Paramagnetic effects on solid state carbon-13 nuclear magnetic resonance spectra of soil organic matter

The effects of paramagnetic species on solid state 13C nuclear magnetic resonance (NMR) spectra were quantified in a series of doping experiments. The degree of signal loss caused by paramagnetic metals was shown to depend not only on the quantity, but also on the nature of the paramagnetic species, as well as the intimacy of contact with the organic substrate and the type of NMR experiment. Two mechanisms of signal loss were distinguished--signal loss via loss of magnetic field homogeneity, which affects all 13C nuclei in a sample, and signal loss via interaction between electronic and nuclear spins, the effects of which were localized to the close environment of the paramagnetic species. Loss of field homogeneity is important for manganese species, but not for copper species, and is equally important for both cross polarization and Bloch decay experiments. The interaction between electronic and nuclear spins is highly dependent on the spin-lattice relaxation rate constant of the free electron (T1e), as cations with very short T1e values (e.g., Pr3+) cause less signal loss than cations with longer T1e values (e.g., Cu2+, Mn2+). Cross polarization spectra are shown to be more susceptible than Bloch decay spectra to this mechanism of signal loss. Signal loss and increased relaxation rates brought about by paramagnetic species can be used to provide information on soil organic matter (SOM) heterogeneity in the submicron range. This is demonstrated for SOM doped with paramagnetic cations where selective signal loss and increased relaxation rates are used to determine the nature of cation exchange sites.     

Effect of methodology in estimating and interpreting water-extractable phosphorus in animal manures

Manure water-extractable phosphorus (WEP) data are used in indices and models to assess P transport in runoff. Methods to measure WEP vary widely, often without understanding the effect on how much P is extracted. We conducted water extractions on five dairy, swine, and poultry manures to assess single and sequential extractions, drying manures, solution to solid (cm3 g(-1)) extraction ratios, and P determination method. We found little difference in WEP of single or sequential extractions. Increasing extraction ratio from 10:1 to 250:1 resulted in more WEP recovered, but in a diminishing fashion so that ratios of 200:1 and 250:1 were not significantly different. Patterns of increased WEP with extraction ratio varied with manure type, presence of bedding material, and drying treatment. Fresh and air-dried manures had similar patterns, but differed substantially from oven-dried (90 degrees C) manures. The differential effect of oven-drying on WEP was greatest for dairy and poultry manure, and less for swine manure. We analyzed water extracts colorimetrically before and after digestion, to examine the potential effect of P determination by inductively coupled plasma (ICP) spectroscopy. Digested extracts always contained more P. For manures with bedding, drying decreased the difference in P measured before and after digestion. The opposite was true for manures without bedding. Results highlight the influence of methodology on manure WEP measurement and caution needed when comparing data across studies using different WEP methods. Overall, our results point to a need for a standard manure water extraction method.     

Drainage Investment and Wetlands Loss: an Analysis of the National Resources Inventory Data

The United States Soil Conservation Service (SCS) conducts a survey for the purpose of establishing an agricultural land use database. This survey is called the National Resources Inventory (NRI) database. The complex NRI land classification system, in conjunction with the quantitative information gathered by the survey, has numerous applications. The current paper uses the wetland area data gathered by the NRI in 1982 and 1987 to examine empirically the factors that generate wetland loss in the United States. The cross-section regression models listed here use the quantity of wetlands, the stock of drainage capital, the realty value of farmland and drainage costs to explain most of the cross-state variation in wetland loss rates. Wetlands preservation efforts by federal agencies assume that pecuniary economic factors play a decisive role in wetland drainage. The empirical models tested in the present paper validate this assumption.     

Bioaccumulation of Selenium by the Bryophyte Hygrohypnum ochraceum in the Fountain Creek Watershed, Colorado

Aquatic bryophytes, Hygrohypnum ochraceum, were deployed “in situ” at 14 sites in the Fountain Creek Watershed, spring and fall, 2007 to study selenium (Se) accumulation. Dissolved, total, and pore (sediment derived) water samples were collected and water quality parameters determined while plants were exposed to the water for 10?days. There was a trend showing plant tissue-Se uptake with distance downstream and we found a strong correlation between Se in the water with total hardness in both seasons. There was a modest association between Se-uptake in plants with hardness in the spring of 2007 but not the fall. Plants bioconcentrated Se from the water by a factor of 5.8?×?10³ at Green Mountain Falls and 1.5?×?10⁴ at Manitou Springs in the fall of 2007. Both are examples of the bioconcentration abilities of the plants, primarily in the upper reaches of the watershed where bioconcentration factors were highest. However, the mean minima and maxima of Se in the plants in each of the three watershed segments appeared similar during both seasons. We found direct relationships between the pore and dissolved Se in water in the spring (R ²?=?0.84) and fall (R ²?=?0.95) and dissolved Se and total hardness in the spring and fall (R ²?=?0.92). The data indicate that H. ochraceum was a suitable indicator of Se bioavailability and Se uptake in other trophic levels in the Fountain Creek Watershed based on a subsequent study of Se accumulation in fish tissues at all 14 sites.     

Bioavailability of permethrin and cyfluthrin in surface waters with low levels of dissolved organic matter

Pyrethroids are widely used insecticides in both agricultural and urban environments, and their potential movement to surface streams and toxicity to susceptible aquatic species is an emerging concern. Natural surface waters usually contain low levels of dissolved organic matter (DOM). Limited data have shown that DOM preparations can significantly alter the bioavailability and toxicity effects of pyrethroids. However, the importance of these effects in natural waters has not been investigated. In this study we measured uptake and acute toxicity of permethrin and cyfluthrin by Daphnia species in 15 surface water samples. Low levels of DOM (3-20 mg L(-1)) inhibited cyfluthrin uptake by Daphnia magna and acute toxicity to Ceriodaphnia dubia in most samples. For permethrin, the effects of DOM on bioavailability and toxicity were generally not significant. The effects of DOM on bioavailability of cyfluthrin could not be explained from the DOC concentration alone, suggesting that properties of DOM were also important in regulating bioavailability. Regression of K DOC with selected DOM properties revealed significant dependence of K DOC on the carboxylic acid content of DOM. Moreover, concentrations sensed by solid-phase microextraction (SPME) fibers were well correlated with the observed changes in bioaccumulation by D. magna and acute toxicity to C. dubia. Therefore, selective sampling methods such as SPME may be used for measuring the bioavailable concentrations of pyrethroids in waters with naturally occurring DOM levels and predicting the actual toxicity effects.     

Assessing the pollutional load from nonpoint sources: Planning considerations and a description of an automated water quality monitoring program

Planning considerations to be evaluated early in the design of water quality monitoring programs are reviewed. These criteria emphasize the importance of isolating the study area, parameter section, and type of measurements required to ensure meaningful results. A demonstration automatic water quality monitoring program is described. Details with respect to type of equipment, coordination of component parts, sampling program, and analysis of specific parameters are reviewed. General costs of implementation and maintenance of such programs are presented.