Superstatistics analysis of the ion current distribution function: Met3PbCl influence study.

A novel analysis of ion current time series is proposed. It is shown that higher (second, third and fourth) statistical moments of the ion current probability distribution function (PDF) can yield new information about ion channel properties. The method is illustrated on a two-state model where the PDF of the compound states are given by normal distributions. The proposed method was applied to the analysis of the SV cation channels of vacuolar membrane of Beta vulgaris and the influence of trimethyllead chloride (Met(3)PbCl) on the ion current probability distribution. Ion currents were measured by patch-clamp technique. It was shown that Met(3)PbCl influences the variance of the open-state ion current but does not alter the PDF of the closed-state ion current. Incorporation of higher statistical moments into the standard investigation of ion channel properties is proposed.

Degradation of alkyllead compounds to inorganic lead in contaminated soil.

In glass columns with sandy soil from a former antiknocking agents factory hydrophobic tetraalkyllead was transformed in oxygen-saturated water to inorganic lead. Up to 324 mg l(-1) trialkyllead, but only very little dialkyllead accumulated. After 740 days 49.1+/-6.7% of the organic lead was converted to inorganic lead. Conversion of hydrocarbons was 39.6+/-5.1%. To reduce toxicity of high trialkyllead concentrations the water of soil columns was replaced by tap water after 450d. Trialkyllead in the new water increased again to more than 150 mg l(-1). If the alkyllead-containing water from these columns was diluted to concentrations of alkyllead compounds that were found in the groundwater after air injection (total alkyllead<10 mg l(-1)) and used as a source of alkyllead compounds in columns with non-contaminated sandy soil, elimination of tetra-, tri- and dialkyllead compounds followed first-order kinetics. In the soil 85.8-93.6% of the alkyllead dissappeared in only 170 days with 51% being converted to inorganic lead. This makes in situ remediation reasonable.

Microbial degradation of tetraethyl lead in soil monitored by microcalorimetry.

Sieved agricultural soil samples were treated with the anti-knock agent tetraethyl lead (Et4Pb), and the resulting effects were analyzed by microcalorimetry. Et4Pb additions resulted in an increase of the heat production rate, provided that oxygen was present and that the soil was not autoclaved. The increased heat production rate was accompanied by degradation of Et4Pb, as verified by speciation analysis (GC-MS) of the remaining Et4Pb and its ionic degradation products (triethyl lead and diethyl lead cations). Conclusive evidence was obtained that these transformations were mediated mainly by microbes. At an initial Et4Pb concentration of 2 g Pb/kg dry weight the biodegradation rate was about 780 mumol day-1 kg dry weight-1, whilst the chemical decomposition was only 50 mumol day-1 kg dry weight-1. A fivefold rise of the initial Et4Pb concentration resulted in a decrease of the biodegradation rate to 600 mumol day-1 kg dry weight-1 and an increase of the chemical decomposition to 200 mumol day-1 kg dry weight-1. The biodegradation rate was not influenced by the addition of glucose, which means that no indication for a co-metabolic attack of Et4Pb was found.

Trimethyl lead degradation by free and immobilized cells of an Arthrobacter sp. and by the wood decay fungus Phaeolus schweinitzii.

The continuing production of leaded petrol generates liquid wastes containing recalcitrant trialkyl lead, for which no suitable chemical treatment has been formulated. This investigation explores the feasibility of using microorganisms to catalyse the rate-limiting step of trimethyl lead degradation to dialkyl lead; this disproportionates chemically to give, ultimately, Pb2+ which is treatable by classical methods. An Arthrobacter sp. and a wood decay macrofungus, Phaeolus schweinitzii provide novel evidence for metabolic trimethyl lead (Me3Pb+) degradation. The retention of this activity in immobilized cell column reactors challenged with Me3Pb(+)-supplemented flows suggests that a future biotreatment process may be possible.

Excretion of tetramethyllead, trimethyllead, dimethyllead and inorganic lead after injection of tetramethyllead to rabbits.

Rabbits were divided to groups of 3, and injected either 9.9 mg of tetramethyllead (Me4Pb)/kg of body weight (7.7 mg Pb/kg) or 39.7 mg/kg (30.8 mg Pb/kg) into the ear vein once only, respectively, and urinary and fecal excretions of lead were studied for chemical species and total lead during the following 7 days. In the group injected 9.9 mg/kg, the urinary total lead excretion was composed of about 73% dimethyllead (Me2Pb2+), about 19% trimethyllead (Me3Pb+), about 6% inorganic lead (Pb2+), and about 2% Me4Pb on the day following the injection, and 100% Me3Pb+ 7 days after the injection. In the group injected 39.7 mg/kg, the urinary total lead excretion was composed of about 67% Me2Pb2+, about 14% Me3Pb+, about 17% Pb2+, and about 2% Me4Pb on the day following the injection, and about 8% Me2Pb2+, about 74% Me3Pb+, about 17% Pb2+, and about 1% Me4Pb 7 days after the injection. In both groups, the fecal total lead excretion during 7 days after the injection was entirely composed of Pb2+. During the 7 days, 1-3% of either administered dose was excreted in the urine, and 7-19% in the feces. The urinary total lead excretion in the rabbits injected Me4Pb was similar to that in the rabbits injected tetraethyllead, but the fecal total lead excretion in the former was extremely smaller. This extremely small fecal excretion of total lead appeared to have resulted from the less elimination of lead into the bile of Me4Pb-injected rabbits.

Metabolism of tetraorganolead compounds by rat-liver microsomal mono-oxygenase. III. Enzymic dealkylation of tetramethyl lead compared with tetraethyl lead.

The enzymic transformation of tetramethyl lead (PbMe4) to the trimethyl lead cation is very rapid with sp. activities of 40-50 nmol/min per mg protein. The reaction has an apparent Km of 1.28 X 10(-5) M. PbMe4 binds to cytochrome P-450 with a type 1 difference spectrum, Ks is 6.65 X 10(-6) M. Comparison of the data with results previously obtained for lead tetraethyl (PbEt4) shows that the 20 times higher metabolic rates observed with PbMe4 are related to an intrinsic higher O2 activation as well as to a more effective O2 utilization by that substrate.

Metabolism of tetraorganolead compounds by rat-liver microsomal mono-oxygenase. II. Enzymic dealkylation of tetraethyl lead.

The biological degradation of tetraethyl lead to the triethyl lead cation by rat-liver microsomes from untreated, phenobarbital-pretreated and methylcholanthrene-pretreated rats has been studied; NADPH and oxygen are essential. The reaction is inhibited by CO and can be reactivated in the presence of O2 by irradiation with u.v. light with a max. at 450 nm. Substrate binding to cytochrome P-450 is of type 1. Apparent Km values for triethyl lead formation in microsomes were determined. The highest activities (i.e. about 2 nmol triethyl lead per nmol cytochrome P-450 per min) and the lowest apparent Km values (i.e. 7 X 10(-6) M) are found in microsomes from methylcholanthrene-pretreated rats. In microsomes from control and phenobarbital-pretreated rats Ks values from substrate-binding studies (about 2 X 10(-6) M) are one order of magnitude lower than the apparent Km values (3 X 10(-5) M).

[Biliary excretion of diethyl lead after administration of tetraethyl lead in rabbits].

In order to investigate into whether the large amount of inorganic lead excreted into the feces following intravenous injection of tetraethyl lead to rabbits is derived from the diethyl lead excreted into the bile, we administered 12 mg/kg of tetraethyl lead to rabbits which had been fistulated into the bile duct for taking the bile out of the body. The total lead excreted into the bile during the first 24 hours after the injection of tetraethyl lead amounted to about 8% of the injected amount of lead (with 97% of the excreted lead made up of diethyl lead). The amount of total lead contained in the cecal contents of unfistulated rabbits 24 hours after the injection of tetraethyl lead was equivalent to about 12% of the injected amount of lead (with inorganic lead accounting for about 90% of the excreted lead), but the counterpart of the fistulated rabbits was equivalent only to about 0.6%. The amount of lead excreted into the bile, when measured in terms of the total lead content of the liver, was slightly less in the fistulated rabbits than in the unfistulated ones. These findings indicated that the amount of total lead excreted into the bile of the fistulated rabbits was almost the same as that contained in the cecal contents of unfistulated rabbits, and that the major portion of the lead contained in the cecal contents or feces was composed of inorganic lead. From these results, we came to the conclusion that the large amount of inorganic lead detected in the feces after the injection of tetraethyl lead is derived from the diethyl lead excreted into the bile.

Tetramethyl lead absorption: a report of human exposure to a high level of tetramethyl lead.

Accidental human exposure to a high level of tetramethyl lead is described. Tetramethyl lead is blended with petrol as an antiknock agent, and it has similar physical properties to tetraethyl lead. The patient had high levels of lead in urine, averaging 4-75 mumol (983 mug) daily for the first four days after exposure and he continued to have raised levels of urinary lead for six months. He had no symptoms or physical signs of lead poisoning and comparisons are made between this case and previously reported cases of poisoning by tetraethyl lead. In the cases of tetraethyl lead poisoning all the patients had symptoms, some severe, yet in no instance did the urinary lead levels approach those described in this patient. The effects of chelation therapy with calcium disodium versenate are discussed and the results are similar to those found in tetraethyl lead poisoning. Blood lead levels of up to 3-91 mumol/l (81 mug/100 g) occurred but these levels were not raised commensurate with the urinary lead output. The levels of deltaaminolaevulinic acid (ALA) in the urine were not significantly raised and this report shows that the urinary lead levels give a better guide to the degree of absorption of tetramethyl lead compared with the blood lead or urinary ALA levels. The report illustrates that tetramethyl lead is less toxic to man than tetraethyl lead.