Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.     

Heavy metal contamination in the seaweeds of the Venice lagoon

The concentrations of heavy metals (Fe, Zn, Cu, Cd, Ni, Pb, Cr, As) were determined in seven seaweeds of environmental and commercial relevance (Ulva rigida C. Ag., Gracilaria gracilis (Stackhouse) Steentoft, L. Irvine and Farnham, Porphyra leucosticta Thuret, Grateloupia doryphora (Montagne) Howe., Undaria pinnatifida (Harv.) Suringar, Fucus virsoides J. Agardh, Cystoseira barbata (Good. et Wood.) Ag.) collected in four sampling sites in the lagoon of Venice, in spring and autumn 1999. Metals were extracted using hot concentrated acids in a Microwave Digestion Rotor and analysed by absorption spectrophotometry using a flame mode for Fe and Zn and a graphite furnace for Pb, Cr, Cd, Cu, Ni and As. High contamination levels, especially for Pb, were detected in Ulva and to a lesser extent in Gracilaria. Brown seaweeds, especially Cystoseira was highly contaminated by As. The least contaminated genera with all metals except As were Porphyra and Undaria. A concentration decrease for Zn and Cd was observed from the inner parts of the central lagoon, close to the industrial district, towards the lagoon openings to the sea.     

Salinity, organic content, micronutrients and heavy metals in pig slurries from South-eastern Spain

The increase in commercial pig production is an opportunity to reuse animal manures in arid and semiarid soils as a source of nutrients and organic matter. However, there are components in pig slurry that are potentially dangerous for the environment. In this study, pig slurries of 36 pig farms in South-eastern Spain were evaluated for salt content (electrical conductivity, chloride and sodium), organic load (BOD5 and COD), micronutrients (Fe, Cu, Mn and Zn), and heavy metals (Cd, Co, Cr, Ni and Pb). Except for electrical conductivity, Cu and Zn, components in pig slurries did not vary considerably between animal production stages, indicating similar management of diverse animal types. Assuming an application rate based on the maximum input of nitrogen from animal manure (210 kg total N/ha/yr), the estimates for soil annual load of Cl and Na, 415 kg/ha, could be a significant salinisation risk. Cu and Zn seemed to be the metals that could be accumulated most in soils where application of pig slurries is common (4 and 15 kg/ha/yr, respectively). The estimated heavy metal (Cd, Co, Cr, Ni and Pb) input to soils would be 260 g/ha/yr, with a relative contribution of Cr>Ni>Pb>Co>Cd.     

Solid waste management in Abuja, Nigeria

The new city of Abuja provided an opportunity to avoid some of the environmental problems associated with other major cities in Africa. The current status of solid waste management in Abuja has been reviewed and recommendations for improvements are made. The existing solid waste management system is affected by unfavourable economic, institutional, legislative, technical and operational constraints. A reliable waste collection service is needed and waste collection vehicles need to be appropriate to local conditions. More vehicles are required to cope with increasing waste generation. Wastes need to be sorted at source as much as possible, to reduce the amount requiring disposal. Co-operation among communities, the informal sector, the formal waste collectors and the authorities is necessary if recycling rates are to increase. Markets for recycled materials need to be encouraged. Despite recent improvements in the operation of the existing dumpsite, a properly sited engineered landfill should be constructed with operation contracted to the private sector. Wastes dumped along roads, underneath bridges, in culverts and in drainage channels need to be cleared. Small-scale waste composting plants could promote employment, income generation and poverty alleviation. Enforcement of waste management legislation and a proper policy and planning framework for waste management are required. Unauthorized use of land must be controlled by enforcing relevant clauses in development guidelines. Accurate population data is necessary so that waste management systems and infrastructure can be properly planned. Funding and affordability remain major constraints and challenges.     

Control of GHG emission at the microbial community level

All organic material eventually is decomposed by microorganisms, and considerable amounts of C and N end up as gaseous metabolites. The emissions of greenhouse relevant gases like carbon dioxide, methane and nitrous oxides largely depend on physico-chemical conditions like substrate quality or the redox potential of the habitat. Manipulating these conditions has a great potential for reducing greenhouse gas emissions. Such options are known from farm and waste management, as well as from wastewater treatment. In this paper examples are given how greenhouse gas production might be reduced by regulating microbial processes. Biogas production from manure, organic wastes, and landfills are given as examples how methanisation may be used to save fossil fuel. Methane oxidation, on the other hand, might alleviate the problem of methane already produced, or the conversion of aerobic wastewater treatment to anaerobic nitrogen elimination through the anaerobic ammonium oxidation process might reduce N2O release to the atmosphere. Changing the diet of ruminants, altering soil water potentials or a change of waste collection systems are other measures that affect microbial activities and that might contribute to a reduction of carbon dioxide equivalents being emitted to the atmosphere.     

Amelioration of physical strength in waste foundry green sands for reuse as a soil amendment

To avoid increasing costs of landfill disposal, it has become increasingly important for U.S. foundries to identify beneficial reuses for the 8 to 12 million tons of waste foundry sand (WFS) generated annually. A major drawback to the reuse of some WFSs as a soil amendment is their high soil strength, under dry conditions, where root growth may be limited. Fifteen WFSs were analyzed for strength to rupture using lab-formed clods, exchangeable cations (Na, Mg, Ca), metal oxide concentration (Fe, Mn, Al, Si), cation exchange capacity (CEC), and % clay. Several WFS samples from gray iron foundries demonstrated high strength to rupture values (> 1.5 MPa), and could potentially restrict root growth in amended soils. The percentage of Na-bentonite exhibited a positive correlation (R(2) = 0.84) with strength to rupture values. When WFSs containing more Na-bentonite were saturated with 1 mol L(-1) Ca ions, strength values decreased by approximately 70%. Waste foundry sands containing less Na-bentonite were saturated with 1 mol L(-1) Na ions and exhibited a threefold increase in strength. Additions of gypsum (up to 9.6 g kg(-1) sand) to high strength waste foundry sands also caused decreases in strength. These results indicate that high strength WFSs have properties similar to hardsetting soils which are caused by high Na(+) clay content and can be ameliorated by the addition of Ca(2+).     

Sorption and mobility of ivermectin in different soils

Avermectins are widely used to treat livestock for parasite infections. Ivermectin, which belongs to the group of avermectins, is particularly hazardous to the environment, especially to crustaceans and to soil-dwelling organisms. Sorption is one of the key factors controlling transport and bioavailability. Therefore, batch studies have been conducted to characterize the sorption and desorption behavior of ivermectin in three European soils (Madrid, York, and artificial soil). The solid-water distribution coefficient (K(d)) for ivermectin sorption to the tested soils were between 57 and 396 L kg(-1) (determined at 0.1 microg g(-1)), while the organic carbon-normalized sorption coefficients (K(oc)) ranged from 4.00 x 10(3) to 2.58 x 10(4) L kg(-1). The Freundlich sorption coefficient (K(F)) was 396 (after 48 h) for the artificial soil over a concentration range of 0.1 to 50 microg g(-1), with regression constants indicating a concentration-dependent sorption. The obtained data and data in the literature are inconclusive with regard to whether hydrophobic partitioning or more specific interactions are involved in sorption of avermectins. For abamectin, hydrophobic partitioning seems to be one of the dominant types of binding, while hydrophobicity is less important for ivermectin, which is probably due to the lower lipophilicity of the molecule. Furthermore, the presence of cations such as Ca(2+) leads to decreasing sorption. Thus, it is presumed that ivermectin binds to soil by formation of complexes with immobile, inorganic soil matter. In contrast to abamectin, hysteresis could be excluded for ivermectin in the studied soils for the evaluation of sorption and desorption. The sorption mechanism is highly dependent on physicochemical properties of the avermectin.     

Whole-stream response to nitrate loading in three streams draining agricultural landscapes

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.     

Empirical models based on the universal soil loss equation fail to predict sediment discharges from Chesapeake Bay catchments

The Universal Soil Loss Equation (USLE) and its derivatives are widely used for identifying watersheds with a high potential for degrading stream water quality. We compared sediment yields estimated from regional application of the USLE, the automated revised RUSLE2, and five sediment delivery ratio algorithms to measured annual average sediment delivery in 78 catchments of the Chesapeake Bay watershed. We did the same comparisons for another 23 catchments monitored by the USGS. Predictions exceeded observed sediment yields by more than 100% and were highly correlated with USLE erosion predictions (Pearson r range, 0.73-0.92; p < 0.001). RUSLE2-erosion estimates were highly correlated with USLE estimates (r = 0.87; p < 001), so the method of implementing the USLE model did not change the results. In ranked comparisons between observed and predicted sediment yields, the models failed to identify catchments with higher yields (r range, -0.28-0.00; p > 0.14). In a multiple regression analysis, soil erodibility, log (stream flow), basin shape (topographic relief ratio), the square-root transformed proportion of forest, and occurrence in the Appalachian Plateau province explained 55% of the observed variance in measured suspended sediment loads, but the model performed poorly (r(2) = 0.06) at predicting loads in the 23 USGS watersheds not used in fitting the model. The use of USLE or multiple regression models to predict sediment yields is not advisable despite their present widespread application. Integrated watershed models based on the USLE may also be unsuitable for making management decisions.