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.

The Erzgebirge, part of the so-called former “Black Triangle”, used to represent the strongest regional air pollution of Central Europe. To test the hypothesis of deposition enhancement with height, an altitudinal gradient along a N-S transect from the Elbe river lowlands to the Erzgebirge summit was chosen to investigate chemical composition, elevation-related variability, temporal changes, and seasonal patterns of ion concentrations from 1993 to 2002. The following questions were to be answered: (1) Which role does orography play on the composition of precipitation?, (2) Does fog occurrence overrule the orographic influence?, (3) Are there changes in the past 10 years, and if so, why?, (4) Do relevant seasonal changes occur and why? Air streams from westerly and to a lesser degree south-easterly directions prevail. The average precipitation was ion-poor (23 μS cm-¹ and acidic (pH 4.5). Sulphate still was the dominant anion (52.3-59.9 μeq L-¹, while NH⁺ ₄ determined the cations (41.9-62.2 μeq L-¹. Ion concentrations decreased with altitude to about 735 m a.s.l. and subsequently increased. The seeder-feeder effect largely explains the chemical composition of precipitation; enhanced in winter through snow crystals. Sub-cloud scavenging does not explain the observed patterns. Fog occurrence enhanced the observed effects at higher altitudes. Deposition amounts doubled from the lowlands to the Erzgebirge summit. From 1993 to 2002, acidity decreased by about 50%, mainly due to reduced SO₂ -emissions.

Deposition and storage of fine sediment on channel beds represents an important component of a catchment's sediment budget and can have important implications for sediment-associated P fluxes, due to storage and remobilisation, and for P concentrations through water-sediment interactions. Spatial and temporal variations in P content and storage in fine bed sediment have been studied in two UK lowland catchments, the Rivers Frome and Piddle in Dorset. Fine bed sediment was sampled in representative reaches on a bi-monthly basis using a re-suspension cylinder, and the resulting samples were analysed for total P, a range of P fractions and particle size. The results demonstrate significant spatial and temporal variability in PP concentrations and storage, with maximum and minimum P concentrations and storage occurring in late summer and winter, respectively. Temporal variations in concentrations reflect residence times of the sediment and ambient P concentrations, while variations in storage are mainly due to hydrological regimes. Spatial variations reflect catchment characteristics, the location of inputs and local variations in hydrological and channel bed conditions.

Soil erosion and associated off-site environmental impacts have attracted increasing attention in recent decades, and there is a growing need for reliable information on rates of soil loss. The potential for using ¹³⁷Cs fallout to quantify rates and patterns of soil redistribution over medium-term timescales (ca. 45 years) has been successfully demonstrated in a wide range of environments around the world. The similar behaviour of fallout ²¹⁰Pb in soils offers potential for its use as an alternative to ¹³⁷Cs, in areas where ¹³⁷Cs inventories are low or are complicated by additional fallout from the Chernobyl accident. There have, however, to date been few attempts to validate the use of fallout ²¹⁰Pb measurements for assessing erosion rates. This paper reports an attempt to explore the use of fallout ²¹⁰Pb to estimate rates of water-induced soil erosion on uncultivated land. It focuses on three small forest/rangeland catchments located in Calabria, southern Italy, for which measurements of sediment output are available. Comparison of the estimates of net soil loss from the catchments derived from ²¹⁰Pb measurements with the measured sediment output, confirmed the validity of the ²¹⁰Pb approach. The soil redistribution rates estimated using ²¹⁰Pb measurements were also consistent with equivalent estimates obtained for the same study catchments using ¹³⁷Cs measurements.

The feasibility of degrading 16 USEPA priority polycyclic aromatic (PAH) hydrocarbons (PAHs) with heat and Fe(II)-EDTA catalyzed persulfate oxidation was investigated in the laboratory. The experiments were conducted to determine the effects of temperature (i.e. 20 [composite function (small circle)]C, 30 [composite function (small circle)]C and 40 [composite function (small circle)] C) and iron-chelate levels (i.e., 250 mg/L-, 375 mg/L- and 500 mg/L-Fe(II)) on the degradation of dissolved PAHs in aqueous systems, using a series of amber glass jars as the reactors that were placed on a shaker inside an incubator for temperature control. Each experiment was run in duplicate and had two controls (i.e., no persulfate in systems). Samples were collected after a reaction period of 144 hrs and measured for PAHs, pH and sodium persulfate levels. The extent of degradation of PAHs was determined by comparing the data for samples with the controls. The experimental results showed that persulfate oxidation under each of the tested conditions effectively degraded the 16 target PAHs. All of the targeted PAHs were degraded to below the instrument detection limits (~4 μ/L) from a range of initial concentration (i.e., 5 μ/L for benzo(a)pyrene to 57 μ/L for Phenanthrene) within 144 hrs with 5 g/L of sodium persulfate at 20 [composite function (small circle)] C, 30 [composite function (small circle)]C and 40 [composite function (small circle)]C. The data indicated that the persulfate oxidation was effective in degrading the PAHs and that external heat and iron catalysts might not be needed for the degradation of PAHs. The Fe(II)-EDTA catalyzed persulfate also effectively degraded PAHs in the study. In addition, the data on the variation of persulfate concentrations during the experiments indicated that Fe(II)-EDTA accelerated the consumption of persulfate ions. The obtained degradation data cannot be used to evaluate the influence of temperature and Fe(II) levels on the PAH degradation because the PAHs under each of the tested conditions were degraded to below the instrument detection limit within the first sampling point. However, these experiments have demonstrated the feasibility of degrading PAHs in aqueous systems with persulfate oxidation. Additional tests are being conducted to evaluate the effectiveness of treating PAHs in soils and obtaining the rate of degradation of PAHs with persulfate oxidation. Two sets of laboratory experiments were conducted to evaluate the ability of sodium persulfate in oxidizing real world PAH-contaminated soils collected from a Superfund site in Connecticut. The first set of soil sample were treated only with persulfate and to the second batch, mixture of persulfate and Fe(II)-EDTA solutions were added. The results of the second test showed that within 24 hours, 75% to 100% of the initial concentrations of seven PAH compounds detected in the soil samples were degraded by sodium persulfate mixed with FE(II)-EDTA.

As part of the NJ Toxics Reduction Workplan for NY-NJ Harbor, ambient water samples were collected at fifteen locations along the tidal portions of the Hackensack, Passaic, Raritan, Rahway and Elizabeth Rivers, and in Newark Bay, the Arthur Kill, and Kill van Kull. A Trace Organics Platform Sampler was used to collect a total of 75 suspended sediment phase samples between June 2000 and May 2002. These samples were analyzed for spatial and wet vs. dry weather trends in the 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs; modified USEPA Method 1613b). Mean total PCDD/F (tPCDD/F) concentrations at the sampling locations ranged between 3.8 and 41.5 ng/g. On average, OCDD accounted for almost 80% of the tPCDD/F concentrations; mean total [PCDD/F - OCDD] concentrations ranged between 0.84 and 5.20 ng/g at the sampling locations. Mean 2,3,7,8-TCDD concentrations ranged between 0.003 and 0.28 ng/g, with the highest concentrations (> 0.10 ng/g) along the tidal Passaic and lower Hackensack Rivers, and in upper Newark Bay. Mean tPCDD/F Toxic Equivalency Quotients (TEQ) ranged between 45 and 344 TEQ pg/g, with the highest levels found in the lower Passaic River. Toxicity was primarily driven by 2,3,7,8-TCDD concentrations in the Passaic and Hackensack Rivers, and in Newark Bay. Examples of congener distribution patterns at some of the sampling locations are also presented.

In a total of 189 water samples collected from Danish streams no traces of the pyrethroid esfenvalerate were detected. However, pyrethroids have previously been found in sediments in 9 out of 30 streams investigated. We found that the shredding activity of the Trichopteran Sericostoma personatum and the amphipod Gammarus pulex was significantly reduced with increased concentration of the pyrethroid lambda-cyhalohtrin adsorbed to the leaves on which they fed. Predation rate on the Plecopteran Leuctra nigra by the leech Erpobdella octoculata increased significantly with increasing concentration of lambda-cyhalothrin on the leaves on which L. nigra was fed. Our results clearly indicate that the ongoing monitoring of pesticides is likely to underestimate pyrethroid occurrence and that sediment-bound pyrethroids have a potential negative impact on ecosystem function and biotic interactions in streams.

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.

The objectives of this work were to characterize and compare the chemical composition of the water-soluble fraction of the PM₁₀ particles (Dp < 10μm) in two sites: one inside the Metropolitan Area of São Paulo (MASP) and another, 250km apart, inside the State Park of Serra do Mar (CUNHA) part of the Atlantic Forest Reserve, both located in São Paulo State, Brazil. The atmospheric particles were collected during dry and wet season. The morphologic parameters of the particles were characterized for the different size fractions of the collected material. In the aqueous extract of the particulate fine fraction the major ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl-, NO₃ -, NH₄ ⁺, SO₄ ²-) and trace elements (Al, Mn, Fe, Pb, Cd, Zn, Ti, Ni, Cu, Co, Ba) were determined. The morphological characteristics of the particles collected within the MASP are typical of polluted environment while in CUNHA there is no evidence of this type of contribution. Regarding the solute concentrations it was observed that the most abundant major ions and trace elements were K⁺, Ca²⁺, Na⁺, Cl- and Pb, for CUNHA and NO₃ -, SO₄ ²-, NH₄ ⁺ and Mn, Ni, Pb, Co, Cd and Ba for MASP. These differences are associated with the different sources of the particles. In the urban area they are predominantly of pollution origin, mainly from vehicle emissions, and road dust suspension, while in the State Park they are mainly of biogenic, terrigenous and oceanic origins. For these reasons the CUNHA region can be considered to be a regional reference site for studies concerning eventual disturbances in the Cunha background site, derived from transported pollution.

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.