Movement of lagoon-liquor constituents below four animal-waste lagoons

Movement of liquor constituents from animal-waste lagoons has the potential to degrade ground water quality. The depth of movement and concentrations of lagoon-liquor constituents in the soil underlying three cattle (Bos taurus)-waste retention lagoons and one swine (Sus scrofa)-waste lagoon were determined. Samples were taken by using a direct-push coring machine, dissected by depth, and analyzed for total N, organic C, CaCO3, pH, cation exchange capacity (CEC), texture, and extractable NO3, NH(4), P, Cl, Ca, Mg, K, and Na. Ammonium N concentrations were greatest in the upper 0.5 m of soil under all four lagoons with concentrations ranging from 94 to 1139 mg kg(-1). Organic N was determined to make up between 39 and 74% of the total N beneath all lagoons. The swine lagoon had 2.4 kg N m(-2) in the underlying soil whereas the cattle lagoon with highest quantity of N had 1.2 kg N m(-2) in the underlying soil. Although N concentrations decreased with depth, N was greater than expected background levels at the bottom of some cores, indicating that the sampling efforts did not reach the bottom of the N plume. Nitrate N concentrations were generally less than 5 mg kg(-1) immediately below the lagoon floor. In the uppermost 0.5 m of soil underlying the swine and three cattle lagoons, NH4+ occupied 44% and between 1 and 22% of the soil cation exchange sites, respectively. The depth of movement of N under these lagoons, as much as 4 m, may pose remediation difficulties at lagoon closure.     

Nitrogen cycling through swine production systems: ammonia, dinitrogen, and nitrous oxide emissions

Ammonia (NH(3)) emissions from animal systems have become a primary concern for all of livestock production. The purpose of this research was to establish the relationship of nitrogen (N) emissions to specific components of swine production systems and to determine accurate NH(3) emission factors appropriate for the regional climate, geography, and production systems. Micrometeorological instrumentation and gas sensors were placed over two lagoons in North Carolina during 1997-1999 to obtain information for determining ammonia emissions over extended periods and without interfering with the surrounding climate. Ammonia emissions varied diurnally and seasonally and were related to lagoon ammonium concentration, acidity, temperature, and wind turbulence. Conversion of significant quantities of ammonium NH(4)(+) to dinitrogen gas (N(2)) were measured in all lagoons with the emission rate largely dependent on NH(4)(+) concentration. Lagoon NH(4)(+) conversion to N(2) accounted for the largest loss component of the N entering the farm (43% as N(2)); however, small amounts of N(2)O were emitted from the lagoon (0.1%) and from field applications (0.05%) when effluent was applied nearby. In disagreement with previous and current estimates of NH(3) emissions from confined animal feeding operation (CAFO) systems, and invalidating current assumptions that most or all emissions are in the form of NH(3), we found much smaller NH(3) emissions from animal housing (7%), lagoons (8%), and fields (2%) using independent measurements of N transformation and transport. Nitrogen input and output in the production system were evaluated, and 95% of input N was accounted for as output N from the system.     

Significance of anion exchange in pentachlorophenol sorption by variable-charge soils

Sorption data and subsequent predictive models for evaluating acidic pesticide behavior on variable-charge soils are needed to improve pesticide management and environmental stewardship. Previous work demonstrated that sorption of pentachlorophenol (PCP), a model organic acid, was adequately modeled by accounting for pH-and pKa-dependent chemical speciation and using two organic carbon-normalized sorption coefficients; one each for the neutral and anionic species. Such models do not account for organic anion interaction to positively charged surface sites, which can be significant for variable-charge minerals present in weathered soils typical of tropical and subtropical regions. The role of anion exchange in sorption of ionizable chemicals by variable-charge soils was assessed by measuring sorption of PCP by several variable-charge soils from aqueous solutions of CaCl2, CaSO4, Ca(H2PO4)2 as a function of pH. Differences in sorption from phosphate and chloride electrolyte solutions were attributed to pentachlorophenolate interactions with anion exchange sites. Suppression of PCP sorption by phosphate ranged from negligible in a soil with essentially no positively charge sites, as measured by negligible anion exchange capacity, to as much as 69% for variable-charge soils. Pentachlorophenolate exchange correlated well with the ratio of pH-dependent anion exchange capacity to net surface charge. Sorption reversibility of PCP by both CaCl2 and Ca(H2PO4)2 solutions was also demonstrated. Results for PCP clearly demonstrate that sorption to anion exchange sites in variable-charge soils should be considered in assessing pesticide mobility and that phosphate fertilizer application may increase the mobility of acidic pesticides.     

Influence of quaternary ammonium on sorption of selected metal cations onto clinoptilolite zeolite

Clay minerals and zeolites have large cation exchange capacities, which enable them to be modified by cationic surfactant to enhance their sorption of organic and anionic contaminants. In this study, the influence of quaternary ammonium surfactants on sorption of five metal cations (Cs+, Sr+, La3+, Pb2+, and Zn2+) onto a clinoptilolite zeolite was investigated. Generally, the metal cation sorption capacity and affinity for the zeolite decreased, indicating that presorbed cationic surfactants blocked sorption sites for metal cations, as the surfactant loading on the zeolite increased. Cesium and Pb2+ sorption was affected to a small extent, indicating that selective sorption for Cs+ and specific sorption for Pb2+ play an important role in addition to cation exchange. Sorption of cationic surfactants on zeolite preloaded with different metal cations showed a strong correlation with the chain length of the surfactant tail group, while the roles of the charges and types of the metal cations were minimal. As the chain length increases, the critical micelle concentration decreases and the surfactant molecules become more hydrophobic, resulting in progressive bilayer coverage. Desorption of presorbed metal cations by cationic surfactants was strongly affected by the surfactant chain length and metal type. More metal cations, particularly Sr2+ and Zn2+, desorbed with an increase in surfactant chain length. The results, in combination with those from organic and oxyanion sorption on surfactant-modified zeolite, may be used for future surfactant modification to target sorption and desorption of a specific type of contaminant or a mixture of different types of contaminants.     

Immobilization of cesium-137 and uranium in contaminated sediments using soil amendments

Batch and dynamic leaching methods were used to evaluate the effectiveness of hydroxyapatite (HA), illite, and zeolite, alone and in combination, as soil additives for reducing the migration of cesium-137 (137Cs+) and uranium (U) from contaminated sediments. Amendment treatments ranging from 0 to 50 g kg(-1) were added to the sediment and equilibrated in 0.001 M CaCl2. After equilibration, the treatment supernatants were analyzed for 137Cs+, U, PO4, and other metals. The residual sediments were then extracted overnight using one of the following: 1.0 M NH4Cl, 0.5 M CaCl2, or the Toxicity Characteristic Leaching Procedure (TCLP) extractant. Cesium was strongly sorbed to the contaminated sediments, presumably due to interlayer fixation within native illitic clays. In fact, 137Cs+ was below detection limits in the initial equilibration solutions, the CaCl2 extract, and the TCLP solution, regardless of amendment. Extractants selective for interlayer cations (1.0 M NH4Cl) were necessary to extract measurable levels of 137Cs+. Addition of illitic clays further reduced Cs+ extractability, even when subjected to the aggressive extractants. Zeolite, however, was ineffective in reducing Cs+ mobility when subjected to the aggressive extractants. Hydroxyapatite was less effective than illite at reducing NH4+-extractable Cs+. Hydroxyapatite, and mixtures of HA with illite or zeolite, were highly effective in reducing U extractability in both batch and leaching tests. Uranium immobilization by HA was rapid with similar final U concentrations observed for equilibration times ranging from 1 h to 30 d. The current results demonstrate the effectiveness of soil amendments in reducing the mobility of U and Cs+, which makes in-place immobilization an effective remediation alternative.     

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+).     

Extra-framework cation release from heulandite-type rich tuffs on exchange with NH(4)(+)

The outgoing cations of Greek heulandite-rich tuff samples (heulandite type-III, 91wt.%, mica 4wt.%, feldspar 5wt. %, CEC 2.22meq/g) were analysed upon exchange with ammonium acetate using atomic absorption spectrometry (AAS). The kinetic curves of each cation were investigated over a total time of contact of 720h with sampling at frequent intervals. The materials were examined by powder X-ray diffraction, SEM-EDS, and AAS. The sorption ability was measured using the ammonium acetate saturation method. It was found that Ca(2+) presents an unexpected extra-framework release and a surprisingly high degree of exchange (90%). The exchange of Mg (57%) is also worthy of note whereas the behavior of K(+) showed an expected rapid initial release. The behavior of Na(+) must be similar. However, its lower concentration in the zeolitic material minimizes its overall significance somewhat. On the other hand, Ca(2+) and Mg(2+) release is kinetically much slower, compared to that of alkali metal ions, and this phenomenon indicates that different exchange energies are needed till final equilibrium.     

Greenhouse gas emissions from two soils receiving nitrogen fertilizer and swine manure slurry

The interactive effects of soil texture and type of N fertility (i.e., manure vs. commercial N fertilizer) on N(2)O and CH(4) emissions have not been well established. This study was conducted to assess the impact of soil type and N fertility on greenhouse gas fluxes (N(2)O, CH(4), and CO(2)) from the soil surface. The soils used were a sandy loam (789 g kg(-1) sand and 138 g kg(-1) clay) and a clay soil (216 g kg(-1) sand, and 415 g kg(-1) clay). Chamber experiments were conducted using plastic buckets as the experimental units. The treatments applied to each soil type were: (i) control (no added N), (ii) urea-ammonium nitrate (UAN), and (iii) liquid swine manure slurry. Greenhouse gas fluxes were measured over 8 weeks. Within the UAN and swine manure treatments both N(2)O and CH(4) emissions were greater in the sandy loam than in the clay soil. In the sandy loam soil N(2)O emissions were significantly different among all N treatments, but in the clay soil only the manure treatment had significantly higher N(2)O emissions. It is thought that the major differences between the two soils controlling both N(2)O and CH(4) emissions were cation exchange capacity (CEC) and percent water-filled pore space (%WFPS). We speculate that the higher CEC in the clay soil reduced N availability through increased adsorption of NH(4)(+) compared to the sandy loam soil. In addition the higher average %WFPS in the sandy loam may have favored higher denitrification and CH(4) production than in the clay soil.     

Ion cycling in hemlock-northern hardwood forests of the southern Lake Superior region: a preliminary study

Upland forests of the southern Lake Superior region are diverse and contain a shifting mosaic of eastern hemlock [Tsuga canadensis (L.) Carr.] and northern hardwood forests dominated by sugar maple (Acer saccharum Marsh.). In this study, we survey the relative effects of management practice (old growth vs. managed), forest cover type (hemlock vs. northern hardwood), and soil great group (Entic Haplorthod vs. Alfic Oxyaquic Fragiorthod) on ion cycling as a precursor to a longer-term, more detailed study. Bulk precipitation, throughfall, and soil leachates at three depths were collected for two growing seasons in eight stands on the Ottawa National Forest in the Upper Peninsula of Michigan. A total of 1210 solutions were analyzed for pH, Na, K, Mg, Ca, Cl, NO3, and SO4. Losses of base cations (Ca, Mg, K) and SO4 from the bottom of the rooting zone generally were greater in old-growth than in managed northern hardwoods on both fragic and nonfragic soils. Leaching losses of base cations and NO3 usually were greater beneath old-growth northern hardwoods than beneath old-growth hemlock on both soil types and for both forest cover types and management practices on fragic than nonfragic soils. Management practice, forest cover type, and soil type all appear to affect ion cycling within these forests. All of the stands featured striking losses of base cations that probably are influenced strongly by NO3 and SO4 in atmospheric deposition.     

A transport model with coupled ternary exchange and chemisorption retention for hydrazinium cations

A numerical model was developed to describe the fate and transport of hydrazinium (N2H5+) and competing Ca2+ and H+ cations applied in acidic solutions to columns of Ca2+/H+-saturated sandy soil during steady saturated flow conditions. Instantaneous ternary H+-Ca2+-N2H5+ cation exchange using the Gaines-Thomas approach was combined with second-order, irreversible, kinetic chemisorption of exchange-phase N2H5+ ions as major retention mechanisms for N2H5+. Exchange-mediated chemisorption is assumed to occur as chemical binding of N2H5+ ions located on carboxyl-group exchange sites to nearby carbonyl groups, consequently decreasing the effective soil cation exchange capacity (CEC). Comparison of simulated and observed breakthrough curves (BTCs) for concentrations of N2H5+ and Ca2+ ions in column effluent was used in model evaluation. The cation transport model with cation exchange coupled with exchange-mediated chemisorption provided a valid first approximation for N2H5+ transport.     

Response of biogeochemical indicators to a drawdown and subsequent reflood

Temporal oscillations in hydrology are a common occurrence in wetlands and can result in alternating flooded and drained conditions in the surface soil. These oscillations in water levels can stimulate microbial activities and result in the mobilization and redistribution of significant amounts of carbon (C), nitrogen (N), and phosphorus (P). The goal of this study was to experimentally simulate a drawdown and reflood of marsh soil from a nutrient-enriched site and a reference site of a wetland (Blue Cypress Marsh Conservation Area, Florida). The goal was to better understand the changes in biogeochemistry and microbial activities present in these soils as a result of hydrological fluctuations. Measurements of dissolved reactive phosphorus (DRP), ammonia, and nitrate in the floodwater indicated significantly higher (alpha = 0.05) NH(4)(+) and DRP fluxes from the nutrient-enriched site; floodwaters in the cores from both sites contained significant NO(3)(-) concentrations (9.6 mg N L(-1)), which was rapidly consumed over the core incubation period (30 d). Water level drawdown and reflooding initially stimulated the soil microbial biomass, methanogenic rates, and extracellular enzyme activities (acid phosphatase and beta-glucosidase). The anaerobic microbial metabolic activities (CO(2)) where initially significantly (alpha = 0.05) enhanced by the reflood, resulting in roughly equivalent rates as the aerobic respiratory activities (CO(2)), presumably as a function of the high water column NO(3)(-) levels. This study illustrates that the reflood event in the hydrological cycles in a wetland can significantly stimulate the activities of hydrolytic enzymes and microbiological communities in these soils.     

Metal immobilization in soils using synthetic zeolites

In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.     

Peat fire effects on some properties of an artificially drained peatland

The management of artificially drained organic soils is a very important issue, since the accelerated mineralization and sometimes peat fires alter physical and chemical properties of soils and the availability of plant nutrients. This study was performed to determine relatively short- and long-term effects of peat fires on some physical and chemical properties of soils in the artificially drained Gavur Lake Peatland of Turkey. To achieve this objective, measured properties of soils burned in 2001, burned in 1965, and unburned were compared. The results indicated that soil bulk density, pH, amounts of soluble salts, CaCO3, and concentrations of ammonium acetate-extractable (AAE) Ca, Mg, K, and Na were significantly higher for both sampling depths in the burned areas. The areas burned in 2001 had higher pH, soluble salts, and the concentrations of AAE Ca, Mg, and K compared with sites burned in 1965, and this was reasoned with leaching losses and plant uptake of these basic cations for four decades in the latter. Percent saturation and organic carbon contents of soils, however, were significantly lower in the burned areas for both sampling depths. Olsen P levels were not significantly different between the sites. This work clearly shows that alterations in soils properties with peat fires do not recover in the long term.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Adsorption-desorption behavior of copper at contaminated levels in red soils from China

Adsorption-desorption of copper (Cu2+) at contaminated levels in two red soils was investigated. The red soil derived from the Quaternary red earths (clayey, kaolinitic thermic plinthite Aquult) (REQ) adsorbed more Cu2+ than the red soil developed on the Arenaceous rock (clayey, mixed siliceous thermic typic Dystrochrept) (RAR). The maximum adsorption values (M(A)) that are obtained from the simple Langmuir model were 25.90 and 20.17 mmol Cu2+ kg(-1) soil, respectively, for REQ and RAR. Adsorption of Cu2+ decreased soil pH, by 0.8 unit for the REQ soil and 0.6 unit for the RAR soil at the highest loadings. The number of protons released per Cu2+ adsorbed increased sigmoidally with increasing initial Cu2+ concentration for the RAR soil, but the relationship was almost linear for the REQ soil. The RAR soil released about 2.57 moles of proton per mole of Cu2+ adsorbed at the highest Cu2+ loading and the corresponding value for the REQ soil was 1.12. The distribution coefficient (Kd) decreased exponentially with increasing Cu2+ loading. Most of the adsorbed Cu2+ in the soils was readily desorbed in the NH4Ac. After five successive extractions with 1 mol L(-1) NH4Ac (p 5.0), 61 to 95% of the total adsorbed Cu2+ in the RAR soil was desorbed and the corresponding value for the REQ soil was 85 to 92%, indicating that the RAR soil had a greater affinity for Cu2+ than the REQ soil at low levels of adsorbed Cu2+.     

Heavy metal release from contaminated soils: comparison of column leaching and batch extraction results

Heavy metals in soils may adversely affect environmental quality. In this study, we investigated the release of Zn, Cd, Pb, and Cu from four contaminated soils by column leaching and single and sequential batch extractions. Homogeneously packed soil columns were leached with 67 mL/g 10(-2) M CaCl2 to investigate the exchangeable metal pool and subsequently with 1400 mL/g 10(-2) M CaCl2 adjusted to pH 3 to study the potential of metal release in response to soil acidification. In two noncalcareous soils (pH 5.7 and 5.1), exchange by Ca resulted in pronounced release peaks for Zn and Cd that were coupled to the exchange of Mg by Ca, and 40 to 70% of total Zn and Cd contents were rapidly mobilized. These amounts compared well with exchangeable pools determined in single and sequential batch extractions. In two soils with near-neutral pH, the effluent concentrations of Zn and Cd were several orders of magnitude lower and no pronounced elution peaks were observed. This behavior was also observed for Cu and Pb in all four soils. When the soils were leached at pH 3, the column effluent patterns reflected the coupling of CaCO3 dissolution (if present) and other proton buffering reactions, proton-induced metal release, and metal-specific readsorption within the soil column. Varying the flow rate by a factor of five had only minor effects on the release patterns. Overall, Ca exchange and subsequent acidification to pH 3 removed between 65 and 90% of total Zn, Cd, Pb, and Cu from the four contaminated soils.     

Biosolids-derived nitrogen mineralization and transformation in forest soils

Utilization of biosolids through land application is becoming increasingly popular among wastewater managers. To minimize the potential contamination of receiving waters from biosolids-derived nitrogen (N), it is important to understand the availability of N after land application of biosolids. In this study, four secondary biosolids (two municipal and two pulp and paper industrial biosolids) were used in a laboratory incubation experiment to simulate N mineralization and transformation after land application. Municipal biosolids were from either aerobically or anaerobically digested sources, while pulp and paper industrial biosolids were from aerated wastewater stabilization lagoons. These biosolids were mixed with two New Zealand forest soils (top 100 mm of a volcanic soil and a brown soil) and incubated at two temperatures (10 and 20 degrees C) for 26 wk. During incubation, mineralized N was periodically leached from the soil-biosolids mixture with 0.01 M CaCl2 solution and concentrations of NH4 and NO3 in leachate were determined. Mineralization of N from aerobically digested municipal biosolids (32.1%) was significantly more than that from anaerobically digested biosolids (15.2%). Among the two pulp and paper industrial biosolids, little N leached from one, while as much as 18.0% of total organic N was leached from the other. As expected, mineralization of N was significantly greater at 20 degrees C (average 22.8%) than at 10 degrees C (average 9.7%). It was observed that more N in municipal biosolids was mineralized in the brown soil, whereas more N in pulp and paper industrial biosolids mineralized in the volcanic soil. Transformation of NH4 to NO3 was affected by soil type and temperature.     

Wildfire effects on soil nutrients and leaching in a tahoe basin watershed

A wildfire burned through a previously sampled research site, allowing pre- and post-burn measurements of the forest floor, soils, and soil leaching near Lake Tahoe, Nevada. Fire and post-fire erosion caused large and statistically significant (P < or = 0.05) losses of C, N, P, S, Ca, and Mg from the forest floor. There were no statistically significant effects on mineral soils aside from a decrease in total N in the surface (A11) horizon, an increase in pH in the A11 horizon, and increases in water-extractable SO4(2-) in the A11 and A12 horizons. Burning caused consistent but nonsignificant increases in exchangeable Ca2+ in most horizons, but no consistent or statistically significant effects on exchangeable K+ or Mg2+, or on Bray-, bicarbonate-, or water-extractable P concentrations. Before the burn, there were no significant differences in leaching, but during the first winter after the fire, soil solution concentrations of NH4+, NO3-, ortho-P, and (especially) SO4(2-) were elevated in the burned area, and resin lysimeters showed significant increases in the leaching of NH4+ and mineral N. The leaching losses of mineral N were much smaller than the losses from the forest floor and A11 horizons, however. We conclude that the major short-term effects of wildfire were on leaching whereas the major long-term effect was the loss of N from the forest floor and soil during the fire.     

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.     

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.