases. The estimated total inorganic nitrogen deposition to the Tampa Bay watershed (excluding Tampa Bay) was 17 kg-N ha-¹ yr-¹ or 9,700 metric tons yr-¹, and the ratio of dry to wet deposition rates was ~2.3 for inorganic nitrogen. The largest contributors to the total N flux were ammonia (NH₃ and nitrogen oxides (NO x at 4.6 kg-N ha-¹ yr-¹ and 5.1 kg-N ha-¹ yr-¹, respectively. Averaged wet deposition rates were 2.3 and 2.7 kg-N ha-¹ yr-¹ for NH₄ ⁺ and NO₃ -, respectively.

Microorganisms are responsible for the bulk of transformations that occur in surficial sediments. They are most active at redox boundaries where they can benefit from access to various oxidants and reductants generated during redox cycling events. To illustrate the dynamics of microbially mediated processes, especially those involving sulfur and metal cycles, processes were compared in habitats either bioturbated by a capitellid worm or inhabited by a salt marsh grass. The presence of macrofauna and macroflora greatly altered the three-dimensional array of redox gradients in sediments, but the type and form of reductants and oxidants provided varied greatly; clastic sedimentary infauna subducted solid phase organic material and iron oxides, whereas plant roots released dissolved organic matter and oxygen. These differences resulted in a bioturbated system that exhibited a rapid sulfur cycle (residence time of minutes), but a slower iron cycle (days), whereas vegetation caused a slow sulfur cycle and rapid iron cycle. Alteration of sediments by higher life forms also greatly affected the composition and relative abundances of sedimentary bacteria, even on short time scales. Although redox cycling at interfaces can be somewhat predictable, variations in response to biological and physical perturbations demonstrated wide differences in the dynamics of redox-mediated processes.

Chemical immobilisation of inorganic contaminants by increasing the sorption capacity of soils and/or promoting the formation of sparingly soluble precipitates may be a cost-effective approach to counteract groundwater pollution. This study focuses on the enhanced retention of arsenic in two contaminated soils by addition of solid iron(II)sulphate. Four lab-scale column experiments were performed under unsaturated conditions with subsoil material sampled at a former timber preservation site and a pigment production plant. Arsenic effluent concentrations indicated 89.9 to 99.8% immobilisation in the treated columns. Sequential extractions showed a shift in contaminant binding forms towards the iron(hydr)oxide and residual fractions. Possible immobilisation mechanisms are the precipitation of FeAs phases, the formation of inner sphere complexes, and/or the occlusion of arsenic in newly formed amorphous/crystalline iron oxides. Bromide breakthrough curves point to the fact that the addition of iron(II)sulphate only moderately affects soil hydraulic properties. In contrast to reduced emissions of arsenic, increased seepage water concentrations were observed for other trace elements (e.g., cobalt, nickel, zinc). Mass balances indicate that this effect is primarily related to the temporary pH-drop caused by the oxidation of ferrous iron. The results show that chemical immobilisation using iron(II)sulphate is a promising way to protect groundwater quality at sites contaminated with timber preservation and pigment production remnants. As a prerequisite, optimum amendment levels need to be established and practical/field tests should be accompanied by a monitoring for a broad range of relevant trace elements.

This study was aimed at elucidating the importance of original Pb-speciation versus soil-characteristics to mobility and distribution of Pb in industrially polluted soils. Ten industrially polluted Danish surface soils were characterized and Pb speciation was evaluated through SEM-EDX studies, examination of pH-dependent desorption, distribution in grain-size fractions and sequential extraction. Our results show that the first factors determining the speciation of Pb in soil are: (1) the stability of the original speciation and (2) the contamination level, while soil characteristics are of secondary importance. In nine of ten soils Pb was concentrated strongly in the soil fines (< 0.063 mm). In all soils, particles with a highly concentrated Pb-content were observed during SEM-EDX. In eight of the soils, the particles contained various Pb-species with aluminum/iron, phosphate, sulfate and various metals (in solder and other alloys) as important associates. In the one soil, where Pb was not concentrated in the soil fines, Pb was precipitated solely as PbCrO₄, while pure (metallic) Pb was repeatedly observed in the last soil. Pb was bound strongly to the soils with > 50% extracted in step III (oxidizing) and IV (residual) of sequential extraction for all soils but one. A significant amount of exchangeable Pb existed only in severely contaminated soils, where the bonding capacity of organic matter and oxides was exceeded. Among soil constituents, Pb was observed to adsorb preferentially to feldspars and organic matter while presence of phosphate increased the strength of the Pb-bonding in phosphate-rich soils.

Danish rivers carry >50% of the phosphorus (P) transport as particulate P (PP). In five of six rivers sampled in November 1998 iron-bound P made up > 59% of PP and loosely adsorbed P ranged between 2% and 13%. This fraction could potentially be released in 14[per thousand] seawater. The behaviour of dissolved and particulate P fractions was studied during seven month in a 2 km long estuary with low freshwater retention time and low tidal range. The river carried ~10% of PP as loosely adsorbed P but increased concentrations of dissolved inorganic P (DIP) relative to the estuarine mixing line was only observed in the summer month with low freshwater flow and was more likely due to DIP release from the bottom sediment. Instead estuarine particles were always enriched with oxidized iron (ox.Fe) and iron-bound P as well as loosely adsorbed P and during May-September this coincided with increasing concentration of PP in estuary. We suggest that flocculation of ox.Fe and adsorption of DIP onto the particles with subsequent transport seawards is a major loss process for P during the summer month. During winter month where 85% of the run-off occurs the dominant process in the estuary is sedimentation of larger particles, however, a comparison of river particles with surface sediment clearly reveals that most PP is mobilized again from the bottom sediments.

The overall objective of this research was to develop a reliable, robust, and maintenance-free passive system for biological denitrification in on-site wastewater treatment systems. The process relies on sulfur oxidizing denitrifying bacteria in upflow packed bioreactors. Since this process consumes alkalinity, it is necessary to add a solid-phase buffer that can scavenge the H⁺ as it is generated by the biologically-mediated reaction and arrest the drop in the pH value. This study investigated the use of limestone, marble chips and crushed oyster shell as solid-phase buffers that provide alkalinity. Two bench-scale upflow column reactors and two field-scale bioreactors were constructed and packed with sulfur pellets and an alkalinity source. The pilot scale bioreactors (~200 L each) were installed at the Massachusetts Alternative Septic System Test Center (MASSTC) in Sandwich, MA. The pilot-scale bioreactors performed better when oyster shell was used as the solid-phase buffer vis-à-vis marble chips. In both (pilot-scale and laboratory-scale) systems, denitrification rates were high with the effluent NO₃ - --N concentration consistently below 8 mg/L.

In August of 2003 a severe wildfire burnt the majority of Fishtrap Creek, a 170 km² catchment in central British Columbia, Canada. The objective of this study was to determine the short-term (15-month) influence of the wildfire on the amount and composition of fine sediment delivery and retention in the system and to compare it to a similar unburnt catchment. In the spring of 2004 automatic water samplers were installed at a gauging site on Fishtrap Creek to collect suspended sediments from the snowmelt runoff and gravel traps were deployed on the channel bed surface to collect composite samples of suspended fine sediment. Jamieson, the reference creek, exhibits similar geology and pre-burn vegetation and was sampled in the same manner for comparison. Composite suspended sediment collected in the traps was removed from the streams in mid-summer and early September. Quantitative estimates of the amount and particle size structure of the naturally stored fine sediment in, and on, the gravel creekbed were obtained in pre-melt, mid and late-summer conditions. Estimates of suspended sediment yields indicated that while the burnt system delivered 66% more material per unit area, the total seasonal suspended sediment yield was low (855 kg km-²) compared to other fire-disturbed systems. While the burnt catchment was primed to deliver sediment, the hydrologic drivers were not of sufficient magnitude to generate a substantial response, suggesting that in this first post-fire year the system was transport-limited, not supply-limited. Differences were noted in the spatial and seasonal composition of the <500 more OM% composite suspended sedimentswith the burnt catchment having significantly (P<=0.05) more OM%. Seasonally a significant increase of OM% in late summer samples was associated with instream biofilms and possible delivery of black carbon. The system's post-fire response was not geomorphically substantial but significant biological differences were noted in the short-term.

To reconstruct a history of polycyclic aromatic hydrocarbon (PAH) pollution in the Gulf of Trieste, one of the largest urbanized areas in the Adriatic Sea, we analyzed three long sediment cores collected between 1996 and 1997. Concentrations of total PAHs, the sum of 16 PAH compounds and six of their methylated analogues, in all three cores show a decrease from 600-800 ng g-¹, at the surface, to levels below 250 ng g-¹ in deepest layers (down to 3 m). The same trend was shown with separate representative pyrogenic PAHs (pyrene, benzofluoranthene and phenanthrene). Using Hg as a recent geochronological tracer, we observe an increasing input of PAHs since the beginning of the 20th Century and, especially, after the Second World War coinciding with increasing industrialization and urbanization of the region. This correlation is supported by PAH ratios that are indication of combustion processes and represent a marker for anthropogenic inputs. No correlation exists between PAHs and black carbon within the core profiles, indicating two different fractions of the 'black carbon continuum'.