Manure history and long-term tillage effects on soil properties and phosphorus losses in runoff

Manure additions to cropland can reduce total P losses in runoff on well-drained soils due to increased infiltration and reduced soil erosion. Surface residue management in subsequent years may influence the long-term risk of P losses as the manure-supplied organic matter decomposes. The effects of manure history and long-term (8-yr) tillage [chisel plow (CP) and no-till (NT)] on P levels in runoff in continuous corn (Zea mays L.) were investigated on well-drained silt loam soils of southern and southwestern Wisconsin. Soil P levels (0-15 cm) increased with the frequency of manure applications and P stratification was greater near the surface (0-5 cm) in NT than CP. In CP, soil test P level was linearly related to dissolved P (24-105 g ha(-1)) and bioavailable P (64-272 g ha(-1)) loads in runoff, but not total P (653-1893 g ha(-1)). In NT, P loads were reduced by an average of 57% for dissolved P, 70% for bioavailable P, and 91% for total P compared with CP. This reduction was due to lower sediment concentrations and/or lower runoff volumes in NT. There was no relationship between soil test P levels and runoff P concentrations or loads in NT. Long-term manure P applications in excess of P removal by corn in CP systems ultimately increased the potential for greater dissolved and bioavailable P losses in runoff by increasing soil P levels. Maintaining high surface residue cover such as those found in long-term NT corn production systems can mitigate this risk in addition to reducing sediment and particulate P losses.     

Biosolids decomposition after surface applications in west Texas

In a semiarid environment, climate is a critical factor in the decomposition of surface-applied biosolids. This study examined the effect of 2- to 7-yr exposure times on the composition of single applications of New York, NY biosolids in western Texas. Exposure time effects on organic matter, N, P, S, Cu, Cr, Pb, Hg, and Zn were studied near Sierra Blanca, TX. Due to organic matter decomposition, total organic C decreased from 340 g kg(-1) in fresh biosolids to 180 g kg(-1) in biosolids after 82 mo of exposure, whereas the inorganic ash content of the biosolids increased from 339 to 600 g kg(-1). Total N decreased from 50 to 10 g N kg(-1) and total S decreased from 12 to 6 g S kg(-1). Bicarbonate-available P in the biosolids decreased from 0.9 to 0.2 g kg(-1). Successive H2O extractions yielded soluble P concentrations consistent with dicalcium phosphate (dical) for fresh biosolids and tricalcium phosphate (trical) for biosolids exposed for 59 months or more. Sparingly soluble phosphates, such as dical and trical, potentially yield > 0.5 mg P L(-1) in runoff waters for extended periods after biosolids applications, especially after multiple applications. Selective dissolution of the biosolids indicated that as much as 66 to 78% of P exists as iron phosphates, 16 to 21% as Fe oxides, and 5 to 12% as insoluble Ca phosphates. Chemical analyses of ash samples suggest that Cu and Zn have been lost from biosolids through leaching or runoff and no losses of Pb, Cr, or Hg have occurred since application.     

The effect of five forage species on transport and transformation of atrazine and isoxaflutole (balance) in lysimeter leachate

A field lysimeter study with bare ground and five different ground covers was established to evaluate the effect of forage grasses on the fate and transport of two herbicides in leachate. The herbicides were atrazine (ATR; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and isoxaflutole [IXF; 5-cyclopropyl-4-(2-methylsulfonyl-4-trifluormethyl-benzoyl)isoxazole], which has the commercial name Balance (Aventis Crop Science, Strasbourg, France). The ground covers included orchardgrass (Dactylis glomerata L.), smooth bromegrass (Bromus inermis Leyss.), tall fescue (Festuca arundinacea Schreb.), timothy (Phleum pratense L.), and switchgrass (Panicum virgatum L.). The results suggested that the total IXF (parent + metabolites) showed higher mobility than ATR and its metabolites. Differences in the timing of transport reflected the rapid degradation of IXF to the more soluble, stable, and biologically active diketonitrile (DKN) metabolite in the system. Although grass treatments did not promote the hydrolysis of DKN, they significantly reduced its transport in the leachate through enhanced evapotranspiration. Grass treatments significantly enhanced ATR degradation in the leachates and soils, especially through N dealkylation, but they did not reduce total ATR transported in the leachate. Leachate from the orchardgrass lysimeters contained the highest proportion of ATR metabolites (64.2%). Timothy and smooth bromegrass treatments also displayed a significant increase in ATR metabolites in leachate. Grass-treated lysimeters showed higher microbial biomass carbon than bare ground. For ATR treatments, the proportion of metabolites in the leachate strongly correlated with the elevated soil microbial biomass carbon in forage treatments. In contrast, DKN degradation was poorly correlated with soil microbial biomass carbon, suggesting that DKN degradation is an abiotic process.     

Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains"

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.     

Effects of static vs. tidal hydrology on pollutant transformation in wetland sediments

This work addressed effects of hydrology on biogeochemical processes relevant to pollutant chemical transformation in wetland sediments. Microcosms were designed to impose three hydrologic conditions on salt marsh sediments: (i) drained-oxidized redox potenial (Eh); (ii) flooded-reduced Eh and, (iii) diurnal tide-oscillating Eh. The test chemicals were N- and/or S-heterocycles (NSHs) including quinoxaline (1,4-benzodiazine), 2-methylquinoxaline(2-methyl-1,4-benzodiazine), 2,3-dimethylquinoxalinen (2,3-dimethyl-1,4-benzodiazine), phenazine (2,3,5,6-dibenzo-1,4-diazine), acridine (2,3,5,6-dibenzopyridine), dibenzothiophene (2,3,5-dibenzothiophene), phenothiazine (dibenzo-1,4-thiazine), and phenanthridine (2,3-benzoisoquinoline). Biogeochemical processes reflected the hydrologic conditions in ways analogous to field settings, e.g., Eh characteristics were drastically different: static (flooded and drained) systems had reduced (mu = -428 mV +/- 57) and oxidized (mu = +73 mV +/- 32) values, respectively, with no evidence of periodic variation while the tidal systems exhibited regularly oscillating Eh (amplitudes 40-250 mV). Sediment trace gases also corresponded to the Eh, with the major species detected being CO2 and H2O (drained, tidal) vs. CO2 + H2O + sulfides + methane (flooded). The NSH transformation rates were different in each hydrologic regime and decreased as follows: tidal > or = drained > flooded. These results indicated that there were subtle differences in NSH processing in drained and tidal systems, but both of these systems transformed NSHs faster and to lower levels than flooded sediments. These data suggest that in situ remediation options that preserve wetland integrity and tidal hydrology can be as or more effective than static conditions that obtain in approaches such as impoundment and excavation-upland placement.     

Relationship between water repellency and native and petroleum-derived organic carbon in soils

Some soils develop severe and persistent water repellency following contamination with crude oil. This study was conducted to characterize and compare the spatial distribution of soil water repellency and residual oil contamination at 12 such sites. The molarity of ethanol droplet (MED) test was used to assess soil water repellency and the content of dichloromethane-extractable organics (DEO) was used to quantify residual oil in soil. We found a relatively strong positive correlation between MED and DEO in soil (r2 = 0.74). Both variables tended to decrease abruptly with depth at 11 of the 12 study sites. Dichloromethane-extractable organics similarly decreased with depth in control adjacent soil (MED = 0 M), but from an average concentration one to two orders of magnitude lower than in water-repellent soil. Using data from corresponding control adjacent and water-repellent soils, we determined that approximately 29 and 10% of measured total organic carbon in water-repellent A- and B-horizon soil, respectively, consists of dichloromethane-insoluble organic carbon of petroleum origin. We propose that this fraction contains most of the causative agents of soil water repellency at the studied sites.     

Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.     

Geographic Analysis of Forest Health Indicators Using Spatial Scan Statistics

Geographically explicit analysis tools are needed to assess forest health indicators that are measured over large regions. Spatial scan statistics can be used to detect spatial or spatiotemporal clusters of forests representing hotspots of extreme indicator values. This paper demonstrates the approach through analyses of forest fragmentation indicators in the southeastern United States and insect and pathogen indicators in the Pacific Northwest United States. The scan statistic detected four spatial clusters of fragmented forest including a hotspot in the Piedmont and Coastal Plain region. Three recurring clusters of insect and pathogen occurrence were found in the Pacific Northwest. Spatial scan statistics are a powerful new tool that can be used to identify potential forest health problems.     

Field testing of particulate matter continuous emission monitors at the DOE Oak Ridge TSCA incinerator. Toxic Substances Control Act

A field study to evaluate the performance of three commercially available particulate matter (PM) continuous emission monitors (CEMs) was conducted in 1999-2000 at the US Department of Energy (DOE) Toxic Substances Control Act (TSCA) Incinerator. This study offers unique features that are believed to enhance the collective US experience with PM CEMs. The TSCA Incinerator is permitted to treat PCB-contaminated RCRA hazardous low-level radioactive wastes. The air pollution control system utilizes MACT control technology and is comprised of a rapid quench, venturi scrubber, packed bed scrubber, and two ionizing wet scrubbers in series, which create a saturated flue gas that must be conditioned by the CEMs prior to measurement. The incinerator routinely treats a wide variety of wastes including high and low BTU organic liquids, aqueous, and solid wastes. The various possible combinations for treating liquid and solid wastes may present a challenge in establishing a single, acceptable correlation relationship for individual CEMs. The effect of low-level radioactive material present in the waste is a unique site-specific factor not evaluated in previous tests. The three systems chosen for evaluation were two beta gauge devices and a light scattering device. The performance of the CEMs was evaluated using the requirements in draft Environmental Protection Agency (EPA) Performance Specification 11 (PS11) and Procedure 2. The results of Reference Method 5i stack tests for establishing statistical correlations between the reference method data and the CEMs responses are discussed.