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.     

Exposure estimates in assessing helath effects of air pollution

Air pollution has been associated with adverse health effects. Difficulties in interpreting studies of health effects of exposure to air pollution arise in estimating exposure. Until recently, studies of effects of air pollution have relied on pollution exposure measurements obtained from fixed location air pollution stations monitoring outside air (to evaluate compliance with air quality standards, rather than to examine population exposure). However, recent evidence suggests that there are substantial differences between air pollution levels measured at such sites and levels to which people are actually exposed, i.e. personal exposure. The present study examines effects of ambient urban air pollution on persons suffering from asthma, healthy non-asthmatic subjects and school children (in 2 Canadian cities, Toronto and Hamilton). Air pollution exposure is being assessed by data obtained from: (1) conventional abatement oriented fixed location air pollution monitoring stations, (2) an extensive population oriented network, (3) inside and (4) outside structures (homes and schools) as well as (5) personal air pollution samplers. The data indicate variability in these different estimates of exposure which have implications on health effects assessment.     

Organochlorine insecticide residues in agricultural soils of the indo-gangetic plain

Multiple residues of organochlorine insecticides were monitored in the agricultural fields near Farrukhabad in the vicinity of the River Ganga in northern India for one year (1991–1992). Almost all soil samples were found to be contaminated with residues of hexachlorocylohexane (HCH) and dichlorodiphenyl-trichloroethane (DDT). Residues of aldrin and endosulfan were also detected in a large number of samples. Heptachlor residues were scarcely detected. Alpha-HCH, pp-DDT and alpha-endosulfan were found to dominate over the other isomers/metabolites of HCH, DDT and endosulfan, respectively. The average concentration of dieldrin was more than that of aldrin. The concentrations of residues progressively increased up to a depth of 1 m.     

Debromination of 1,4-Dibromobenzene and 4,4′-Dibromobiphenyl: A Model for Cleansing of PCBs

The aim of this study is to develop a catalytic method which has advantages over current method to detoxify and degrade environmentally harmful polychlorinated biphenyls (PCBs). A variety of catalysts have been employed in a preliminary study on 1,4-dibromobenzene and 4,4-dibromobiphenyl which may be considered to represent simple analogues of PCBs. The most satisfactory catalysts are those involving [Pd(dppf)] [dppf = 1,1-bis(diphenylphosphino)ferrocene], generated in situ from PdCl2(dppf) or Pd(dppf)2. In the presence of the reducing reagent, namely NaBH4, debromination has been achieved at relative mild conditions with high product yields (> 70%). Thus, our results indicate the possibility of dechlorination of PCBs with such catalysts.     

Toxicity of a complex mixture of atmospherically transported pesticides to Ceriodaphnia dubia

The presence of several anthropogenic chemicals has been documented in the atmosphere of the Canadian prairies. The deposition of these chemicals as a mixture is of importancesince little is known of the combined effects of these chemicalson aquatic organisms. This study was designed to evaluate theacute and chronic toxicity of a complex mixture of nineatmospherically transported pesticides to Ceriodaphniadubia. The nine selected pesticides (bromoxynil, dicamba, 2,4-D,MCPA, triallate, trifluralin, pentachlorophenol, lindane, and4,4-DDT) were detected in appreciable quantities in dryatmospheric deposits. The concentration of each pesticide in themixture was based on maximum measured daily dry deposition ratesfor central Canada, except for pentachlorophenol, which wasestimated based on atmospheric concentrations. The 48-h LC50estimate for C. dubia exposed to the pesticide mixture was174.60 g L^-1 (340 times the measured total dry deposition concentration). The estimated NOEC and LOEC for bothsurvival and reproduction, as determined in the 7-d chronic toxicity test, were 51.3 (100 times) and 154 g L^-1 (300 times), respectively. A basic risk assessment, using the toxic unit approach, suggested that the toxicity of the pesticide mixture was mainly due to 4,4-DDT. Overall, this atmospherically transported complex mixture of pesticides appearsto pose a negligible toxicological risk to non-target aquatic invertebrates such as zooplankton.     

Environmental and Biological Monitoring of Organochlorine Residues after the Plague Epidemic in Surat, India - A Preliminary Study

In late August 1994, an outbreak of human pneumonic/bubonic plague was reported in Surat, India. During the epidemic, large amounts of pesticides, such as benzene-hexachloride (BHC) and other organochlorinated compounds were used to control the vector that might have transmitted the plague. In order to evaluate the extent of contamination, both environmental samples (9 water samples and 4 soil samples) and biological samples (5 blood and urine samples) were collected and analyzed for organochlorine residues. Samples were analyzed after hexane extraction by gas chromatography equipped with electron capture detector (GC-ECD), using a PTE-5 capillary column. The results showed that the levels of 1,1-(2,2-dichloroethenylidene)-bis[4-chlorobenzene] (DDE), a major metabolite of DDT, were low in environmental samples (water, soil), while BHC levels were relatively high in one of the water sample as well as two soil samples. The BHC and DDE levels in the biological samples were not higher than those reported earlier from India, except for serum DDE. Further studies are needed to evaluate the effect of long-term exposure as the present study was based on limited samples.     

Temporal variability of the elemental composition in urban street dust

Urban Street dust is recognized as a source of urban air and runoff degradation. This paper takes a preliminary step toward a better understanding of temporal variability in street dust chemistry and of the controlling mechanisms. Street dust samples, collected over four seasons in the city of Hamilton, Canada, show a variability dependent on element and source-anthropogenic sources exhibiting the greatest temporal variability. In addition, elements attributed to common sources exhibit similar temporal patterns. The use of generic or even one-time samples may seriously misrepresent the elemental make-up of urban street dust. Based on the samples collected in this study, a number of questions/insights are posed to further the study of street dust temporal variability.     

A survey of benthic invertebrates in the Suwannee River,Florida

Benthic invertebrate communities were surveyed in a 233 km reach of the middle and lower Suwannee River in Northwestern Florida in the winter 1987 and early summer 1988 to determine their abundance and distribution as potential foods of the Gulf sturgeon, Acipenser oxyrhynchus desotoi, and to determine the effects of possible natural and human-induced disturbances to the communities. In substrates of the tidal oligohaline to mesohaline lower reach of the East Pass site I (km 2) and site II West Pass (km 5) near the Gulf of Mexico, densities of tube dwelling and free swimming amphipods, polychaetes, oligochaetes, and dipterans in the PONAR grabs were moderate (100–999 {iex} individuals/m²) to abundant (1000–9999 {iex} individuals m^–2). Also, at sites I and II, low (10–99 {iex} individuals m^–2) to moderate densities of dipteran Chironomidae and olive nerite snail were collected in hardboard multiplate artificial substrate samplers. Diversities of benthic invertebrates in both grabs and hardboard multiplates were relatively low. Baetid mayflies were moderately abundant in the dip net samples. Upriver from sites I and II, the transition of an oligohaline tolerant benthic community to a freshwater one was abrupt due to strong freshwater flow. At sites III (km 48) and IV (km 89), benthic invertebrate populations were low to moderate in hardboard multiplate and dip net samples. In the middle reach (km 101 to km 233), aquatic insects were predominant and included; chironomids, mayflies, and beetles, and also, freshwater gammarid amphipods, gastropods, and the Asian clam. In winter, the bottom substrates at sites VII (km 153) and VIII (km 205) contained diverse and dense populations of Chironomidae (5932 m^–2), the greatest density for a major taxonomic group recorded in this survey. Crayfish were collected in low densities only in artificial substrate samplers from sites IV to IX. Leeches were widespread in the study area. Empirical Biotic Index values that reflect impacts of organic wastes on benthic invertebrate communities were within a narrow range, 3.16 to 6.38, and indicated slightly enriched to enriched water. Of the total 186 benthic invertebrate taxa, 82% had quality values 0 to 5 that indicate overall clean water conditions. The predominant benthic invertebrates in the Suwannee River were detritivorous and the communities reflected oligotrophic to mesotrophic waters.     

The effect of atmospheric pollution on α-glycerophosphate dehydrogenase activity in the satin moth (Leucoma salicis (L.))

The purpose of this study was to investigate how various combinations of atmospheric pollutants may affect -GPDH activity in the satin moth. Enzyme activity was measured in crude larva and pupa as well as in hoogenates from the fat body and thoracic muscles of adults. The insects were divided into five groups and treated with dust (containing heavy metals) and gaseous pollutants (SO₂, NO_x) in different concentrations. Specific activity of -GPDH was the highest in thoracic muscles of adult satin moth and was significantly higher in males, regardless of their origin. Low concentration of SO₂ caused stimulation of enzyme activity but simultaneous action of SO₂, NO_x and heavy metal containing dust with accompanied acid precipitation caused inhibition of -GPDH activity, probably as the result of sulphite bounds with pyridine and flavin nucleotides.     

Tree species in relation to soil moisture regime in northwestern Ontario,Canada

Selected data on site, vegetation cover, and soil, including soil moisture regime (SMR), were collected from 2 167 field plots in northwestern Ontario, Canada. SMR provides an estimate of an averaged, annualized soil moisture supply throughout a complete vegetation cycle. SMR is based upon a relative scale that subjectively ranks sites from , 0, and 1 through 9 along a soil moisture continuum which relates to a dry to wet gradient. SMR may be generally correlated to tree growth, stand composition, degree of competition, nutrient availability and overall site quality.This paper reports on relationships between SMR and major tree species. Results highlight relationships between SMR class and the broad ecological ranges of several tree species. In northwestern Ontario, the determination of SMR can help resource managers to better understand the ecology of boreal sites.     

Groundwater NO3 and F Contamination Processes in Pushkar Valley, Rajasthan as Reflected from 18O Isotopic Signature and 3H Recharge Studies

Agricultural activity in the Pushkar Valley, Rajasthan is constrained due to limited availability of good quality water. In this context, occurrence of nitrate and fluoride in the groundwater was investigated and reported. Integration of stable isotope (18O) data with recharge characteristics (based on 3H-tracer studies) helps in clearly characterizing the processes controlling contamination by point and non-point sources. High nitrate and fluoride groundwaters are associated with high 18O waters. This indicates that significant quantities of evaporated (isotopically enriched) surface run-off water and rain water infiltrate along with nitrate and fluoride salts in the soil. The applicability of this approach under different hydrometeorological conditions is also confirmed.