Using environmental analytical data to estimate levels of community consumption of illicit drugs and abused pharmaceuticals

A solid phase extraction (SPE) method has been developed and applied in conjunction with a previously reported liquid chromatography tandem mass spectrometry (LC-MS-MS) procedure for the determination of illicit drugs and abused pharmaceuticals in treated wastewater and surface water samples at the ng L(-1) level. A full method validation was also performed and determined levels of analytical sensitivity were found to lie in the 1-10 ng L(-1) range using river water as a test sample matrix and a sample size of 500 mL. The developed procedure was successfully applied for the determination of the chosen analytes in wastewater treatment plants in Dublin, Ireland and rapidly expanding commuter towns in the surrounding counties. Cocaine was detected in 70% of the collected samples in the range of 25-489 ng L(-1), its primary metabolite, benzoylecognine (BZE) was also detected in the range of 22-290 ng L(-1). Other substances detected included morphine, Tempazepam and the primary metabolite of methadone.     

Source to sink tracking of selected human pharmaceuticals from two Oslo city hospitals and a wastewater treatment works

The occurrence of twenty pharmaceutical compounds was quantitatively determined in effluents from two major Oslo city hospitals, Rikshospitalet and Ullev?l, along with influent, sludge and final effluent from the city's VEAS wastewater treatment works (WTW). Composite hospital effluents were collected over a twelve week period and were showed to contain paracetamol, metoprolol, diclofenac, ibuprofen, 17beta-Estradiol, estriol, estrone, oxytetracycline, tetracycline, doxycycline, chlorotetracycline, demeclocycline, trimethoprim, ciprofloxacin, sulfamethoxazole, cyclophosphamide and ifosfamide. Three pharmaceuticals were not detected above the limit of detection; cefuroxime, 17alpha-ethinylestradiol and meclocycline. Composite influent, sludge and effluent samples were collected from VEAS WTW over a seven week period. The influent into VEAS WTW contained all of the same selected substances detected in the hospital effluents, except for oxytetracycline, chlorotetracycline, demeclocycline, cyclophosphamide and ifosfamide. The percentage of pharmaceuticals entering the works from the hospitals was <10% for all of the selected compounds. VEAS sludge samples contained a different profile of substances reflecting their physico-chemical properties. Hydrophobic antibiotics, such as oxytetracycline, tetracycline and ciprofloxacin, were detected in all of the collected sludge samples. Their absence in the collected influent samples suggests that they enter the works bound to effluent particles, with the dissolved fraction observed in the hospital effluents partitioning onto particulate matter within the sewerage network. The final effluent from VEAS WTW contained reduced concentrations of many pharmaceuticals, including paracetamol, ibuprofen and sulfamethoxazole. For other compounds, such as metoprolol, diclofenac and trimethoprim, there were often higher concentrations in the effluent than the influent. These effluent concentrations represent median inputs varying from low g day(-1) (e.g. paracetamol and ibuprofen) to nearly 200 g day(-1) (e.g. metoprolol and trimethoprim) into Oslofjord. A simple risk assessment showed that the antibiotic ciprofloxacin may at times pose an acute risk to the Oslofjord aquatic environment.     

Organic pollutants in compost and digestate. Part 1. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular markers

In Europe, 9.3 x 10(6) t(dry weight (dw)) of compost and digestate are produced per year. Most of this is applied to agricultural land, which can lead to considerable inputs of organic pollutants, such as polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) to soil. This paper presents an inventory of the pollutant situation in source-separated composts, digestates and presswater in Switzerland by a detailed analysis of over 70 samples. PCB concentrations ( summation PCB 28, 52, 101, 118, 138, 153, 180) were significantly higher in urban (median: 30 microg kg(-1)dw, n = 52) than in rural samples (median: 14 microg kg(-1)dw, n = 16). Together with low concentrations in general, this points to aerial deposition on compost input material as the major contamination pathway. Enantiomeric fractions of atropisometric PCB were close to racemic. Median PAH concentration was 3010 microg kg(-1)dw( summation 15PAH, n = 69), and one quarter of the samples exhibited concentrations above the relevant Swiss guide value for compost (4000 microg kg(-1)dw). The levels were influenced by the treatment process (digestate > compost), the season of input material collection (spring-summer > winter > autumn), the particle size (coarse-grained > fine-grained), and maturity (mature > less mature). The main source of PAH in compost was pyrogenic, probably influenced mainly by liquid fossil fuel combustion and some asphalt abrasion, as suggested by multiple linear regression. This study, together with a companion paper reporting on other organic contaminates including emerging compound classes, provides a starting point for a better risk-benefit estimation of the application of compost and digestate to agricultural soil in Switzerland.     

Reproductive success of monogamous and polygynous pied flycatchers (Ficedula hypoleuca)

One of the most interesting aspects of the mating system of pied flycatchers is the regular occurrence of polygyny. Here we present data on the reproductive success of polygynously paired pied flycatcher males compared to monogamous males based on paternity analyses through DNA fingerprinting. Males paired with two females suffered a higher loss in reproductive output per female compared to monogamous males due to (1) a greater proportion of unhatched eggs in their broods, (2) greater nestling mortality and (3) a greater probability of being cuckolded. Nevertheless, the number of fledglings was significantly greater for polygynous males. Based on the number of nestlings that returned for subsequent breeding seasons, however, the reproductive success of monogamous and polygynous males did not differ significantly. These data raise the question as to why males attempt polygyny. Received: 16 August 1999 / Received in revised form: 15 March 2000 / Accepted: 18 March 2000     

Chemical defense of the mint plant, Teucrium marum (Labiatae)

Summary. The mint plant, Teucrium marum (family Labiatae), sometimes called cat thyme, contains two methylcyclopentanoid monoterpenes, dolichodial and teucrein. The former compound is potently anti-insectan. It is repellent to ants (Monomorium pharaonis) and induces preening reflexes in flies (Phormia regina) and cockroaches (Periplaneta americana). Evidence is presented suggesting that dolichodial, which is presumed to be the plant's chief defensive agent, is stored in the tiny epidermal capsules that beset the leaves. It is only when the leaves are injured (and the capsules ruptured) that the leaves become repellent. Teucrein, in contrast, has no anti-insectan potency. It is present predominantly in the leaf buds, unlike dolichodial, which is present mostly in mature leaves. It is argued that teucrein is the storage compound from which dolichodial is generated during leaf development.     

An experiment on the ability of free-ranging turkey vultures (Cathartes aura) to locate carrion by chemical cues

((without abstract.))     

Oviposition of carrot fly (Psila rosae) in response to foliage and leaf surface extracts of host plants

Summary. Foliage of twelve host and two non-host species and surrogate leaves treated with the respective leaf extracts were presented to laboratory populations of the carrot fly (Psila rosae) in oviposition choice assays. The stimulatory activity of dichloromethane surface extracts and the diethyl ether fraction of hot water extracts did not reflect accurately the differences in acceptability observed among intact leaves. A better correlation was found using hexane extracts prepared in a microwave oven. Two out of five fractions of this crude hexane extract obtained by silica gel column chromatography stimulated oviposition. The diethyl ether fraction, which contained the previously identified oviposition stimulants (propenylbenzenes, furanocoumarins, polyacetylenes), could account for only a minor part of the variation in the acceptability of host leaves. The preference hierarchy for intact leaves corresponded better to the ranking of species according to activity of the methanolic fraction, which apparently contains unknown stimulatory compounds.? The water fractions of the hot water extracts were shown to reduce egg-laying underneath surrogate leaves treated with a stimulatory extract. This oviposition-deterring effect was particularly strong with the non-preferred species Pimpinella major, which is also highly resistant in the field. Hence, unidentified inhibitory compounds may also contribute to differential accept ability of host plants. It is concluded that antixenotic (non-preference) resistance of host plants to carrot fly attack depends on complex mixtures of semiochemicals. Received 11 June 1997; accepted 26 November 1997.     

Biological effect monitoring in dab (<Emphasis Type="Italic">Limanda limanda</Emphasis>) using gene transcript of CYP1A1 or EROD—a comparison

BACKGROUND, AIM, AND SCOPE: Gene expression analyses with real-time (RT)-polymerase chain reaction (PCR) gains importance in marine monitoring. This new technique has to be compared to the classical approaches like the well known biomarker ethoxyresorufin-O-deethylase (EROD) to test their suitability for monitoring programmes. The goal of the present study is to compare EROD activity and CYP1A1 mRNA expression in the important monitoring fish species dab (Limanda limanda) and to answer the question of whether these parameters reflect the polycyclic aromatic hydrocarbon (PAH) contamination of the fish. Further on, glyceraldehyd-3-phosphate dehydrogenase (GAPDH) was investigated as a potential housekeeping gene. MATERIALS AND METHODS: Female dab were caught in the summer of 2004 in the North Sea and in the Baltic. EROD activity was determined in liver samples by a kinetic fluorimetric assay according to a standard protocol. The gene expression of CYP1A (cytochrome P450 1A) and GAPDH were determined by means of RT-PCR. Results were compared to gonado somatic index and to the concentration of PAH metabolite 1OHPyr (1-hydroxypyrene) analysed in the bile fluids of the fish, respectively. RESULTS: Dab from all stations showed a considerable individual variation in the levels of both CYP1A mRNA and EROD. Highest mean values for CYP1A mRNA and EROD were detected in the northern part of the sampling area. In contrast, the PAH metabolite 1OHPyr was found at the highest concentration in fish caught near the German coast. CYP1A mRNA and EROD showed only a minor but significant correlation (r = 0.32, p < 0.05, n = 123). 1OHPyr in bile correlated significantly (p < 0.05) with the amount of GAPDH mRNA content in the liver. DISCUSSION: The significant but low correlation of CYP1A mRNA and EROD activity on an individual basis illustrates that these two parameters are apparently not closely linked. However, maximum EROD values correspond with maximum CYP1A mRNA concentrations when station means are regarded. Because EROD and CYP1A mRNA in dab follow different physiological principles, their application will lead to related but not identical monitoring results. This should be taken into account when future marine monitoring programmes are designed. The results also indicate that PAH are not the crucial factor for CYP1A and EROD levels in dab from the off-shore areas in the North Sea. This is remarkable because the PAH metabolism is known to be CYP1A-dependent and the widely used biomarker EROD has been recommended for monitoring PAH-related effects in fish from the North Sea. Due to a correlation between GAPDH and 1OHPyr, GAPDH was not suitable as housekeeping gene for dab. CONCLUSIONS: Neither the results from EROD nor from CYP1A1 mRNA measurements in dab reflected their exposure to PAH as measured by the PAH metabolite 1OHPyr. Thus, the question arises of whether EROD or CYP1A mRNA is a suitable biomarker at all to indicate PAH exposure in dab from the open North Sea. RECOMMENDATIONS AND PERSPECTIVES: For future biological effect monitoring, it is advisable to measure more and predominately independent parameters by RT-PCR and to incorporate more components of the detoxification system.     

Uptake of some selected aquatic pollutants in semipermeable membrane devices (SPMDs) and the polar organic chemical integrative sampler (POCIS)

The uptake characteristics of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs) were examined for mono, di and tributyltin, triphenyltin, pyrene, benzo[a]pyrene, 4-tert-butylphenol, 4-n-nonylphenol, PCBs 77 and 153, PBDE 47, lindane, triclosan and DDT. Exposure in a flow through system continued for 28 days with samplers removed every 7 days in order to study the relevant uptake kinetics. Uptake remained linear for POCISs with sampling rates (Rs) of up to 0.2 L d(-1). For SPMDs uptake varied from linear to approaching equilibrium with Rs values of up to 14 L d(-1). 7 out of 9 results for SPMDs could be explained by an empirical model (nonylphenol and lindane were exceptions). None of the four organo-tin compounds studied were detected in POCISs and only tributyltin was accumulated significantly by SPMDs. The establishment of these sampling rates allows the calculation of time weighted water concentrations for several important contaminants. Using presented methods, sampling rates and exposure conditions, theoretical detection limits for selected compounds by SPMDs were between 11-68 pg L(-1), which is well below the environment quality standard proposed for those compounds that are included in the European Water Framework Directive.