Incubation time effects on imazaquin desorption as determined by nonequilibrium thin-soil disc flow

Because organic sorption in soil may never reach equilibrium, a thin-disc flow nonequilibrium method may be helpful in understanding herbicide-soil interactions. This research was conducted to (i) determine the influence of incubation time on imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] desorption from soil, (ii) examine the influence of solution flow velocities on desorption, and (iii) elucidate the most appropriate kinetic model to describe imazaquin leaching. Soil at 7.5% moisture w/w was treated with imazaquin and incubated for 24, 72, and 168 h. Treated soil was sealed in an in-line filter apparatus and rinsed with 5.0 mM CaCl2 at 0.33, 0.67, or 1.0 mL min(-1). Effluent was collected as 1.0-mL fractions for a total of 50 mL. Flow was stopped for 24 h. When flow resumed, fractions were collected for an additional 15 mL. After the initial desorption, 79% of the imazaquin incubated for 24 h was leached. Increasing incubation time beyond 24 h reduced imazaquin leaching. After both desorption events, 13% of the initially applied imazaquin remained in the soil incubated for 168 h, compared with 7% with soil incubated for 24 h. Elovich and Freundlich kinetics accounted for 98% of the variance observed in the imazaquin desorption curves. First-order and diffusion kinetics accounted for 91% of the variance. Incubating soil for 72 h before desorption reduced the rate of imazaquin desorption by approximately 12%, compared with the 24-h incubation treatment. Imazaquin desorption was not affected by wash solution flow rate. These data suggest that the kinetics of desorption in prolonged desorption events are limited by transport phenomena (i.e., particle and film diffusion).     

Using nonequilibrium thin-disc and batch equilibrium techniques to evaluate herbicide sorption

Nonequilibrium disc-flow techniques may better reproduce dynamic soil-pesticide interactions than traditional batch sorption studies. Batch kinetic and equilibrium experiments and dual-label thin-disc flow experiments were conducted with atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazine-2,4-diamine) and imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] using a Demopolis silt loam (loamy-skeletal, carbonatic, thermic, shallow Typic Udorthent; 8% clay, 62 g kg(-1) organic matter, 7.6 pH). Batch kinetic studies with both herbicides revealed an almost instantaneous rapid phase and a much slower gradual phase. The rapid phase was complete after 5 min and equilibrium was reached at 24 h. The rapid phase accounted for 74% and 12 to 30% of the total amounts adsorbed for atrazine and imazaquin, respectively. The sorption of both the rapid and 24-h isotherms for each herbicide best fit the Freundlich equation. The rapid and 24-h K(f) values of atrazine were 1.38 and 2.41, respectively, and the N value of both phases was approximately 0.93. For imazaquin, the rapid and 24-h K(f) values were 0.056 and 035, respectively, and the N value for the rapid phase of imazaquin was 0.71, compared with 0.86 for the 24-h isotherm. In the dual-label thin-disc flow experiments, the average partition coefficient for atrazine at the peak soil concentration point was 1.54. This value closely agreed with the observed rapid-phase K(f) value of 1.38. In contrast, the thin-disc flow experiments failed to detect any imazaquin retention. The thin-disc flow method can allow for a greater resolution of rapid sorption kinetics, which is impractical with batch studies. Along with dynamic partitioning data, the thin-disc flow method may provide kinetics data that may better complement environmental models than coefficients generated with batch techniques.     

Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

Water-quality effects of incorporating poultry litter into perennial grassland soils

Poultry litter provides a rich source of nutrients for perennial forages, but the usual practice of surface-applying litter to pastures can degrade water quality by allowing nutrients to be transported from fields in surface runoff, while much of the NH4-N volatilizes. Incorporating litter into the soil can minimize such problems in tilled systems, but has not been used for perennial forage systems. In this study, we minimized disturbance of the crop, thatch, and soil structure by using a knifing technique to move litter into the root zone. Our objective was to determine effects of poultry litter incorporation on quantity and quality of runoff water. Field plots were constructed on a silt loam soil with well-established bermudagrass [Cynodon dactylon (L.) Pers.] and mixed grass forage. Each plot had 8 to 10% slopes, borders to isolate runoff, and a downslope trough with sampling pit. Poultry litter was applied (5.6 Mg ha(-1)) by one of three methods: surface-applied, incorporated, or surface-applied on soil-aeration cuts. There were six treatment replications and three controls (no litter). Nutrient concentrations and mass losses in runoff from incorporated litter were significantly lower (generally 80-95% less) than in runoff from surface-applied litter. By the second year of treatment, litter-incorporated soils had greater rain infiltration rates, water-holding capacities, and sediment retention than soils receiving surface-applied litter. Litter incorporation also showed a strong tendency to increase forage yield.     

New approach to studies of heavy metal redistribution in soil

The bioavailability and mobility of heavy metals in soils is dependent upon redistribution processes between solution and solid phases and among solid-phase components. This paper reviews the definitions and applications of two newly developed parameters, the redistribution index and the reduced partitioning parameter, in quantifying redistribution processes of heavy metals in contaminated soils. The redistribution index depicts the removal/attainment of metal-contaminated soils from/to the fractional distribution pattern characteristic of non-amended soils, while the reduced partitioning parameter quantifies the relative binding intensity of heavy metals in soils. Over time, metal salt-spiked and sludge-amended soils approached the fractional distribution pattern of non-amended soils. The rates of redistribution of metals and their binding intensity in soils were affected by the metal species, loading levels and soil properties. Metals in contaminated soils at low loading levels approach the fractional distribution pattern of non-amended soil more rapidly than those at high loading levels. The sequence order of approach by metals to the fractional distribution pattern of non-amended soil was: Cd>Cu>Ni=Zn>Cr. In both non-amended and contaminated soils, Cr had the highest binding intensity, Cd the lowest, and Cu, Ni and Zn, intermediate values. In addition to our own data, primarily on metal salt-spiked soils, these two indices are also used to evaluate redistribution processes of heavy metals in sewage sludge-amended soils from other published reports.     

Molecular structures and associations of humic substances in the terrestrial environment

Here we show, for the first time, evidence of the primary molecular structures in humic substances (HS), the most abundant naturally occurring organic molecules on Earth, and their associations as mixtures in terrestrial systems. Multi-dimensional nuclear magnetic resonance (NMR) experiments show us that the major molecular structural components in the mixtures operationally defined as HS are aliphatic acids, ethers, esters and alcohols; aromatic lignin derived fragments; polysaccharides and polypeptides. By means of diffusion ordered spectroscopy, distinct diffusion coefficients consistent with relatively low molecular weight molecules were observed for all the components in the mixtures, and saccharides were the largest single class of component present. Liquid chromatography NMR confirmed that HS components can be easily separated and nuclear Overhauser effect (NOE) enhancements support the finding that the components are of relatively low molecular weight <~2,000 Da. The widely recognized properties of HS, i.e., characteristics indicative of crosslinked, macromolecular networks, can now be explained as aggregation of mixtures, most likely instigated by complexation with metal cations.     

Accumulation, distribution, and toxicity of copper in sediments of catfish ponds receiving periodic copper sulfate applications

Copper sulfate (CuSO4) is applied periodically to commercial channel catfish (Ictalurus panctatus) ponds as an algicide or parasiticide. Current understanding of the chemistry of copper in soil-water systems suggests that copper may accumulate in pond sediments, although the forms and potential bioavailability of copper in catfish pond sediments are not known. This study investigated the accumulation and distribution of copper in the sediment of catfish ponds receiving periodic additions of CuSO4.5H2O. All ponds were constructed in Sharkey (very-fine, smectitic, thermic Chromic Epiaquert) soil. Nine 0.40-ha ponds received 59 applications of 2.27 kg CuSO4.5H2O per application per pond over 3 yr; no CuSO4.5H2O applications were made to nine additional ponds. Total Cu concentration in the sediments of CuSO4.5H2O-amended catfish ponds (172.5 mg kg(-1)) was four to five times higher than that in the sediments of nonamended ponds (36.1 mg kg(-1)). Copper accumulated in catfish pond sediments at a rate of 41 microg kg(-1) dry sediment for each 1 kg ha(-1) of CuSO4. 5H2O applied to ponds. Copper in the sediments of amended ponds was mainly in the organic matter-bound (30.7%), carbonate-bound (31.8%), and amorphous iron oxide-bound (22.1%) fractions with a considerable fraction (3.4%; 3 to 8 mg kg(-1)) in soluble and exchangeable fractions. This indicates that Cu accumulates differentially in various fractions, with proportionally greater initial accumulation in potentially bioavailable forms. However, toxicity bioassays with amphipods (Hyallela azteca) and common cattail (Typha latifolia L.) indicated that the effect of exposure to amended or nonamended pond sediments was not different.     

黏性颗粒在滤料表面沉积的动态模拟及规律

为研究颗粒黏性对过滤除尘性能的影响,分析了颗粒沉积过程的受力情况,应用颗粒流计算软件PFC2D对颗粒在滤料表面的沉积行为进行了数值模拟。结果表明:颗粒形成粉尘层的过程中主要受到风流力、惯性力等压缩力和范德华力、滚动摩擦力偶矩等压缩阻力的作用,颗粒黏性的增加,会使颗粒间滚阻系数和摩擦系数显著增加;PFC可实现粉尘颗粒在滤料表面沉积过程的可视化,得到不同黏性颗粒在滤料表面的沉积形态,滚阻系数或摩擦系数越大,粉尘层孔隙率越大,过滤阻力越小,其中,摩擦系数的影响作用弱于滚阻系数。     

Industrial age anthropogenic inputs of heavy metals into the pedosphere

Heavy metals have been increasingly released into our environment. We present here, for the first time, the global industrial age production of Cd, Cu, Cr, Hg, Ni, Pb, and Zn, and their potential accumulation and environmental effects in the pedosphere. World soils have been seriously polluted by Pb and Cd and slightly by Zn. The potential industrial age anthropogenic Pb, Hg, and Cd inputs in the pedosphere are 9.6, 6.1, and 5.2 times those in the lithosphere, respectively. The potential anthropogenic heavy metal inputs in the pedosphere increased tremendously after the 1950s, especially for Cr and Ni. In 2000, the cumulative industrial age anthropogenic global production of Cd, Cr, Cu, Hg, Ni, Pb, and Zn was 1.1, 105, 451, 0.64, 36, 235, and 354 million tonnes, respectively. The global industrial age metal burdens per capita (in 2000) were 0.18, 17.3, 74.2, 0.10, 5.9, 38.6, and 58.2 kg for Cd, Cr, Cu, Hg, Ni, Pb, and Zn, respectively. Acidification may increase the bioavailability and toxicity of heavy metals in the pedosphere. The improvement of industrial processing technology reducing the metal dispersion rate, the recycling of metal-containing outdated products, by-products and wastes, and the development of new substitute materials for heavy metals are possible strategies to minimize the effects of heavy metals on our environment.