Sequential extraction analysis of heavy metals using a chelating agent (NTA) to counteract resorption

The geochemical partitioning of Pb, Ni and Zn in contaminated quartz-rich sediment and soil samples was characterized by sequential extraction analysis in the presence and absence of nitrilotriacetic acid (NTA). With NTA, levels of metals recovered are higher in the earlier steps and lower in the later steps of the procedure. This suggests that post-extraction resorption is effectively counteracted by chelation, thereby improving the accuracy of the method. An NTA concentration of 200 mg liter(-1) appears to be sufficient for counteracting resorption without causing significant dissolution of non-targeted phases in the samples studied. However, experiments using reference materials spiked with solutions containing Pb, Ni, Cu and Zn suggest that resorption will remain a problem when large amounts of strong sorbents such as organic matter are present. The results also show that although post-extraction resorption does occur in the absence of NTA, the magnitude of resorption is small (<20 to 30% of the summed total of metal present in the sample) in quartz-rich sediments.     

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.     

Long-term trends and sources of organochlorine contamination in Canadian tundra Peregrine Falcons, Falco peregrinus tundrius

Levels of eggshell thinning, and organochlorine residues in egg contents, blood plasma of adults and juveniles, tissue samples, and prey species were determined for a population of migratory Peregrine Falcons (Falco peregrinus tundrius) breeding in the Canadian Arctic. Temporal trends were assessed by comparing data collected during 1991-1994, with data from 1982-1986, for the same population. Shells (n=54) from 1991-1994 averaged 15% thinner than eggs produced prior to the introduction of DDT. No improvement in shell thickness was detected between decades. Mean DDE residue levels in eggs showed a decline from 7.6 mg kg (1982-1986) to 4.5 mg kg (1991-1994), but there was no significant change in SigmaPCB residues. Moreover, the proportion of clutches with eggs exceeding critical SigmaPCB, DDE, and dieldrin residue levels (10%) did not change between decades. Relative to Greenland and Alaskan populations, F. p. tundrius at Rankin Inlet show high levels of organochlorine contamination and little reduction in residues over the last decade. These Tundra Peregrines continue to be exposed to organochlorines in Latin America; however, results also link relatively high levels in the study population with waterfowl species that do not leave Canada in winter.     

Biomass and production of amphipods in low alkalinity lakes affected by acid precipitation

Population biomass and production of the amphipod Hyalella azteca (Saussure) were found to be related to alkalinity (ranging from 0.2 to 58.1 mg liter(-1)) in 10 Canadian Shield lakes in south-central Ontario. Biomass and production of amphipods in the two lakes characterized by spring depressions of pH below 5.0 were found to be lower than those for populations inhabiting lakes that did not experience such acid pulses. The proportional biomass of amphipods in relation to the total littoral zoobenthos community was lower in lakes of low alkalinity than in circumneutral or hardwater lakes. Because production in these amphipod populations is known to depend closely on population abundance, the labour-intensive derivation of production rates yields relatively little information for biomonitoring that cannot be obtained from abundance data alone.     

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.     

Patterns of soil copper contamination and temporal changes in vegetation in the vicinity of a copper rod rolling factory

Patterns of soil copper contamination have been examined in the vicinity of a copper rod rolling plant in Prescot, Merseyside, UK. The site, established in 1975, was found to possess clear patterns of soil copper contamination, with the highest levels of HNO3 and water-extractable fractions encountered in the factory grounds adjacent to the location of the furnace chimney. The majority of the copper had accumulated in the upper soil horizons. The site is surrounded by planted lawns, established at different times after the commissioning of the plant. The species composition of the extant grassland communities, found at sites with differing soil copper levels, was compared to the composition of the original seed mixtures sown at each of ten sites. These surveys clearly showed that different levels of soil copper contamination had produced significant changes in grassland composition with time. At the most polluted site, copper tolerant Agrostis capillaris clones were the main grasses present only two years after the area was sown with a four-species mixture of non-tolerant grass seed. Lolium perenne possessed extreme sensitivity to copper. A number of dicotyledonous species, normally considered sensitive to elevated copper levels, were found to be unaffected where such conditions had arisen after plants had established from seed.     

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.     

Effects of air pollutants on the growth and antioxidative system of Norway spruce exposed in open-top chambers

Grafted Norway spruce trees were subjected to exposure beginning in April 1988, to one of four different air treatments in open-top chambers: Charcoal filtered air (CF), non-filtered air (NF), non-filtered air with the addition of O(3) during summer (NFO), and SO(2) plus NO(2) during winter (NFOSN). CF trees were considered as the reference group. No effects on growth parameters were observed. Samples of the two youngest needle year classes were taken late in November 1989 for enzyme determinations. The activity of ascorbic acid peroxidase (A-POD) increased the same level in all treatments, and activities of catalase and dehydroascorbic acid reductase (DHA-R) increased only in NF and NFO treatments. A higher level of activity in the NFOSN treatment was observed only for glucose-6-phosphate-dehydrogenase (Glc-6-P-DH) and non-specific peroxidase (POD). Isoelectric focusing of POD showed a changed pattern in the NFOSN treatment. Neither activity nor isoelectric focusing of superoxidase dismutase (SOD) was changed in any of the treatments.     

Petroleum and hazardous chemical spills in Newark Bay, New Jersey, USA from 1982 to 1991

Newark Bay, New Jersey, is particularly vulnerable to ecological damage from petroleum and chemical spills, as a result of the enclosed nature and shallow depth of the bay, the high frequency of shipping traffic, and the numerous chemical and petroleum transfer terminals located alongs its shores. To evaluate the potential impacts to the natural resources of this coastal estuarine ecosystem, chemical and petroleum accidents reported to the US Coast Guard (USCG) between 1982 and 1991 were compiled to determine the frequency and volume of these incidents in Newark Bay and in each of its major tributaries. Records obtained from the USCG National Response Center's computerized database indicated that more than 1453 accidental incidents, resulting in the release of more than 18 million US gallons of hazardous materials and petroleum products, occurred throughout Newark Bay during this period of time. The bulk of the materials released to the aquatic environment consisted of petroleum products, specifically No. 6 Fuel Oil (103 spills, 12 829 272 US gal) and gasoline (207 spills, 48 816 US gal). The majority of the reported incidents occurred in the Arthur Kill and its tributaries, as well as in the Kill Van Kull and the Passaic River. The results of this study indicated that the accidental discharge of petroleum and hazardous chemicals represents a significant source of chemical pollution in Newark Bay. Based on the frequency of spills and the volume of materials released to the aquatic environment, it is likely that these events are having a deleterious effect on the Newark Bay ecosystem.