Prediction of the temperature dependency of Henry's law constant using poly-parameter linear free energy relationships

The ability to predict the temperature dependence of air/water partitioning is important for the environmental fate modeling of organic pollutants. Here, literature data for the temperature dependence of air/water partitioning of some 200 compounds have been used to derive poly-parameter linear free energy relationships (pp-LFER) for predicting air/water partition coefficients at temperatures between 0 and 45 degrees C. The compounds used for calibrating the pp-LFERs span a range of almost 10 orders of magnitude in the partition constants and they cover a large variety of functional groups. Very good fits (r(2)>0.99) were obtained at all temperatures. Hence, these pp-LFERs should serve as a valuable tool for integrating the temperature dependence of air/water partitioning into fate modeling of organic compounds. In the environment one will quite often encounter a situation where water and air do not have the same temperatures. This situation is shortly discussed in the appendix.     

Analysis of the biomechanical response of kidneys under blunt impact

OBJECTIVE: This study addresses the biomechanical response of isolated kidneys to traumatic insult. METHODS: Kidneys were subjected to blunt impact by using a freely swinging right cylindrical pendulum. Force-deformation characteristics were derived for 65 impacted adult pig kidneys. Renal injuries were classified by autopsy, and an injury risk analysis was performed. In addition a finite element model that simulated the experiments was implemented. RESULTS/CONCLUSIONS: The kidneys showed a viscoelastic response. An energy-based injury threshold was identified, with a strain energy density of 21 kJ/m(3) corresponding to a 50-percent risk of renal injury level AIS3 or higher. Finally, the impact tests were simulated using a finite element model of the kidney to investigate relevant injury mechanisms. The model predicted the renal capsule and underlying parenchyma to first fail at an impact energy level of 4.0 J, consistent with experimental results.     

Response of Drinking-water Reservoir Ecosystems to Decreased Acidic Atmospheric Deposition in SE Germany: Signs of Biological Recovery

Strongly decreasing atmospheric emissions and acidic deposition during the 1990s have initiated chemical reversal from acidification in several drinking-water reservoirs of the Erzgebirge, SE Germany. We studied responses of phytoplankton, zooplankton and fish stocks in five reservoirs and at enclosure scale after experimental neutralization of 1,200 m³ of lake water. About 4 months after this treatment, diatoms and cryptomonads replaced the predominating chrysophytes and dinoflagellates. The colonization by acid-sensitive species of green algae, cryptomonads, rotifers and Cladocera (e.g. Bosmina longirostris) is explained by the occurrence of dormant stages or by survival of individuals in very low abundances. Analogous to the enclosure experiment, three reservoirs showed significantly (p < 0.01) falling trends of chlorophyll a and phytoplankton biovolume, mainly due to the decline of dinoflagellates. Picoplankton and diatoms increased slightly in two reservoirs. The zooplankton communities were dominated by rotifers and small Cladocera. Representatives of the genus Daphnia were lacking. Two reservoirs were re-colonized by zooplanktivorous fish populations of either perch (Perca fluviatilis) or sunbleak (Leucaspius delineatus). The latter exhibited extremely high fluctuating abundance and biomass and even suffered from a population crash. This natural mortality was caused by a limited food supply. Hence, severe top-down control may delay the recovery of larger zooplankton species like daphnids. Fishery management comprising the introduction of predatory fishes can help to control zooplanktivorous fish populations and to prevent their mass mortality.     

Forward pricing and efficiency in the silver market

If futures prices ‘fully reflect’ all available information, then these prices may be interpreted as market anticipations of spot (cash) prices at the delivery date of the futures contract. This hypothesis, which has tended to find most support among established markets for storable commodities, is investigated for the Chicago silver futures market. Using instrumental variable estimation and a joint (χ²) test, the unbiased prediction hypothesis is rejected, and a tentative explanation is offered for this outcome. This result, however, does not necessarily imply that the market is inefficient, and two tests of the weak form efficient markets hypothesis suggest that, while there is some slight dependence in past prices, this is only marginally more than would be expected from normal sampling variation.     

RELATION OF PHYSICAL AND MINERALOGICAL PROPERTIES TO STREAMBANK STABILITY1

ABSTRACT. Alluvial streambank materials from nine unstable and six stable reaches showed little variation in physical and mineralogical properties. The bulk density of all the samples was so similar that they could be considered from the same population. Particle size distributions showed that the clay fractions were slightly, but significantly, higher for the stable reaches. The mineralogy of all samples was also quite similar. The sand-sized grains of the stable areas were less rounded than those of the unstable areas. This somewhat angular shape of the grains may have produced an interlocking between grains that added stability to the bank material. Also, clay coatings on the sand-sized grains from the stable areas may have caused cementation between grains that also strengthened the material.     

Evaluating coal tar-water partitioning coefficient estimation methods and solute-solvent molecular interactions in tar phase

Equilibrium partitioning coefficients between an industrial coal tar sample and water (K(CT/w)) were determined for 41 polar and nonpolar solutes in batch systems. Together with literature values, 69 K(CT/w) data were analyzed using the following model approaches: Raoult's law, the single parameter linear free energy relationship (SPLFER) with octanol-water partitioning coefficients (K(ow)), the linear solvation energy relationships (LSERs), SPARC and COSMOtherm. Estimations by Raoult's law and the SPLFER agreed well with the experimental log K(CT/w) values for the investigated coal tar, with root mean square errors (RMSE) of 0.31 and 0.33, respectively. LSER resulted in as good estimations (RMSE=0.29) as the previous two. The LSER analysis revealed significant hydrogen (H)-bond acceptor properties of the studied coal tar phase. Using naphthalene as a surrogate solvent for the coal tar phase, SPARC and COSMOtherm provided fairly good predictions (RMSE of 0.63 and 0.65, respectively) of log K(CT/w), without any additional empirical parameter. Further calculations using SPARC and COSMOtherm for partitioning between water and other tar-components (e.g., benzofuran, phenol and quinoline) suggested that minor components in coal tar do not significantly influence K(CT/w) of nonpolar solutes, and that Raoult's law and the SPLFER thus may be generally applied to these types of solutes, e.g., polycyclic aromatic hydrocarbons and alkylbenzenes, regardless of coal tar compositions. In contrast, partitioning of H-bonding solutes (e.g., phenols) can significantly vary depending on the amount of polar tar-components such as N-heterocyclic aromatic compounds. Therefore, the presented successful applications of Raoult's law and SPLFER to the studied coal tar could be a special case, and these simple approaches may not provide reasonable estimations for partitioning of H-bonding solutes from compositionally different coal tars.     

Environmental benefits and economic costs of manure incorporation on dairy waste application fields

Model simulations performed representing dairies in a 93000 ha watershed in north central Texas suggest that manure incorporation results in reduced phosphorus (P) losses at relatively small to moderate cost to producers. Simulated manure incorporation with a tandem disk on fields double-cropped with sorghum/winter wheat resulted in up to 33, 45, and 37% reductions in per hectare sediment-bound, soluble, and total P losses in edge-of-field runoff, relative to simulated surface manure applications. The effects of incorporation were evaluated at three different manure application rates. On aggregate across all three manure application rates, significant declines in P losses were obtained with incorporation except for sediment-bound P losses under the N-based manure application rate scenario.We found that the practice of incorporating manure shortly after it has been broadcast on the soil surface could help reduce P losses in such situations where P-based rates alone prove inadequate. The cost the producer incurs when manure is incorporated is on average about 1% of net returns when manure is applied at the N rate and 2-3% when it is applied at alternative P-based rates. In practice the costs could be lower because producers may substitute the manure incorporation operation for a tandem disk operation performed prior to manure application. As more and more dairy producers switch to the use of sorghum and corn silage in dairy rations and consequent on-farm production of these forages, the practice of manure incorporation may help to reduce phosphorus losses resulting from dairy manure applications to fields with these forage crops.     

Contamination in Ontario farmstead domestic wells and its association with agriculture:: 1. Results from drinking water wells

Groundwater provides about 30% of water requirements in Ontario, but farm families depend almost entirely on private wells. Major potential contaminants on farms are nitrate (NO₃⁻), pathogenic microorganisms, pesticides and petroleum derivatives. A survey of farm drinking-water wells was conducted throughout the Province of Ontario, Canada, in 1991 and 1992 and tested for these contaminants. The main objectives of the survey were to determine the quality and safety of drinking water for farm families, and determine the effect of agricultural management on groundwater quality at a provincial scale. Four farm wells were chosen in each township where >50% of the land area was used for agricultural production. Elsewhere one well per township was usually sampled. Within each township the types of farming activity and dominant soils were additional criteria for selection. The network comprised 1292 of the estimated 500,000 water-wells in Ontario, and the study conformed to a stratified random survey. A subset of 160 wells, chosen by farm type, soil, and the presence or absence of a fuel storage tank, was investigated for the presence of petroleum derivatives: benzene, toluene, ethyl benzene, and xylene. About 40% of farm wells tested contained one or more of the target contaminants above the maximum acceptable concentration; 34% of wells had more than the maximum acceptable number of coliform bacteria, 14% contained NO₃⁻-N concentrations above 10 mg l⁻¹ limit and about 7% were contaminated with both bacteria and NO₃⁻. Only six wells contained pesticide residues above the interim maximum acceptable concentration (IMAC), but pesticides were detected in 7% of wells in winter and in 11% in summer. No wells contained detectable petroleum derivatives. These results for NO₃⁻ contamination were not significantly different from those reported for a survey of Ontario wells for the period 1950–1954, but the frequency of contamination by Escherichia coli was greater in the present study. None of the point sources investigated contributed significantly to the NO₃⁻ contamination. The percentage of wells contaminated by coliform bacteria decreased significantly with increasing separation of the well from the feedlot or exercise yard on livestock farms. A full statistical model including the type of well construction, depth, age and soil hydrologic group was developed to describe the frequency of NO₃⁻ contamination.