Comparison of measured and predicted concentrations of selected pharmaceuticals in wastewater and surface water: a case study of a catchment area in the Po Valley (Italy).

The aim of this study is to compare measured and predicted concentrations of 11 antibiotics and the antiepileptic carbamazepine in wastewater and surface water and to discuss the accuracy and usefulness of applied predictive models in assessing their concentrations. The occurrence (exposure assessment) of the target compounds was monitored in the influent and effluent of a large municipal wastewater treatment plant, and in its receiving water body, situated in the Po Valley, Italy. Information on the consumption and sales of pharmaceuticals in Italy, along with data related to their excretion and removal during wastewater treatment, were used to predict the concentrations of the selected pharmaceuticals for the studied site. The measured and predicted concentrations were compared for all three sampling points, and according to a criterion available in literature and already adopted in similar studies, the prediction was considered "acceptable" when the ratio of predicted and measured concentrations was between 0.5 and 2. The results show that the concentrations were accurately predicted for ciprofloxacin in wastewaters, and for azithromycin, trimethoprim and carbamazepine in surface water. For all the other compounds and sampling points, the difference between the measured and the predicted concentrations was very high. Possible reasons for these discrepancies are discussed and the main potential factors that influence both measured and predicted concentrations are identified by means of an assessment of the uncertainties in the measured values and sensitivity of all the parameters required for predicting concentration ones. The potential factors are sampling mode for measured values and dilution factor, removal and excretion for predicted ones.

Transformation products and reaction pathways of carbamazepine during photocatalytic and sonophotocatalytic treatment.

This study examines the degradation of the antiepileptic carbamazepine (CBZ) by sonolysis, TiO2-based heterogeneous photocatalysis under UV-A and simulated solar irradiation, and by the combined use of UV-A and ultrasound irradiation (i.e. sonophotocatalysis) in demineralized water, ground water and effluent wastewater. The processes were compared with respect to substrate conversion rate and the extent of DOC reduction as a measure of mineralization. CBZ was degraded following a pseudo-first order kinetics. Sonophotocatalysis provided the highest rate of CBZ transformation over the time-course of the experiment while the degree of DOC removal in pure water was similar for all the studied treatments (around 40%), and always lower than CBZ conversion. This indicated that a considerable organic load remained in the treated solutions that could also be attributed to the presence of persistent oxidation products. UPLC-(+ESI)-QToF-MS was employed to determine major CBZ-related transformation products. Several recalcitrant hydroxy- and keto-derivatives of CBZ were tentatively identified. A Daphnia magna bioassay was used to evaluate the potential toxicity of the samples collected at different time points showing that the mixtures were highly toxic to D. magna.

Monitoring release of pharmaceutical compounds: occurrence and environmental risk assessment of two WWTP effluents and their receiving bodies in the Po Valley, Italy.

This study describes an investigation on the occurrence of 27 pharmaceutical compounds, belonging to different classes, in the effluent from two wastewater treatment plants (WWTPs) and their receiving water bodies in the sensitive area of the Po Valley (northern Italy). These canals were monitored upstream and downstream of the effluent discharge points in order to evaluate the effluent impact on the quality of surface waters, commonly used for irrigation. An environmental risk assessment was also conducted by calculating the risk quotient, i.e. the ratio between measured concentration and predicted no effect concentration. Collected data show that, although average values of the selected compounds were in general higher in the effluent than in the surface waters, some compounds not detected in the WWTP effluent were detected in the receiving water (upstream as well as downstream), indicating that sources other than treated effluents are present as contaminations during extraction and analysis have to be excluded. The most critical compounds for the environment were found to be the antibiotics sulfamethoxazole, clarithromycin and azithromycin. The study shows that the potential toxicological effects of persistent micropollutants can be mitigated to some extent by a high dilution capacity, i.e. a high average flow rate in the receiving water body with respect to the effluent.

Determination of pharmaceuticals in sewage sludge by pressurized liquid extraction (PLE) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS).

In this study, we aimed at optimizing a sensitive and reliable method for a simultaneous determination of 31 pharmaceuticals belonging to predominant therapeutic classes identified in different types of sewage sludge proceeding from conventional and advanced wastewater treatment. Freeze-dried sewage sludge was extracted by pressurized liquid extraction technique using accelerated solvent extractor Dionex 300. In order to minimize interferences with matrix components and to preconcentrate target analytes, solid phase extraction was introduced in the method as a clean-up step. The entire method was validated for linearity, precision, accuracy, and method detection limits (MDLs). The method turned out to be specific, sensitive, and reliable for the analysis of sludge of different composition, type, and retention time in the process. The developed sample preparation protocol and previously published method for LC-MS/MS analysis (Gros et al., Talanta 70:678-690, 2006) were successfully applied to monitor the target pharmaceuticals in different types of sewage sludge, i.e., primary sludge, secondary sludge, treated sludge, and sludge proceeding from pilot-scale membrane bioreactors (MBRs) operating in parallel to the conventional activated sludge treatment. Among the investigated pharmaceuticals, 20 were detected in the sludge proceeding from full-scale installations, whereas the MBR sludge concentrations were below MDLs for several compounds. The highest concentrations were recorded for treated and primary sludge. For example, the mean concentration of ibuprofen in the digested sludge was 299.3 +/- 70.9 ng g(-1) dw, whereas in the primary sludge, it was enriched up to 741.1 ng g(-1) dw. Other pharmaceuticals detected at relatively high concentrations were diclofenac, erythromycin, glibenclamide, ketoprofen, ofloxacin, azithromycin (up to 380.7, 164.2, 190.7, 336.3, 454.7, 299.6 ng g(-1) dw in the primary sludge, respectively), gemfibrozil, loratidine, and fluoxetine (up to 189.1, 189.7 and 174.1 ng g(-1) dw in the treated sludge, respectively).

Prevalence of markers of hepatitis B virus infection among the general population of the municipality of Slavonski Brod.

To assess the prevalence of hepatitis B viral infection in general population of the Community of Slavonski Brod, sera from 2,142 apparently healthy individuals were tested for the hepatitis B virus (HBV) markers: surface antigen and antibody (HBsAg and anti-HBs), and core antibody (anti-HBc), by radio and enzyme-immunoassay. The HBsAg results showed a general prevalence of 1.8%(38/2,142): for males 1.9% and for females 1.6%. The highest HBsAg incidence rates (2.1% and 1.9%) were found in young adults aged 21-30, respective in older children and adolescents, from 11 to 20 years. The lowest HBsAg prevalence (1.0%) was proved in children from 1 to 5 years, while in sera of 68 examined sucklings HBsAg was not detected. The HBsAg incidence was 1.9% (21/1132) in urban and 1.7% (17/1010) in rural inhabitants. The overall prevalence rate of total HBV infection in 13.7% (294/2,142) examinees was found. There was no difference in the prevalence of HBV infection in males 15.7% (177/1130) and females 11.6% (117/1012), as well as in persons living in rural 12.5% (126/1010) or in urban 14.8% (168/1132) areas. The prevalence rate of anti-HBs and anti-HBc gradually increased with increasing age, starting at about 3.2% in the youngest, and reaching 15.5% in adults over 50 years. The results obtained have place the Community of Slavonski Brod among areas with an intermediate endemicity of HBV infection.

[Fractures of the clavicle in neonates]. / Frakture klavikule u novorodencadi.

One hundred and twenty-five newborn infants (6.26%) with clavicular fractures were detected among 1995 neonates seen at the maternity hospital over a period of 16 months. Physical and only exceptionally X-ray examinations were performed. Clinical picture with the subsequent occurrence of callus were pathognomonic signs. The following parameters were taken into consideration for this study: infant's birth weight, sex, risk factors, way of delivery, delivery line, Apgar score, seasonal distribution and complications. Newborn infants with clavicle fracture were infants whose weight was more than 3500 g (3763.36 +/- 360.58 g, chi 2 = 65.605, P < 0.05), most frequently from mothers with the second childbirth (48.8%), babies born in a normal and natural way (58.4%), and in 71. 33% of the cases with some risk factors and Apgar score more than 7. One thousand seven hundred and forty-two out of a total of 1995 neonates had birth weight less than 4000 g and in 92 of these 1742 infants (5.29%) clavicular fractures were found, while in 253 newborn infants with birth weight more than 4000 g, 33 neonates (13.05%) had clavicular fractures. Clavicle fractures were more frequently found among the infants with birth weight more than 4000 g (P < 0.05). Three out of a total number of infants had paresis plexus brachialis, two of which belonged to the group of children with clavicle fractures. This study suggests that the approach to the childbirth conducting should be changed, so that the percentage of clavicle fractures can be reduced or noticed in time by help of more frequent and systematic clinical examinations.(ABSTRACT TRUNCATED AT 250 WORDS)

[The Brachmann-de Lange syndrome]. / Brachmann-de Lange sindrom.

On occasion of the 120th anniversary of Cornelia de Lange's birth, the recognized Dutch pediatrician, and the 40th anniversary of her death, we report a case with Brachmann-de Lange syndrome. The patient was hospitalised several times, immediately after the birth, within the 3rd year of life, and finally at the age of 13 years. The diagnosis was already established in the neonatal period by relevant symptomes. The phenotypical variations remained unchanged during that period and the patient presented with a great number of symptoms typical for this entity. The characteristics of the head and face were specially prominent, then the anomalies of the upper extremities and malrotation of the intestines. Since there is a great similarity with other syndromes, karyogram is indispensable for the diagnosis of this condition.

[Epidemiologic characteristics of acute and recurrent middle ear inflammation in childhood]. / Epidemioloske karakteristike akutnih i recidivirajucih upala srednjeg uha u djecjoj dobi.

The authors studied the incidence of acute and relapsing inflammations of the middle ear, together with factors relating to inflammation in 393 children aged up to 36 months. The results revealed that of 393 children followed up for 12 months, 175 (44.52%) had acute otitis media and 40 (22.85%) had relapses. No relationship was found between age and acute inflammation, but the rate of relapses was significantly higher during the first year of life. There was no significant influence of the sex of the child, socioeconomic status and place of living on the appearance of the inflammations. The attendance of infant nurseries and day-care centres had significant influence on higher rate of acute inflammations but not on relapses. There was no influence of acute otitis media of the members of the family on incidence of the same disease in their children, but there was evidence of influence on relapses. The highest incidence of inflammation occurred in autumn and winter months, November, December and January (61.67%) versus only 1.76% in summer months (July, August). Only 2 children had scars of the eardrums presenting as an early consequence of the disease, while none had any complications of the middle ear inflammation.

[The effect of certain factors on the occurrence of sudden infant death syndrome]. / Utjecaj nekih faktora na pojavu sindroma iznenadne smrti dojenceta (SIDS).

Although sudden infant death syndrome (SIDS) has been well known for a long time, in our country it has not been registered adequately yet and has seemed not to be present those years. But, it has not been true. A number of predisposing factors make that this phenomenon has a high share in postneonatal mortality, especially in those environments where the infant's mortality rate is low. A pathologist is imperative to establish a diagnosis following not only inadequate clinical picture and sudden death but also uncertain autopsy finding which does not make clear the cause of death in the majority of cases. In this paper, the frequency of SIDS during the epidemic of acute respiratory infection caused by respiratory syncytial virus being the potential indirect cause of the infants' deaths is presented. In 2/3 of cases this have been the infants born with perinatal risk factors and more often they have been males. SIDS has usually occurred at night, during autumn and winter and with infants coming from lower socio-economic and culturo-hygienic environments. In our environment, the frequency of SIDS has amounted to 22% of the total infant mortality rate.

[A bronchiolitis epidemic caused by respiratory syncytial viruses]. / Epidemija bronhiolitisa uzrokovana respiratorno sincicijalnim virusom.

In the typical period of the year (autumn-winter 1986-1987) an outbreak of bronchiolitis in infants caused by respiratory syncytial virus (RSV) occurred. The acute course of the illness, a severe clinical picture, and a very fast spread of infection called for the very rapid techniques for detecting the etiological agent. Applying the direct immunofluorescent antibody test (DFTA) in samples of nasopharyngeal secretions, RSV was found to be responsible for the epidemic. Later the same samples of the material were inoculated into tissue cultures and RSV was isolated. Fourfold or higher titres of complement fixing antibodies in paired serum samples confirmed the infection with RSV. During the outbreak of bronchiolitis 72 children aged under 15 months (only one child was older than one year) were hospitalized. The majority of cases of RSV bronchiolitis was noticed in infants in the first six months of life (81.9%, chi 2 = 31.1, p less than 0.01). Boys against girls were in relation as 1.25:1. Because of the broncho-obstructive component of the illness, respiratory failure was the dominant sign in the clinical picture of bronchiolitis; 34.7% of the patients were afebrile, 16.7% were in the state of hyperpyrexy and 48.6% with temperature up to 38 degrees C. Oxygen and symptomatic therapy were the basic treatment. In severe cases corticosteroids and antibiotic were administered for a short time. The classical type of bronchiolitis in infancy as the most severe among acute infections of respiratory organs because of its poor prognosis at the very beginning and the long-term sequels is a serious medical problem. Emphasis is laid on the importance and usefulness of the virologic diagnosis, especially the application of rapid DFTA techniques in the acute stages of bronchiolitis caused by infections with respiratory syncytial virus during the epidemic occurrence of this agent.

[The Ellis-van Creveld syndrome]. / Ellis-van Creveldov sindrom.

A case of Ellis-Van Creveld syndrome is presented. The diagnosis was established after birth and was based on three major symptoms: unproportionally small stature, hexadactylism and ectodermal dysplasia. The heart finding was normal and the other laboratory tests were negative. Other symptoms were less important for this syndrome. It is a chondroectodermal dysplasia of autosomal recessive type. Reports from the literature are discussed as well, especially symptoms that are rarely found in such patients. This report is intended to point out the effective role of ultrasonography in establishing the early diagnosis of this syndrome in prenatal period.