Illicit drugs in wastewater of the city of Zagreb (Croatia) - Estimation of drug abuse in a transition country

A comprehensive study of various psychoactive substances and their metabolites was performed in the wastewater treatment plant of the city of Zagreb (780 000 inhabitants) using liquid chromatography/tandem mass spectrometry (LC-MS-MS). The estimation of drug abuse for five different illicit drugs, including heroin, cocaine, marijuana, amphetamine and ecstasy, was made on the basis of their representative excretion rates, which were determined over a period of 8 months. Marijuana (1000 kg/year), heroin (75 kg/year) and cocaine (47 kg/year) were found to be the most frequently consumed illicit drugs, while the consumption of amphetamine-type drugs was much lower (1-3 kg/year). A comparison with other reports indicated that drug abuse profiles in transition countries might be different from those reported for Western Europe, in particular with respect to the comparatively increased consumption of heroin. Enhanced consumption of stimulating drugs (cocaine and ectasy) was systematically detected during weekends.     

Verteilung verkehrsbedingter Edelmetallimmissionen in Böden

Contents and distribution of platinum-group-elements (PGE) in soils caused by automobile emissions were investigated at three transects perpendicular to the road at various depths. Concentrations of platinum, rhodium and palladium were determined by ICP-MS after separation and preconcentration by nickel-sulphide fire-assay. Platinum contents in roadside soils range from 250 μg/kg to the local background values which are below 0.5–0.8 μg/kg. Ratios of platinum and rhodium (about 6∶1) are similar to the ratios in catalytic converters. There is evidence for a significant correlation of PGE input and local parameters such as traffic-conditions, distance from the trafficlane, prevailing wind direction, and barriers such as vegetation or morphology.     

Effects-directed analysis of organic toxicants in wastewater effluent from Zagreb, Croatia

The organic toxicants present in the effluent of the main sewer of the city of Zagreb, Croatia were isolated and identified through the use of effects-directed characterisation techniques. At the time of investigation, the wastewater effluent received no treatment and was comprised of a mixture of effluent from domestic and industrial sources. The organic load of the wastewater was isolated by solid phase extraction and toxicity profiles obtained using reverse-phase HPLC. All procedures were evaluated through the analysis of a series of reference compounds of widely differing polarity. Toxicity profiles for EROD activity (CYP1A induction), vitellogenin induction (estrogenic activity), cytotoxicity (membrane stability and metabolic inhibition) were obtained using a rainbow trout (Oncorhynchus mykiss) primary hepatocyte bioassay. The suite of bioassays showed biological responses after exposure to the raw extracts for all the endpoints tested. However, a combination of mixture toxicity and cytotoxicity in the complex raw extract had some masking effect on the sub-lethal responses of vitellogenin and EROD induction. Bioassay testing of the fine fractions obtained by HPLC produced a range of endpoint-specific toxicity profiles for each sample. A number of compounds were identified by the use of GC-MS and LC-MS/MS as responsible for the observed effects. The steroid estrogens 17 beta-estradiol and estriol were identified by LC-MS/MS as estrogen receptor agonists in two of the estrogenic fractions. In addition, GC-MS analysis identified different alkylphenols, benzophenone and methylparaben which also contributed to the estrogenic activity of the sample. Polycyclic aromatic hydrocarbons (PAHs), alkyl substituted PAHs, nitro-polycyclic aromatic compounds (nitro-PACs), carbazoles and alkyl substituted carbazoles and other known CYP1A inducers were identified by GC-MS analysis as responsible for some of the observed EROD activity. Some active compounds remain unidentified.     

Prioritisation of organic contaminants in a river basin using chemical analyses and bioassays

Region-specific contaminant prioritisation is an important prerequisite for sustainable and cost-effective monitoring due to the high number of different contaminants that may be present. Surface water and sediment samples from the Sava River, Croatia, were collected at four locations covering a 150-km-long river section characterised by well-defined pollution gradients. Analysis of contaminant profiles along the pollution gradients was performed by combining toxicity screening using a battery of small-scale or in vitro bioassays, which covered different modes of action, with detailed chemical characterisation based on gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). A large number of contaminants, belonging to different toxicant classes, were identified in both analysed matrices. Analyses of water samples showed that contaminants having polar character occurred in the highest concentrations, while in sediments, contributions from both non-polar and amphiphilic contaminants should be taken into account. Estimated contributions of individual contaminant classes to the overall toxicity indicated that, besides the classical pollutants, a number of emerging contaminants, including surfactants, pharmaceuticals, personal care products and plasticizers, should be taken into consideration in future monitoring activities. This work demonstrates the importance of the integrated chemical and bioanalytical approach for a systematic region-specific pollutant prioritisation. Finally, the results presented in this study confirm that hazard assessment in complex environmental matrices should be directed towards identification of key pollutants, rather than focusing on a priori selected contaminants alone.     

Localisation and quantification of elements within seeds of Cd/Zn hyperaccumulator Thlaspi praecox by micro-PIXE

Cd, Zn and Pb accumulation, spatial distribution within seeds and germinating seedlings, and seeds fitness of metal hyperaccumulating Thlaspi praecox were investigated in order to gain more knowledge on plant reproductive success at metal polluted sites. The seeds contained up to 1351 microg g-1 (dry weight) of Cd, 121 microg g-1 of Zn and 17 microg g-1 of Pb. Seed fitness was negatively influenced by seed Cd hyperaccumulation. Nevertheless, the viability of seeds was decreased by maximally 20%, indicating very efficient tolerance of the plant embryos to Cd. Localisation by micro-PIXE revealed preferential storage of most elements in the embryonic axis. Cd and Zn were preferentially localised in the epidermis of cotyledons. The restriction of seed Pb and Zn uptake and hyperaccumulation of Cd, accompanied by partitioning of Cd in the epidermal tissues of cotyledons, may enable the survival of T. praecox embryos and seedlings in Cd polluted environments.     

Changes in elemental uptake and arbuscular mycorrhizal colonisation during the life cycle of Thlaspi praecox Wulfen

Elemental uptake and arbuscular mycorrhizal (AM) colonisation were studied during the life cycle of field collected Cd/Zn hyperaccumulating Thlaspi praecox (Brassicaceae). Plant biomass and tissue concentrations of Cd, Pb, Zn, Fe and Ni were found to vary during development, while no variation in P, K, Ca, Mn and Cu tissue concentrations were observed. The lowest Cd bioaccumulation in rosette leaves (BAF(RL)) observed during seeding was partially attributed to lower translocation from roots to rosette leaves and partially to high translocation to stalks, indicating a high Cd mobility to reproductive tissues, in line with our previous studies. The highest intensity of AM colonisation (M%) was observed in the flowering phase and was accompanied by increased root Cd, Zn, Pb and Fe contents. In addition, a positive correlation between AM colonisation and Fe contents in rosette leaves was found. The results indicate developmental dependence of AM formation, accompanied by selective changes in nutrient acquisition in T. praecox that are related to increased plant needs, and the protective role of AM colonisation on metal polluted sites during the reproductive period.     

Chemical indicators of anthropogenic impacts in sediments of the pristine karst lakes

The anthropogenic impact on the pristine karst lakes was investigated using combination of specific parameters, including multielemental analysis of major inorganic constituents (Al, K, Fe) and trace metals (Li, Ag, Cd, Sn, Pb, Bi, Cr, Co, Ni, Cu, Zn and Sb), polycyclic aromatic hydrocarbons (PAHs) and anionic surfactants of linear alkylbenzene sulfonate (LAS) type. The study was performed in the Plitvice Lakes National Park, situated in a sparsely populated area of the northwestern Dinarides, central Croatia. Dated cores of recent sediments from the two biggest lakes, Lake Prosce and Lake Kozjak, were analysed for the selected contaminants using highly specific methods, involving inductively coupled plasma mass spectrometry (ICP/MS), gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The concentration of inorganic constituents reflected primarily the geological background of the area as well as geomorphological and geochemical characteristics of the Plitvice Lakes. Due to the higher terrigenous input, the concentration of all elements was significantly higher in the Lake Prosce. The concentration of toxic metals was relatively low in both lakes, except for Cd (>1 mg kg⁻¹) and Pb (up to 40 mg kg⁻¹). The vertical profiles of these metals suggested that elevated concentrations of Cd were of natural origin, derived from the erosion of the Jurassic dolomite bedrock, while Pb was predominately of recent anthropogenic origin. A similar distribution pattern, suggesting the same prevailing mechanism of input, was observed for pyrolytic PAHs. The characteristic diagnostic PAH ratios revealed that higher PAHs prevailingly originated from the combustion of biomass and fossil fuels. LAS, which represent highly specific indicators of untreated wastewaters, were found in rather high concentrations in the recent sediment layers (up to 4.7 mg kg⁻¹), suggesting that contaminated household and hotel wastewaters reach the Lakes, very probably by leaking through the porous karst rocks.     

Colonisation of a Zn, Cd and Pb hyperaccumulator Thlaspi praecox Wulfen with indigenous arbuscular mycorrhizal fungal mixture induces changes in heavy metal and nutrient uptake

Plants of the Zn, Cd and Pb hyperaccumulator Thlaspi praecox Wulfen (Brassicaceae) inoculated or not with indigenous arbuscular mycorrhizal (AM) fungal mixture were grown in a highly Cd, Zn and Pb contaminated substrate in order to evaluate the functionality of symbiosis and assess the possible impact of AM colonisation on heavy metal uptake and tolerance. The results suggest AM development in the metal hyperaccumulating T. praecox is favoured at elevated nutrient demands, e.g. during the reproductive period. AM colonisation parameters positively correlated with total soil Cd and Pb. Colonised plants showed significantly improved nutrient and a decreased Cd and Zn uptake as revealed by TRXRF, thus confirming the functionality of the symbiosis. Reduced heavy metal uptake, especially at higher soil metal contents, indicates a changed metal tolerance strategy in colonised T. praecox plants. This is to our knowledge the first report on AM colonisation of the Zn, Cd and Pb hyperaccumulator T. praecox in a greenhouse experiment.     

Integral approach to industrial effluent quality control in favour of preventing the Rijeka bay pollution

Abstract

INA‐Petrochemical Industry Omi?alj, Yugoslavia is currently producing low density polyethylene, vinyl chloride monomer and ethylene dichloride.

Because of a potentially great hazard for environmental pollution, particularly by low molecular weight chlorinated hydrocarbons, the company has been putting significant effort into its anti‐pollution programme.

Modern technology, polyfunctional organization and proper control of all waste materials has enabled, thus far, no evident or noticable impact on the environment.

Wastewater treatment from the source to final discharged effluent and environmental control results are described.     

Bioaccumulation of the lipophilic metabolites of nonionic surfactants in freshwater organisms

Nonylphenol (NP), nonlyphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) were determined in different freshwater organisms from the surface waters in the Glatt Valley, Switzerland. Rather high concentrations of the compounds investigated have been found to occur in macrophytic algae, particularly Cladophora glomerata (up to 38 mg kg(-1), 80 mg kg(-1), and 28 mg kg(-1) of NP, NP1EO and NP2EO, respectively), the bioconcentration factors of NP reaching up to 10,000. The concentrations in fish were much lower (NP: < 0.03-1.6 mg kg(-1), NP1EO: 0.06-7.0 mg kg(-1), and NP2EO: <0.03-3.1 mg kg(-1) indicating that biomagnification did not take place. Similar concentrations to those in the fish were determined in different tissues of a wild duck. The estimated bioconcentration factors in fish tissues ranged from 13 to 410 for NP, 3 to 300 for NP1EO and 3 to 330 for NP2EO.