Adsorption of pesticides from water by functionalized organobentonites

Replacement of natural inorganic cations of clay minerals with organic cations has been proposed as a strategy to improve the adsorptive capacity of clay minerals for organic compounds, including pesticides. The organic cations most commonly used for this purpose have been quaternary ammonium ions containing alkyl or aryl chains without specific functional groups. In this work, we evaluated the ability of two bentonites (SWy-2 and SAz-1) exchanged with four natural organic cations containing diverse functional groups (L-carnitine, L-cysteine ethyl ester, L-cystine dimethyl ester, and thiamine) as adsorbents of pesticides varying in their chemical structures (simazine, hexazinone, triadimefon, alachlor, carbaryl, and imazethapyr). For comparison purposes, the adsorptive properties of two "classical" organobentonites, hexadecyltrimethylammonium- and phenyltrimethylammonium-exchanged bentonites, were also determined. Most organobentonites displayed higher affinity for the pesticides than the untreated bentonites, but the improvement in adsorption capacity varied depending on the characteristics of the pesticide and the interlayer organic cation. Triadimefon, carbaryl, and imazethapyr displayed the highest affinity for carnitine (K(f) = 229-2377)-, thiamine (K(f) = 83-354)-, and cystine (K(f) = 96-100)-treated bentonites, respectively, whereas alachlor was adsorbed similarly by all organobentonites. In general, pesticide adsorption-desorption hysteresis was greater for adsorbents with the highest adsorption capacities. The results demonstrate that selective modification of smectitic clay minerals with natural organic cations containing appropriate functional groups can be a useful strategy to improve their performance for the removal of specific pesticides from the environment.     

Onset of luteal activity in foaling and seasonally anoestrous mares treated with artificial light.

Sixty-four mares (27 foaling, 37 barren or maiden), mainly Finnhorses, were subjected to treatment with 14.5 h of light and 9.5 h of darkness, starting at the beginning of December. The onset of cycling in non-foaling mares was estimated by weekly serum progesterone determinations. All of the non-foaling mares cycled in the middle of March. They started to cycle on average in the middle of February, 11.1 weeks after the beginning of the trial. There were statistically significant differences in relation to breed (Finnhorses started to cycle 2 weeks later than warm blooded, p less than 0.02) and in relation to age (brood mares with mean age 10 years, started to cycle 10 days later than those 3 years old, p less than 0.03). However, there was no statistical significant relation to previous lactation, although lactating mares lactating up to the previous autumn started to cycle 7 days later than dry mares (p less than 0.15). Artificial insemination of 14 mares in the 2nd oestrus of the year, in March, resulted in 12 foalings in the subsequent year (86%). The following winter, all pregnant mares (N = 27) were exposed to the same kind of light treatment, starting on 1st December. The 1st mare foaled at the end of January. The time from foaling to 1st post partum ovulation was significantly longer (17.0 days) in foalings taking place within 10 weeks from the beginning of the light treatment period, than in foalings occurring after more than 10 weeks of lighting (12.1 days) (p less than 0.01).     

Onset of luteal activity in non-foaling mares during the early breeding season in Finland.

The luteal activity in mares was studied in the Equine Research Station (ERS) and in trotting stables (TS) in South-Finland. The mares were Standardbreeds in the TS and mainly Finnhorses in the ERS. Between January and June blood was collected once a week for serum progesterone determinations. The mares in the ERS were distributed in 1 of 3 groups: three-years old not yet in training (N = 38), brood mares (N = 21) and mares in training (N = 47). A 4th group was the mares in training in the trotting stables (N = 73). Every 5th mare in the ERS and every 4th mare in the trotting stables were cycling already at the beginning of the year. Onset of luteal activity in anoestrous mares was most common in the middle of May. Over 95% of the mares were cycling at the beginning of June. In the ERS 40% of the Finnhorse mares in training were cycling through the winter. The three-years old and the brood mares were all anoestrous during winter. They started to cycle on average before the middle of May. Anoestrous training mares started before the middle of April. Anoestrous Finnhorse mares began to cycle later than warm blooded mares in all of the groups studied. Mares which had foaled the previous year were more often anoestrous during the winter than dry mares. The time of year when cycling began in a particular mare tended to be the same from year to year (p less than 0.01).     

Runoff and leaching of alachlor under conventional and soil-specific management

Abstract. The influence of conventional and soil-specific management on leaching and runoff losses of soil-applied alachlor (2-chloro-2',6'-diethyl- N -(methoxymethyl) acetanilide) was studied across a soil catena (landscape) with varied slope and drainage characteristics. The catena consisted of: a well-drained Ves (fine-loamy, mixed, mesic Udic Haplustoll) soil on the backslope (1–4%), a Ves soil on the sideslope (6–12%), and a poorly drained Webster (fine-loamy, mixed, mesic Typic Haplaquoll) soil on the toeslope (0–3%). In general, the concentration of alachlor in runoff water was greater in the Ves soil than in the Webster. In 1992 alachlor concentrations in runoff (water, sediment + water) were less for soil-specific rates (2.20 or 2.80 kg/ha) than for a uniform rate (3.36 kg/ha) in both Ves soils. There was no significant difference in alachlor concentration related to application rates (soil-specific rate 3.66 kg/ha) in the runoff from the Webster soil. Averaged across soils and events, the concentrations of alachlor in runoff (water, sediments + water) were less for soil-specific rates than for the uniform rate. Alachlor was not detected in soil samples obtained from depths greater than 15 cm in any soil or treatment after the first sampling. At the first sampling in 1992 (7 days after application) alachlor was detected down to 45 and 90 cm in the Ves and Webster soils, respectively. Detectable amounts (≥0.1 μg/1) of alachlor were observed in soil water samples extracted from all three soils during some sampling dates. No particular trends were observed with soils or application rates.     

Major compositional units of the moon: lunar prospector thermal and fast neutrons

Global maps of thermal and fast neutron fluxes from the moon suggest three end-member compositional units. A high thermal and low fast neutron flux unit correlates with the lunar highlands and is consistent with feldspathic rocks. The South Pole-Aitken basin and a strip that surrounds the nearside maria have intermediate thermal and fast neutron flux levels, consistent with more mafic rocks. There appears to be a smooth transition between the most mafic and feldspathic compositions, which correspond to low and high surface altitudes, respectively. The maria show low thermal and high fast neutron fluxes, consistent with basaltic rocks.     

Lunar Fe and Ti abundances: comparison of lunar prospector and clementine data

The Lunar Prospector neutron spectrometer data correlate well with iron and titanium abundances obtained through analysis of Clementine spectral reflectance data. With the iron and titanium dependence removed, the neutron spectrometer data also reveal regions with enhanced amounts of gadolinium and samarium, incompatible rare earth elements that are enriched in the final phases of magma crystallization. These regions are found mainly around the ramparts of the Imbrium impact basin but not around the other basins, including the much larger and deeper South Pole-Aitken basin. This result confirms the compositional uniqueness of the surface and interior of the Imbrium region.     

Characterization of triadimefon sorption in soils using supercritical fluid (SFE) and accelerated solvent (ASE) extraction techniques

Sorption–desorption of the fungicide triadimefon in field‐moist silt loam and sandy loam soils were determined using low‐density supercritical fluid extraction (SFE). The selectivity of SFE enables extraction of triadimefon from the soil water phase only, thus allowing calculation of sorption coefficients (K_d) at field‐moist or unsaturated conditions. Triadimefon sorption was influenced by factors such as soil moisture content and temperature; sorption increased with increased moisture content up to saturation, and decreased with increased temperature. For instance, K_d values for triadimefon on the silt loam and the sandy loam soils at 40 °C and 10% water content were 1.9 and 2.5 ml g⁻¹, respectively, and at 18% water content, 3.3 and 6.4 ml g⁻¹, respectively. Isosteric heats of sorption (ΔH_i) were −42 and −7 kJ mol⁻¹ for the silt loam and sandy loam soils, respectively. Sorption–desorption was also determined using an automated accelerated solvent extraction system (ASE), in which triadimefon was extracted from silt loam soil by 0.01 M CaCl₂. Using the ASE system, which is basically a fast alternative to the batch equilibration system, gave a similar ΔH_i value (−29 kJ mol⁻¹) for the silt loam soil (K_f = 27 µg^{1 − 1/n} ml^1/n g⁻¹). In order to predict transport of pesticides through the soil profile more accurately on the basis of these data, information is needed on sorption as a function of soil water content. © 2000 Society of Chemical Industry     

Organogenesis and foetal haemodynamics during the normal gestation of healthy black‐rumped agoutis (Dasyprocta prymnolopha,Wagler, 1831) bred in captivity

The objective of this study was to define the patterns of organogenesis and foetal haemodynamics during the normal gestation of healthy agoutis (Dasyprocta prymnolopha) kept in captivity. Thirty pregnant agoutis that ranged in size from small to medium and weighed between 2.5 and 3 kg underwent B‐mode and Doppler ultrasonography for the biometric evaluation of the foetal organs. The foetal aortic blood flow proved to be predominantly systolic, and the measured flow velocity was 78.89 ± 2.95 cm/s, with a maximum pressure gradient of 2.12 ± 0.27 mmHg. The liver was characterized by its large volume, occupying the entire cranial aspect of the abdominal cavity, and it was associated cranially with the diaphragm and caudally with the stomach. The flow velocity in the portal vein was estimated to equal 12.17 ± 2.37 cm/s, with a resistivity index of 0.82 ± 0.05. The gallbladder was centrally located and protruded cranially towards the diaphragm. The spleen was visualized as an elongated structure with tapered cranial and caudal extremities, and the foetal kidneys were visualized bilaterally in the retroperitoneal region, with the right kidney positioned slightly more cranially than the left. The morphological characterization and hemodynamic analysis of the foetal organs of black‐rumped agoutis via B‐mode and Doppler ultrasonography allow determination of the vascular network and of reference values for the blood flow required for perfusing the anatomical elements essential for maintaining the viability of foetuses at different gestational ages.     

Sequential changes of IgG and antitrypsin in different compartments during the colostral-intestinal transfusion of immunity to the newborn foal

IgG levels and tryptic inhibition were investigated in sequentially collected mare's colostrum and milk, foal serum and urine. The colostral trypsin-inhibitor was "transfused" to the newborn foal by the colostral intestinal route in parallel with IgG. However, the trypsin-inhibitor as a small molecular weight inhibitor became excreted into urine peaking at about 20 hours. The physiological proteinuria in foals during the first 2 days is mostly due to immunoglobulin fragments and colostral-derived trypsin-inhibitor. Analysis of urine for IgG light chains or trypsin inhibitor will therefore reveal ingestion of colostrum.     

Changes in sorption/bioavailability of imidacloprid metabolites in soil with incubation time

Changes in sorption/bioavailability of two metabolites, imidacloprid-urea {1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidinone} and imidacloprid-guanidine {1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine} of the insecticide imidacloprid {1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine} with aging in different soils were determined. Soil moisture was adjusted to -33 kPa and ¹⁴C- and analytical-grade imidacloprid-urea and imidacloprid-guanidine were added to the soil at a rate of 1.0 mg kg^-1. Spiked soils were incubated at 25°C for 8 weeks. Replicate soil samples were periodically extracted successively with 0.01 N CaCl₂, acetonitrile, and 1 N HCl. Imidacloprid-urea sorption, as indicated by sorption coefficient values, was highest in the soil with highest organic C content, and increased by an average factor of 2.6 in three soils during the 8-week incubation period. Imidacloprid-guanidine sorption increased by a factor of 2.3 in the same soils. The increase in sorption was the result of a decrease in the metabolite extractable with CaCl₂ (solution phase); the amount of metabolite extractable with acetonitrile and HCl (sorbed phase) did not significantly change with incubation time. It appears the increase in sorption was because the rate of degradation in solution and on labile sites was faster than the rate of desorption from the soil particles. It may have also been due to metabolite diffusion to less accessible or stronger binding sites with time. Regardless of the mechanism, these results are further evidence that increases in sorption during pesticide aging should be taken into account during characterization of the sorption process for mathematical models of pesticide degradation and transport.