Cationic surfactant as a sensitizer for the spectrophotometric determination of hydrogen sulphide in air and evaluation of a new absorbing medium containing triethanolamine-zinc acetate-sodium hydroxide

An extractive spectrophotometric method for the determination of trace amounts of hydrogen sulphide after fixing the gas in triethanolamine (TEA)-zinc acetate-sodium hydroxide solution is described. The method is based on the reaction of iodate with hydrogen sulphide in the presence of acid and excess chloride ion leading to the formation of ICl2- species which is used to iodinate 2',7'-dichlorofluorescein to form 2',7'-dichloro-4',5'-diiodofluorescein. The iodinated product formed is extracted into an organic solvent and sensitized by equilibrating with a cationic surfactant, cetrimide, in the presence of acetate buffer (pH 5.9 +/- 0.1). The colour system obeys Beer's law over the range 0-1 microg of hydrogen sulphide and the relative standard deviation is 2.4% for 10 determinations at 0.75 microg of hydrogen sulphide. The effect of interfering gases on the determination is discussed. The proposed absorbing solution has been evaluated using a hydrogen sulphide permeation device. This absorbing solution has an absorption efficiency of > 93% at a flow rate of 1.5 litre min(-1) for a sampling period of 2 h. The fixed H2S is stable for 40 days. The method has been applied to determine residual H2S levels in a laboratory fume hood and in the vicinity of sewage pumping station. The method can be used to determine as little as 0.05 microg of hydrogen sulphide.     

Influence of reduced dietary calcium on the accumulation and effects of lead, cadmium, and aluminum in birds

The influence of low dietary calcium on the accumulation and effects of dietary lead, cadmium and aluminum was examined in zebra finches and ring doves. In zebra finches fed a diet containing 0.3% Ca, the hepatic and renal accumulation of lead was enhanced approximately 400% and of cadmium about 150-200%, compared to birds fed a 3.0% Ca diet. Low dietary Ca also caused bones of female finches to lose an average of about 60% of their normal Ca content. Loss of bone-Ca was also observed in male finches, but was less than in females. In reproductively active ring doves, low (0.4%) dietary Ca enhanced the accumulation of lead and cadmium, but not of aluminum, compared with accumulation in doves consuming a 2.0% Ca diet. Enhanced accumulation of lead and cadmium was accompanied by increased synthesis of the metal-binding protein metallothionein and by greater inhibition of delta-aminolevulinic acid dehydratase activity. These results indicate that, under conditions of reduced dietary Ca availability, such as can occur in acid-impacted environments, wild birds risk increased uptake of certain toxic metals and may accumulate toxic concentrations of these metals more rapidly. Researchers should take account of dietary Ca levels when interpreting results of dosing studies in which metals such as lead and cadmium are administered to birds.     

Selectivity in the complexation of actinides by humic substances

The interactions of a range of actinide elements (Th, U, Np, Pu, Am) with humic substances from the Needle's Eye natural analogue site were studied by gel permeation chromatography. Bulk humic substances were isolated by ammonia extraction, followed by dialysis against distilled water and freeze-drying. The gel permeation results suggest that Needle's Eye humic substances can be fractionated into three incompletely resolved fractions with average molecular weights determined by analytical ultracentrifugation around 49 000 for Fraction 1, around 14 700 for Fraction 2 and around 8000 for Fraction 3. Although there are significant differences between the organic matter elution patterns in individual gel permeation experiments, presumably due to differences in column packing, these are much smaller than the differences between metal ions. The uranium that is naturally present in these humic substances is largely bound in the late-eluting fraction. Spikes of the early actinides, including Np and Pu in controlled valency states, have been added to the humic substances, and gel permeation of the spiked humic substances shows that the three humic fractions vary greatly in their effectiveness and selectivity as ligands for early actinides.     

The influence of particle surface characteristics on pollutant metal uptake by cells

The phosphatic mineral, hydroxyapatite, and two ion exchange resins have been used as artificial sediment particles. The surface properties of these materials have been studied using the Langmuir adsorption isotherm to calculate the binding capacity (B(max)) and the adsorption constant (K(L)) for zinc and cadmium ions. Mussels (Mytilus edulis) were fed on the particles and their digestive glands were subsequently removed and subjected to cell fractionation. The supernatant fraction was used to determine cytosol metal levels as a measure of the materials absorbed from the ingested particles. The level of cytosol zinc and cadmium was correlated with the K(L) values of the artificial sediments. It is suggested that phagocytosis of sediment particles plays an important part in transferring pollutants into benthic organisms and that the efficiency of this process is related to the adsorption coefficient of the particle surfaces.     

Distribution of Organochlorine Pesticides in the Chao Phraya River, Thailand

Water samples from the Chao Phraya River, the main river in Thailand were collected and analyzed during 1988–1994. Organochlorine pesticides such as HCHs, DDTs, aldrin, dieldrin and chlordanes were determined. Aldrin and dieldrin had high frequencies of occurrence in water samples. The concentration median of the pesticides was approximately one order of magnitude higher than those of total HCHs and DDTs. Levels of aldrin were relatively high in the upstream while levels of DDTs were high in the urban area of Bangkok during 1989–1990. p,p-DDE levels were relatively higher in 1992. No clear trends in the levels of pesticides were observed.     

The impact of constituent ions of acid mist on assimilation and stomatal conductance of Norway spruce prior and post mid-winter freezing

Norway spruce seedlings were sprayed twice weekly with one of a range of artificial mists at either pH 2.5, 3.0 or 5.6, for three months. The mists consisted of either (NH4)2SO4 (pH 5.6), NH4NO3 (pH 5.6), water (pH 5.6), HNO3 (pH 2.5), H2SO4 (pH 2.5). In late December 1988 and early January 1989 the light response of assimilation and stomatal conductance were assessed in the laboratory following a 4-day equilibration period at 12 degrees C. The intact trees were then subjected to a mild (-10 degrees C), brief (3 h) frost in the dark and the recovery of light saturated assimilation (Amax) was followed during the subsequent light period. The same trees were then subjected to a second 3 h (-18 degrees C) frost. The recovery of Amax during the next day was followed. All ion-containing mists stimulated Amax and apparent quantum yield relative to control trees, irrespective of pH. The mists containing SO4 made stomatal conductance unresponsive to light flux density and caused the stomata to lock open. Frosts of -10 degrees C and -18 degrees C did not inhibit the Amax of control trees for longer than 200 min into the light period. In contrast, the ion-containing mists exerted a significant inhibitory effect upon the recovery of Amax. Nitric acid inhibited Amax to 35% of the pre-frost value, whilst the remaining treatments inhibited Amax between 15% and 40% of the pre-frost value. It is concluded that SO4 causes increased mid-winter frost sensitivity and NO3 ameliortes this effect. The results are discussed in relation to forest decline.     

The fate of endosulfan in aquatic ecosystems

Endosulfan, one of the major pesticides used in cotton-growing, is of environmental concern because of its toxicity to fish and its apparent persistence in the environment. This study examines the distribution and degradation pathways for endosulfan in an aquatic system and the processes by which it is removed. In the alkaline waters of the cotton region, hydrolysis is the dominant degradation process. By this mechanism alone, the expected half-lives for the alpha- and beta-endosulfan isomers were found to be 3.6 days and 1.7 days, respectively. Partitioning studies showed, however, that the major proportion of endosulfan would associate with the sediments (log Koc(alpha) 3.6 and log Koc(beta) 4.3). Field studies confirmed the presence of high concentrations in sediments. Microcosm experiments showed that loss of endosulfan was slower than predicted from hydrolysis rates. Models are presented to explain how desorption from sediment limits the loss of endosulfan from a system.     

The response of Lemna trisulca L. to cadmium

Lemna trisulca was grown, using aseptic culture techniques in a filter-sterilized medium, a portion of which was replaced regularly during experiments. L. trisulca responded to the addition of 0.64 microM Cd with a reduction in multiplication rate (MR) 2 +/- 1 days after exposure. The internal Cd content reached 1000 +/- 140 microg Cd/g (dry wt) within 2 days exposure to 0.64 microM Cd. The final yield was reduced by an average of c.8% for each day of exposure to 0.64 microM Cd in a 14 day experiment. This implies that an equilibration period should be used for short-term bioassay tests before the effect of a toxicant is determined. Pretreating L. trisulca with 0.08 or 0.32 microM Cd for 6 weeks had no significant effect on MR or Cd uptake when plants were subsequently exposed to a range of Cd concentrations or grown in a control medium. This suggests that L. trisulca does not become acclimated to elevated Cd concentrations. The MR of L. trisulca fluctuated over a period of almost 600 days and the doubling time ranged from 1.6 to 2.4 days. This produced more than a fivefold difference in final yield in experiments of 14 days duration. The reduction in MR in response to 0.32 microM Cd during this same 600 days period averaged 24% with a coefficient of variation of 38%, and varied with the MR of control cultures. Fluctuations in the intrinsic growth rate and the effect of a toxicant on L. trisulca could potentially confound the assessment of toxicity and must be carefully considered when designing test protocols for aquatic plants.     

Effects of mercury exposure on ionic regulation in the crayfish Orconectes propinquus

Hemolymph sodium, potassium and calcium concentrations were determined in crayfish (Orconectes propinquus) exposed to (203)HgCl(2) mixed with food to a concentration of 1 microg Hg g(-1). Dummy-fed animals were exposed to Hg-dosed food wrapped in dialysis tubing to control for mercury reaching the animals via leaching from food to water. Hemolymph analyses were made following 14-day Hg exposures and again after a further 21-day 'depuration' period during which all animals were fed Hg-free food. After 14 days, the mercury reached a concentration of 0.175 microg g(-1) in the hepatopancreas and approximately half this level in the gills of Hg-fed animals. No depuration occurred from the hepatopancreas although the gills lost approximately two-thirds of their labelled mercury during the depuration period. Hemolymph sodium concentrations in Hg-exposed crayfish, both fed and dummy-fed, after 14 days were significantly lower than in Hg-free controls and remained low following the 21-day depuration period. Hemolymph calcium concentrations were lower in Hg-fed animals than in dummy-fed and control animals after 14 days although calcium levels rose in all treatments after 35 days. This may have been due to the incidence of pre-molt animals in all experimental groups, although the relationship between this and mercury exposure was not established unequivocally. Hemolymph potassium levels showed no differences between treatments.     

Ammonium excretion by gelationous zooplankton and their contribution to the ammonium requirements of microplankton in Chesapeake Bay

Ammonium excretion rates of recently collected specimens of gelatinous zooplankton, the scyphomedusan Chrysaora quinquecirrha DeSor and the etenophore Mnemiopsis leidyi A. Agassiz, were correlated with body mass and water temperature in measurements made from April to October 1989 and 1990. Rates ranged between 3.5 and 5.0 g atoms NH ₄ ⁺ -N (g dry wt)^-1h^-1 for C. quinquecirrha and 3.0 to 4.9 g atoms NH ₄ ⁺ -N (g dry wt)^-1h^-1 for M. leidyi. Excretion rate equations and in situ data on the size distributions and biomasses of gelatinous zooplankters and water temperature were used to estimate the contribution of ammonium by medusae and ctenophores to mesohaline Chesapeake Bay waters on several dates during April to October 1989 and 1990. We then compared the estimated contributions to direct measurements of ¹⁵NH ₄ ⁺ uptake by microplankton. The maximum estimated regeneration by gelatinous zooplankton was 5.8 g atoms NH ₄ ⁺ -N m^-3h^-1 at night in August 1990, when medusae biomass was greatest. This represents about 4% of the ammonium required by the microplankton. During the daytime on all dates, less than 1% of the ammonium required by microplanktion was supplied by gelatinous zooplankton. Therefore, gelatinous zooplankton appear to play a minor role in the ammonium cycle of Chesapeake Bay.