Determination of potentially bioaccumulating complex mixtures of organochlorine compounds in wastewater: a review

Organic chlorine compounds can be persistent environmental contaminants and may be accumulated through the food chain to the aquatic organisms, to fish and humans, depending basically on their hydrophobic properties. Consequently, there is an interest to measure these organic compounds from both the scientific and regulatory communities. The analytical essays have been improved for measuring specific organic chlorine compounds that present the most toxicological potential (polychlorinated biphenyls [PCBs], certain pesticides and dioxins), although they are tedious and time-consuming procedures. The existing tests to measure adsorbable organic halogens (AOX) or extractable organic halogens (EOX) do not distinguish the more hydrophobic organic chlorine matter. The intention of this paper is to make a review of the existing methods to measure the potentially bioaccumulating organochlorine compounds (OCs) from wastewater and propose a methodology to a standardisation procedure for complex mixtures of OCs in wastewater, such as pulp mill effluents. A new method has been proposed for determining the most hydrophobic part of the extractable organic halogens (EOX(fob)), the lowest reported value is 0.6 microg/l, expressed as chloride, and the relative standard deviation at 20 microg/l is 7% on laboratory samples and 30% on real effluents. This new procedure could be a valuable tool to complement environmental risk assessment studies of wastewater discharges.     

Lead and cadmium levels in coastal benthic algae (seaweeds) of Tenerife,Canary Islands

Lead and cadmium levels of some species of brown-algae (Phaeophyta) from the mesolittoral (intertidal area) of the Island of Tenerife (central-eastern Atlantic) were determined by Atomic Absorption Spectrometry. The quality control was carried out using a standard "CRM 279 Ulva lactuca".The mean, minimum and maximum concentrations were 11.21, 2.090 and 81.795 microg/g/dw; and 1.13, 0.190 and 5.130 microg/g/dw for lead and cadmium, respectively. The fact that samples registering the highest cadmium concentrations were the same as those which showed the highest lead level corresponding to a sampling station nearby an urban water outlet could be relevant.     

Fractionation of elements by particle size of ashes ejected from Copahue Volcano,Argentina

The volcano Copahue, Neuquén province, Argentina has shown infrequent explosive eruptions since the 18th century. Recently, eruptive activity and seismicity were registered in the period July-October, 2000. As a consequence, ash clouds were dispersed by winds and affected Caviahue village located at about 9 km east of the volcano. Samples of deposited particles from this area were collected during this episode for their chemical analysis to determine elements of concern with respect to the health of the local population and its environment. Different techniques were used to evaluate the distribution of elements in four particle size ranges from 36 to 300 microm. X-ray powder diffraction (XRD) was selected to detect major components namely, minerals, silicate glass, fragments of rocks and sulfurs. Major and minor elements (Al, Ca, Cl, Fe, K, Mg, Mn, Na, S, Si and Ti), were detected by energy dispersive X ray analysis (EDAX). Trace element (As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, U, V and Zn) content was quantified by inductively coupled plasma-mass spectrometry (ICP-MS). Nuclear activation analysis (NAA) was employed for the determination of Ce, Co, Cs, Eu, Hf, La, Lu, Rb, Sc, Sm, Ta and Yb. An enrichment was observed in the smallest size fraction of volcanic ashes for four elements (As, Cd, Cu and Sb) of particular interest from the environmental and human health point of view.     

Development of a harmonised phosphorus extraction procedure and certification of a sediment reference material

A harmonised procedure for the determination of the forms of phosphorus in freshwater sediments, developed in the frame of the European Programme, Standards, Measurements and Testing (SMT) has been used for a certification campaign for a reference material. This operationally defined scheme is a good compromise between method performance and reproducibility. Furthermore, the method is rather simple to implement and could be used by water managers on a routine basis. A homogeneous and stable sediment reference material has been prepared and will be available before mid 2001. The so-called SMT protocol, together with the reference material, are useful tools in the field of water management, especially at a time when quality assurance is of paramount importance in laboratory analyses. Knowledge of the bioavailable forms of phosphorus is important not only for analysis of sediments but also for sludge and soils. Therefore, the SMT protocol could be extended to these materials.     

Analytical approaches to the determination of phosphorus partitioning patterns in sediments

Three methods for phosphorus fractionation in sediments based on chemical extractions have been applied to fourteen aquatic sediment samples of different origin and characteristics. Two of the methods used different approaches to obtain the inorganic fractions. The Hieltjes and Lijklema procedure (HL) uses strong acids or bases, whereas the Golterman procedure (G) uses chelating reagents. The third one, the Standards, Measurements and Testing (SMT) protocol, was proposed in the frame of the SMT Programme (European Commission) which aimed to provide harmonisation and the validation of such methodologies. This harmonised procedure was also used for the certification of the extractable phosphorus contents in a sediment certified reference material (CRM BCR 684). Principal component analysis (PCA) was used to group sediments according to their composition and the three extraction methods were applied to the samples including CRM BCR 684. The data obtained show that there is some correlation between the results from the three methods when considering the organic and the residual fractions together. The SMT and the HL methods are the most comparable, whereas the G method, using a different type of reagent, yields different distribution patterns depending on sample composition. In relation to the inorganic phosphorus, the three methods give similar information, although the distribution between non-apatite and apatite fractions can be different.     

Antimony: a traffic-related element in the atmosphere of Buenos Aires, Argentina

Vehicular traffic is one of the main sources of antimony in highly populated urban areas like Buenos Aires where an overall traffic density of 1 500 000 vehicles per day (corresponding to 7500 vehicles km(-2)) is estimated. In this context, a study was undertaken to ascertain the levels of Sb and other traffic-related elements (TRE) in the atmosphere of this city. To this end, sixty-seven samples of PM-10 particulate matter were collected during eight days in nine representative sampling sites located downtown Buenos Aires and spread over an area of about 30 km2. The collection of particulate matter was performed on ash-free glass-fibre filters using high volume samplers with PM-10 sampling heads. A combination of aqua regia and perchloric acid was used for leaching metals from filters. The resulting solutions were evaporated and then diluted with 0.1 mol l(-1) HCl. Antimony was determined by inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) at ng g(-1) levels. Concentrations of Sb varied from 12.9 +/- 0.9 to 375 +/- 23 microg g(-1)(equivalent to 0.87 +/- 0.06 to 15.3 +/- 0.8 ng m(-3)). Statistical analysis was performed on the data set including the measured PM-10 mass and Sb concentrations for the monitored period. Correlations of Sb with other TRE namely, Cu and Mo were also assessed. The highest concentrations of Sb were detected at two sites (Hospital Alemán and Casa Rapallini) located in streets with traffic consisting mostly of passenger cars and showing a "stop-and-go" pattern in peak hours. Antimony levels in the Buenos Aires PM-10 are by far below the level of 0.5 mg m(-3)(for an 8 hour workday, 40 hour work week) set by the US Occupational Safety and Health Administration (OSHA) for occupational exposure. However, monitoring of Sb and other TRE should be carried out in a systematic fashion to detect the possibility of increases in from the present levels.     

In vivo effects of deltamethrin on some biochemical parameters of carp (Cyprinus carpio L.)

Thein vivo effects of deltamethrin (DM) on the blood sugar level, the acetylcholinesterase (AChE, EC 3.1.1.7) activities of the blood serum and various organs (heart, liver and intestine), the lactate dehydrogenase (LDH, EC 1.1.2.3), glutamic-oxaloacetic transaminase (GOT, EC 2.6.1.1), and glutamic-pyruvic transaminase (GPT, EC 2.6.1.2) activities of the blood serum, the adenosine triphosphatases (EC 3.6.1.3; Na⁺/K⁺-ATPase and Mg²⁺-ATPase) activities of the erythrocyte plasma membrane and the catalase (EC 1.11.1.6) activity of the liver were examined throughout 96 h in adult carp (Cyprinus carpio L.) Two sublethal concentrations, 1.0 and 1.5 µg/l of deltamethrin, were used. All fish survived the experiment except one, in an aquarium containing 1.5 ppb of DM, which died after 72 h.The AChE specific activity was significantly inhibited in the heart and intestine after 96 h at both concentrations compared to that in the control animals (P<0.05, Student'st-test), while there was no detectable difference between the two treatment. At the same time there was no detectable change in the liver. In the serum, the AChE activity almost remained unchanged; the only significant decrease could be measured after 96 h at 1.5 µg/l deltamethrin concentration. The blood glucose content exhibited interesting changes: after 24 h fish exposed at 1 µg/l DM seemed to be stressed, although this increase was not significant. When these fish became used to the new conditions (in practice this meant the presence of DM), the glucose level decreased, especially after 72 h. At the same time the control animals kept in similar circumstances showed a small insignificant decrease. Meanwhile fish in aquaria containing 1.5 µg/l DM reacted to the treatment with an increased blood glucose level after 48 h, and this did not change until the end of the treatment. The Na⁺/K⁺-ATPase activity decreased in a dose-dependant manner, while Mg²⁺-ATPase was less affected. A small increase in LDH level was observed, indicating damage of different muscle tissues. However, this phenomenon appeared only with the small dosage after 24 h (P<0.05). It has to be mentioned that the individual values varied to a large extent among of the eight fish.The GOT activities of the serum increased during the treatment. However, significant changes were only expressed after 72 and 96 h at 1 µg/l DM concentrations (P<0.01 andP<0.05), and after a similar long treatment at the high dosage (P<0.05, 72 and 96 h). The GPT did not change significantly in aquaria containing 1 µg/l DM. The only larger increase was measured after 96 h at 1.5 µg/l DM concentration (P<0.05). The catalase activity in the liver of treated carp remained practically at the same level compared to that in control fish.All these changes (concerning the primary effects of this compound) demonstrate the effect of DM on different fish enzymes, at low concentrations under laboratory conditions, which might be useful in practice for biomonitoring using fish.     

Dissolved oxygen content as an index of water quality in San Vicente Bay,Chile (36 degrees 45'S)

The present report describes some effects of industrial and municipal effluents on the waters of San Vicente Bay. Analyses ofthe main substances contained in the fishing industry effluentsuggest rating criteria based on the oxygen saturation of thewater as an assessment of organic pollution. Six cruises were carried out throughout the Bay, from June to December 1996. Watersamples were analyzed for dissolved oxygen, oil and grease content, and sediment samples for organic matter content. Waterparameters (salinity, temperature) were used to characterize theBay's hydrography, and to calculate values for oxygen saturation. The measurements demonstrated a local broad range of oxygen deficit, with a maximum of 45% in the winter to 95% in the spring. In November more than 65% of the Bay's area showed oxygendeficits greater than 40%. Organic matter was unusually high insediments along the northern sector of the Bay. The results suggest that the oxygen depletion was a representative parameterfor establishing a relative scale of water quality in this Bay.     

The behaviour of heavy metals from the Guadalquivir estuary after the Aznalcóllar mining spill: field and laboratory surveys

The spill at `Los Frailes caused a large input of metals intothe riverine, estuarine and coastal ecosystems. Metal behaviourin natural waters can be studied both by performing fieldmeasurements, and by undertaking laboratory simulationexperiments. Here is described the behaviour of the heavymetals Zn, Cd, Pb and Cu in the Guadalquivir estuary usingincubation experiments and the results compared to thoseobtained during field assessments. If the toxic waste water hadbeen discharged untreated into the environment, it could haveraised the heavy metal concentrations in the estuary water tohigh values, such as 20.65 M for Zn and 40 × 10^-3 M for Cd. These values are several times higher than thoseobtained in samples collected in the area during the monitoringof the early impact. The metals present a non-conservative behaviour, with a high loss to waters of low salinity values.     

Environmental and socio-economic evaluation of four different sites for a domestic airport

During World War II, a military airport was built inside the city of Reykjavik. This airport then became the centre of domestic aviation for the whole country. Today, 50 years later, the airport tract has become valuable for urban development. The city government therefore wants the airport relocated. Four different sites have been considered. The first alternative is to maintain the airport in the same place. A second alternative is based on reclaiming land alongside the present airport. A third possible site is in a rugged lava field south of Reykjavik, and the fourth alternative is to move the domestic traffic to Keflavik International Airport about 60 km away. The relocation has become a hot issue in the country. The people living in the countryside want to keep the airport in the same place. On the other hand, people living in Reykjavik see the airport land as valuable potential for urban development close to the city centre. To approach this debate in an orderly fashion, the four sites have been studied from an environmental and socio-economic point of view. The four alternatives are classified by four different categories: (1) economy and capital investment, (2) social impacts, (3) direct environmental consequences, and (4) public safety. Firstly, the last three categories were evaluated and weighted, and all four alternatives graded according to their environmental quality. Secondly, using the results of a separate cost-effectiveness study, a Pareto optimality solution is suggested. Finally, sensitivity analysis was carried out to investigate how the “environmental” factors through their variation can influence the final selection.