Sequential Determination of Trace Metals in Sea Water by Inductively Coupled Plasma Mass Spectrometry After Electrothermal Vaporization of their Dithiocarmabamate Complexes in Methyl Isobutyl Ketone

A sensitive method for sequential determination of V, Mn, Fe, Co, Ni, Cu, Zn, Mo and Sb in sea water using an inductively coupled plasma mass spectrometry (ICP-MS) after electrothermal vaporization of their dithiocarbamate complexes in methyl isobutyl ketone (MIBK) has been investigated. All analyte elements were simultaneously concentrated 20 fold in a single extract and introduced into the plasma using a graphite rod electrothermal vaporizer (ETV). A sensitivity enhancement due to a chemical modification using a mixed modifier of palladium nitrate and magnesium nitrate was observed for all analyte elements. The limits of detection of the method ranged from 2 ng l-1 for Co to 329 ng l-1 for V. For the replicate determinations of the analyte elements in a sea water sample, the repeatability was within 10% (as a coefficient variation), except for V (12.8%). The recovery test performed on a sea water sample resulted in values ranging from 87% for Sb to 119% for V. With the exception of Mo, the application of this method for the determination of the analyte elements in sea water samples collected from the surface to the depth of 5000 m at the sampling station of 34°12.08N, 141°57.50E (Oct. 12, 1994) in the northwest Pacific Ocean resulted in vertical distributions and concentration ranges which were in a good agreement with those reported in literatures.     

Persistent organochlorine residues in fish and water birds from the Biobio river,Chile

Concentrations of polychlorinated biphenyls (PCBs), DDT and its metabolites, HCH isomers and hexachlorobenzene (HCB) were determined in fish and birds from different locations in the Biobio river basin (central Chile). Samples collected near the mouth of the river contained high concentrations of PCBs, reflecting the massive use of these xenobiotics in the urban and industrial areas of Concepcion and Talcauano. Samples collected in the central part of the basin contained very high concentrations of lindane that coincide with the widespread use of lindane-based pesticides (purified -HCH) in this area. DDT was distributed homogeneously throughout the basin, except at Laguna Icalma, the source of the river in the Andes. Most PCB residues in fish and birds consisted of congeners between penta- and hepta-chlorobiphenyls. In fish, the predominant congeners were the pentachlorobiphenyl 23445 (IUPAC number 118) and the hexachlorobiphenyl 2234455 (PCB-153); in birds 224455 (PCB-180) prevailed.     

Polychlorinated biphenyls, organochlorine pesticides and chlorobenzenes content of livers from Atlantic cod (Gadus morhua) caught off Halifax Nova Scotia

The mean levels ± s.d., (ranges) of organochlorines, pesticides, chlorobenzenes and polychlorinated biphenyl were determined in the livers of 100 Atlantic cod (Gadus morhua) caught off the east coast of Canada in 1980 and were as follows: PCB 1.71±0.90 (0.24–4.33); p,p-DDE 0.28±0.15 (0.01–0.84); p,p-DDD 0.10±0.09 (trace-0.84); p,p-DDT 0.15±0.09 (ND-0.58); -HCH 0.06±0.02 (trace-0.10); -HCH (ND-trace); heptachlor 0.02±0.01 (ND-0.04); heptachlor epoxide 0.15±0.37 (ND-2.16); dieldrin 0.06±0.11 (ND-0.71); hexachlorobenzene 0.02±0.01 (trace-0.05) mg kg^–1 (wet wt.). The levels of these compounds in 1980 have not changed over the previous eight years with the exception of PCB and the DDT group where there appears to be a general decline between 1972 and 1975 with no significant change thereafter.     

Methane in ocean waters: Concentration and carbon isotope variability at East Pacific Rise and in the Arabian Sea

Methane concentrations and stable carbon isotope ratios of water samples from the East Pacific Rise (EPR) at 21°S and the Arabian Sea (24°N, 65°E) have been determined. EPR surface water is in equilibrium (ca. 50 nl/L and –50<¹³CH₄<–46) with atmospheric methane. Deep background water has the signature of the remaining fraction of atmospheric methane partially oxidized in the water column by bacteria. Bottom near, hydrothermally influenced vent methane (>100nl/L and –30<¹³CH₄<–22) is detectable only close to the seep site. There is no input of hydrothermal methane into the atmosphere. EPR water is considered to be rather a sink than a source of atmospheric methane. Surface waters of the Arabian Sea are enriched in methane relative to the atmosphere (source for atmospheric methane). Carbon isotope ratios point to a bacterial origin of methane (¹³CH₄<–55) that is generated in the surface waters. Concentration changes and variations of carbon isotope ratios also suggest that methane seeping from the sea floor sediments of the Arabian Sea is oxidized by bacterial activity and does not reach the atmosphere.     

The contamination of fish with chlorinated hydrocarbons in Portugal: continental coast and Azores islands

In a baseline study, muscle and liver from important commercial fish belonging to different trophic levels were analysed for organochlorines. Samples of sole, sardine and hake were collected from seven locations off the Continental coast and greater forkbeard and horse mackerel off two Azores islands. Residues of ppDDT, ppDDE and PCBs were present in all muscle and liver samples. ppDDD occurred in all liver samples and in most muscle samples, except in sole where it occurred in 29% of the samples. Dieldrin was detected less frequently and did not occur in samples from the Azores. The residue levels were generally similar to those detected in related species from the North Sea, except for samples of sole collected between the Tagus and Sado estuaries where much higher residues were obtained. In view of the low consumption of insecticides in the Azores, it is proposed that long-range transport of organochlorines by winds and/or marine currents is responsible for their presence in this area. The organochlorine residues found in these fish showed no relationship with their position in the food chain but the values did increase with the quantity of lipids present. An unknown compound analysed by GC-MS interfered with DDE quantification in one sample of greater forkbeard.     

PCB and p,p′-DDE in Lake Geneva brown trout (Salmo trutta L.), and their use as bioenergetic indicators

Gross growth efficiency of Lake Geneva brown trout (Salmo trutta) was estimated by monitoring age-related PCB and p,p-DDE accumulation, food contamination and annual growth.Estimation was carried out using 3-, 4-, and 5-yr old fish. Roach (Rutilus rutilus) were determined as the main component of trout diet. Estimated growth efficiency coefficients were 0.4 (3–4 yr old fish) and 0.17 (4–5 yr old fish). Nevertheless numerous parameters can affect the result; their respective influences are discussed.Related to fish age, PCB and p,p-DDE concentrations increase if expressed on a wet weight basis, but not if expressed on a lipid weight basis.At the same age, organochlorine residue concentrations keep similar values for trout and roach in spite of different trophic levels. Growth must be considered as a more dilution factor of PCB and p,p-DDE in trout compared with roach.     

Organochlorine insecticide residues in Ganga river water near Farrukhabad,India

Multiple residues of organochlorine insecticides were monitored in Ganga river water in the district of Farrukhabad in northern Indian for one year (1991–1992). Almost all the samples were found to be contaminated with residues of HCH and DDT. Residues of aldrin, endosulfan and heptachlor were also detected in a larger number of samples. Alpha-HCH, pp-DDT and alpha-endosulfan were found to dominate over the other isomers of HCH, DDT and endosulfan, respectively. Enhanced percentage of beta-HCH suggests accumulation of this isomer in the aquatic environment. The average concentration of aldrin was more than that of dieldrin. Aldrin residues often exceeded the WHO guideline value for drinking water and the concentration of heptachlor occasionally exceeded the specified limits.     

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.     

Trends of Contaminants and Effects in Bald Eagles of the Great Lakes Basin

Bald eagle (Haliaeetus leucocephalus) numbers in North America have increased since the ban of DDT and other organochlorine compounds in the 1970s. The decrease in the environmental concentrations of p,p-DDE has lead to the lessening of egg-shell thinning and has been a major reason for the current resurgence of bald eagle populations in temperate North America, however, this recovery has not been uniform. Eagles nesting along the shorelines and islands of the Great Lakes have continued to experience impaired productivity. In order to examine some of the reasons for the current recovery of bald eagles in the Great Lakes Basin and the potential use of eagles as a bioindicator species of Great Lakes water quality, we analyzed trends in reproductive activity, concentrations of PCBs and p,p-DDE in unhatched eggs, and rates of developmental deformities. Numbers of occupied nests, fledged young, and yearly productivity rates have increased across the basin. No trends have been observed in changes in the concentrations of p,p-DDE nor Total PCBs in unhatched eggs. An increasing rate in the incidence of developmental deformities in nestlings has been observed in Michigan. The recovery of the bald eagle population along the Great Lakes is most likely due to immigration of relatively uncontaminated adults from Interior regions.     

Efficiency of a standardized artificial substrate for biological monitoring of river water quality

Before using macroinvertebrates in water quality assessment in the Chusovaya River (Russia, the Urals, 50°55N, 60° E), preliminary results of three sampling methods were compared: handnet, circular shovel and a standardized artificial substrate sampler. The artificial substrate consisted of glass marbles ( 20 mm). To compare the efficiency of these sampling methods the total numbers of taxa found at each location per sampling data were considered to be 100%. The highest efficiency was reached with the artificial substrate sampler. 75–100% of the taxa at the different locations were collected with this sampler. Only 5–19% and 10–20% of the taxa at each location per sampling date were collected with the circular shovel in the sand and gravel substrate respectively, being the lowest efficiency. Intermediate results were obtained with the hand net. 23–38% of the taxa were collected with this net. Based on these results and requirements placed upon sampling methods in general, the standardized artificial substrate sampler has been considered to be an optimal sampling device for macroinvertebrates in biological monitoring.