Partitioning of formaldehyde between air and ice at −35°C to −5°C

The equilibrium partitioning of formaldehyde (HCHO) between air and snow was studied in a series of laboratory experiments conducted at −5°C, −15°C, and −35°C, in order to understand how partitioning of HCHO between air and polar snow varies with temperature, and thus seasonally on the ice sheet. Measured partitioning coefficients were 56, 93, and 245 mol l⁻¹ atm⁻¹ for −5°C, −15°C and −35°C, respectively, showing a similar trend as the values previously estimated from field observations. Estimates of the pseudo-first-order rate coefficient for air–snow exchange for the same three temperatures were 4.1×10⁻⁴, 1.1×10⁻⁴, and 1.1×10⁻⁵ s⁻¹, respectively. This implies a time scale for air–snow equilibration of the order of hours to days for HCHO accumulated at or near the ice–air interface on snow grains. Comparing the current laboratory partitioning coefficients with those estimated from measurements of air and freshly fallen snow in Greenland during summer demonstrates that the snow is supersaturated and should degas HCHO to the surrounding air. During this degassing, polar snow should be a significant source of HCHO to the lower troposphere.     

The solution phase complexing of atrazine by fulvic acid: Equilibria at 25°c

Abstract

The solution phase complexing equilibria of atrazine by fulvic acid at 25°C±1.° have been investigated over the pH range of 1.3 to 6.0. Experiments with 0.1MKC1 and chelated Cu(II) are compared with those without metal ions. The use of a fulvic acid having calibrated acidic and Cu(II) chelation properties has made it possible to obtain stoicheometricly “exact”; chemical information. This is correlated with previous hydrolysis kinetics work. It is concluded that atrazine is hydrogen bonded in a labile equilibrium, to an identifiable set of protonated carboxyl groups, which act as Brönsted acid catalysts for hydrolysis. 0.1M KC1 changes (1‐α_A), the degree of protonation of the carboxyl groups, without otherwise affecting the atrazine complexing. Cu(II) chelation both reduces and weakens the complexing through a combination of carboxyl group blocking, and fulvic acid aggregation. Simple equations are presented for predictive calculations.     

Meridional and vertical CO and CH4 distributions in the background troposphere (70°N-60°S; 0–12 km altitude) from scientific aircraft measurements during the stratoz III experiment (June 1984)

During the STRATOZ III experiment (June 1984) designed for a study of trace gases in the atmosphere, more than 2000 concurrent measurements of CO and CH₄ by gas chromatography were obtained from a series of flights aboard a scientific aircraft “Caravelle 116” between 70°N and 60°S, and up to a cruising altitude of 12 km, over the Atlantic Ocean and along the American, African and European continents.While a global interpretation of the data must await the examination of the whole series of compounds measured, a preliminary analysis of the results obtained for CO and CH₄ is reported here.The CO and CH₄ mixing ratios are found to be higher in the Northern Hemisphere than in the Southern, which reflects the meridional distribution of their sources and the influence of tropospheric photochemistry. A prominent CO difference between the two hemispheres is observed in the continental air (NH: 100–200 ppb; SH: 80–90 ppb) while the oceanic air is much more homogeneous (NH: 80–90 ppb; SH: 60–70 ppb). In the case of CH₄, a regular decrease is observed between the high latitudes of the Northern Hemisphere and those of the Southern.For the Southern Hemisphere, the CO values are in agreement with literature data, but for the Northern they are lower than previously reported. The CH₄ results suggest the possible existence of natural sources in the Southern Hemisphere (Amazonia; South Pacific).A comparison of the measurements made in the Southern Hemisphere with reliable data sets previously reported in the literature confirms an increase rate of 1.2 ± 0.3 % per year for CH₄, but does not provide any evidence for a long term variation of the CO content.The comprehensive data reported here will be of valuable interest to improve the understanding of the physico-chemistry of the troposphere and its evolution.     

The metabolic fate of 14C‐parathion by some fresh water phytoplankton and its possible effects on the algal metabolism

Abstract

The growth and total carbohydrate contents of Nostoc muscorum and Tolypothrix tenuis were greatly and significantly reduced by the application of parathion. “Chlorophyll a”, carotene biosynthesis and the rate of glucose absorption were enhanced after supplementation of parathion to the culture media of both cyanobacteria. Nitrogen released to the media, total nitrogen content and total nitrogen fixed were increased in both organisms‐ Increase in protein content was accompanied by remarkable drop in amino, peptide and ammonia fractions‐ Phosphorus uptake, RNA, DNA and total phosphorus content were accelerated to reach maximum accumulation at the highest insecticide level. In metabolism study using ¹⁴C‐labelled compound, parathion was readily degraded by Nostoc and Tolypothrix. Following ten days incubation, the aqueous fractions contained 21.1% and 18.1% of the initial activity in Nostoc and Tolypothrix respectively. TLC analysis of the hydrolytic products revealed the presence of three metabolites: p‐aminophenol, p‐nitrophenol and aminoparathion.     

Aged and bound herbicide residues in soil and their bioavailability part 2: Uptake of aged and non‐extractable (bound) [carbonyl‐14C] methabenzthiazuron residues by maize

Abstract

[Carbonyl‐ C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0–2,5 cm soil layer was removed from the lysimeter. This soil contained about 40 % of the applied radioactivity. Using 0,01 M CaCl₂ solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non‐extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3,6; 2,2; and 0,9 % of the radioactivity from soils containing aged MBT residues, MBT residues non‐extractable‐with 0,01 MCaCl₂ or MBT residues non‐extractable with organic solvents, respectively. About 20 % of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0,01 M CaCl₂ and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.