Trihalomethane formation during water disinfection in four water supplies in the Somes river basin in Romania

Background, aim and scope

After the discovery of chloroform in drinking water, an extensive amount of work has been dedicated to the factors influencing the formation of halogenated disinfections by-products (DBPs). The disinfection practice can vary significantly from one country to another. Whereas no disinfectant is added to many water supplies in Switzerland or no disinfectant residual is maintained in the distribution system, high disinfectant doses are applied together with high residual concentrations in the distribution system in other countries such as the USA or some southern European countries and Romania. In the present study, several treatment plants in the Somes river basin in Romania were investigated with regard to chlorine practice and DBP formation (trihalomethanes (THMs)). Laboratory kinetic studies were also performed to investigate whether there is a relationship between raw water dissolved organic matter, residual chlorine, water temperature and THM formation.

Materials and methods

Drinking water samples were collected from different sampling points in the water treatment plant (WTP) from Gilau and the corresponding distribution system in Cluj-Napoca and also from Beclean, Dej and Jibou WTPs. The water samples were collected once a month from July 2006 to November 2007 and stored in 40-mL vials closed with Teflon lined screw caps. Water samples were preserved at 4°C until analysis after sodium thiosulfate (Na₂S₂O₃) had been added to quench residual chlorine. All samples were analysed for THMs using headspace GC-ECD between 1 and 7 days after sampling. The sample (10 mL) was filled into 20-mL headspace vials and closed with a Teflon-lined screw cap. Thereafter, the samples were equilibrated in an oven at 60°C for 45 min. The headspace (1 mL) was then injected into the GC (Cyanopropylphenyl Polysiloxane column, 30 m × 53 mm, 3 μm film thickness, Thermo Finnigan, USA). The MDLs for THMs were determined from the standard deviation of eight standards at 1 μg/L. The MDLs for CHCl₃, CHBrCl₂, CHBr₂Cl and CHBr₃ were 0.3, 0.2, 0.3 and 0.6 μg/L, respectively. All kinetic laboratory studies were carried out only with water from the WTP Gilau. The experiments were conducted under two conditions: baseline conditions (pH 7, 21°C, 2.5 mg/L Cl₂) to gain information about the change of the organic matter in the raw water and seasonally variable conditions to simulate the actual process at the treatment plant and the distribution system.

Results and discussion

This study shows that the current chlorination practice in the investigated plants complies with the THM drinking water standards of the EU. The THM concentrations in all samples taken in the four treatment plants and distributions systems were below the EU drinking water standard for TTHMs of 100 μg/L. Due to the low bromide levels in the raw waters, the main THM formed in the investigated plants is chloroform. It could also be seen that the THM levels were typically lower in water supplies with groundwater as their water resource. In one plant (Dej) with a pre-ozonation step, a significantly lower (50%) THM formation during post-chlorination was observed. Laboratory chlorination experiments revealed a good correlation between chloroform formation and the consumed chlorine dose. Also, these experiments allowed a semi-quantative prediction of the chloroform formation in the distribution system of Cluj-Napoca.

Conclusions

CHCl₃ was the most important trihalomethane species observed after the chlorination of water in all of the sampled months. However, TTHM concentrations did not exceed the maximum permissible value of 100 μg/L (EU). The THM formation rates in the distribution system of Cluj-Napoca have a high seasonal variability. Kinetic laboratory experiments could be used to predict chloroform formation in the Cluj-Napoca distribution system. Furthermore, an empirical model allowed an estimation of the chloroform formation in the Gilau water treatment plant.

     

Prenatal diagnosis of thalassemia: The viewpoint of patients

Twenty-eight young people with thalassemia major expressed their opinion about prenatal diagnosis. All of them stated that they intended to marry and have children; thirteen of them (46 per cent) said that they would have also accepted a thalassemic carrier as a partner and that if married to a carrier they would have undergone prenatal diagnosis and selective abortion. All but one refused the prospect of an affected child. When asked if they would have preferred that before their birth their parents had undergone prenatal diagnosis and abortion, 19 patients (68 per cent) gave an affirmative answer. These results clearly indicate that even people affected by thalassemia major, who are the potential victims of prenatal diagnosis and selective abortion, largely accept prenatal diagnosis as a means of preventing their disease.     

Psychological consequences of prenatal diagnosis in a case of familial Angelman Syndrome

Angelman Syndrome (AS), characterized by mental retardation, absence of speech, seizures and motor dysfunction, is caused by genetic defects leading to loss of expression of the maternal copy of the chromosome 15q11–13 imprinted region. Most cases are sporadic, being caused by de novo deletion of maternal chromosome 15q11–13 (75%) or by paternal uniparental disomy (3–4%). Familial cases can occur, due to mutations in the UBE3A gene or in the imprinting center. We describe the case of a pregnant woman having two nephews with AS caused by a UBE3A mutation; lack of communication within the family led the woman to be completely unaware of the risk of disease recurrence until 15 weeks of gestation. UBE3A genetic testing revealed she carried the familial mutation 892–893delCT. Prenatal diagnosis was performed on amniotic fluid and demonstrated that the fetus had inherited the mutation. The unexpected diagnosis and the subsequent termination of the pregnancy caused the woman to undergo acute psychological distress showing relevant psychopathological symptoms. Nevertheless, at 2-year follow-up, adverse consequences were minimized, and the couple was planning a new pregnancy. Factors affecting the psychological outcome of abortion and the role of psychological support in reducing the risk of long-term unfavorable consequences are discussed. Copyright © 2006 John Wiley & Sons, Ltd.     

SOIL ZINC CONTAMINATION FROM CORROSION OF GALVANIZED STRUCTURES

The present work relates to galvanized structures with several years of time life subjected to atmospheric corrosion, like galvanized high tension steel pylons. The mass and fate of zinc released is evaluated both via empirical and experimental procedures. The corrosion rate determination requested atmospheric condition characterization, especially for SO 2 concentration and experimental activities focused on soil sampling around pylons. The soil zinc content, total and exchangeable, is determinates by different analytical procedures. The zinc diffusion in environment and the zinc extension under the top soil is evaluated using 1-dimensional mathematical model for miscible species in porous soil.     

Heavy Metals and Chlorinated Hydrocarbon Concentrations in the Red Fox in Relation to Some Biological Paramaters

Heavy metals and organochlorine contamination were analyzed in tissues of red foxes (Vulpes vulpes) from the Province of Siena (central Italy). Mercury (Hg), cadmium (Cd) and lead (Pb) concentrations were assessed in liver tissues and the data were analyzed for differences in relation to sex and age. Overall Hg, Cd and Pb mean values were 0.16, 0.62 and 0.64 g g^_1 d.w., respectively. HCB, DDT and PCB concentrations were assayed in fatty tissues and muscle. The highest levels of those pollutants were found in muscle (0.47, 1.16 and 20.2 g g^_1 lipid basis of HCB, DDTs and PCBs respectively), rather than in fat (0.23, 0.49 and 7.2 g g^_1 l.b. of HCB, DDTs and PCBs respectively). Pollutant accumulation was analyzed in relation to sex, age and sexual maturity of females.     

Trihalomethane formation during water disinfection in four water supplies in the Somes river basin in Romania

Background, aim and scope  

After the discovery of chloroform in drinking water, an extensive amount of work has been dedicated to the factors influencing the formation of halogenated disinfections by-products (DBPs). The disinfection practice can vary significantly from one country to another. Whereas no disinfectant is added to many water supplies in Switzerland or no disinfectant residual is maintained in the distribution system, high disinfectant doses are applied together with high residual concentrations in the distribution system in other countries such as the USA or some southern European countries and Romania. In the present study, several treatment plants in the Somes river basin in Romania were investigated with regard to chlorine practice and DBP formation (trihalomethanes (THMs)). Laboratory kinetic studies were also performed to investigate whether there is a relationship between raw water dissolved organic matter, residual chlorine, water temperature and THM formation.     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca,Romania

Background, aim, and scope

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.

Materials and methods

The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide.

Results and discussion

The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly: caffeine (400–2,000 g/day), carbamazepine (78–213 g/day), galaxolide (140–684 g/day), ibuprofen (84–108 g/day). After the upgrade of the WWTP Cluj-Napoca, the concentrations in the Somes of caffeine, pentoxifylline, cyclophosphamide, galaxolide, and tonalide were significantly reduced (over 75%). One might be cautious comparing both studies because the relative efficiency of the WWTP’s removal of PPCP was not evaluated. However, the significantly lower concentrations of most compounds after the upgrade of the WWTP Cluj-Napoca allow one to infer that the technical measures at the source substantially reduced inputs of contaminants to the receiving river. Dej loads of the poorly biodegradable substance carbamazepine increased by a factor of 2–3 as a result of wastewater discharges into the river. The disproportionate increase in caffeine loads by a factor of 4 below Cluj-Napoca indicates inputs of untreated wastewater from the Somes Mare due to the discharge of untreated wastewater derived from Bistrita, Nasaud, and Beclean (115,000 inhabitants).

Conclusions

The relative contribution of treated and untreated wastewater in surface water might be assessed by measuring chemical markers. Recalcitrant pharmaceuticals like carbamazepine are suitable as chemical markers for estimating the relative contribution of wastewater in surface water. The easily degradable caffeine might be a good indicator for raw sewage and hardly treated wastewaters.

Recommendations and perspectives

Municipal WWTPs have the potential of a significant contribution in reducing the load of contaminants to ambient waters. The efficiency of the wastewater treatment in Cluj-Napoca improved considerably after the upgrade of the WWTP. Therefore, it is crucial that several WWTPs must be implemented or improved in the Somes Valley Watershed in order to reduce the discharge of contaminants in the Somes River from these point sources.

     

Low to negligible photoactivity of lake-water matter in the size range from 0.1 to 5 μm

We found that the photochemical generation of reactive transients such as singlet oxygen and triplet states upon irradiation of different lake water samples is mostly accounted for by components smaller than 0.10 μm. Larger components often showed a much lower absorption and/or scattering of radiation compared with the smaller ones, with one exception where the minor to negligible photochemical activity of larger species was associated with significant radiation absorption/scattering. It is also shown that filtration of the lake water samples at 0.10 μm was able to effectively remove the suspended particles, differently from the usually suggested filtration at 0.45 μm.     

VOC destruction by water diluted hydrogen mild combustion

This study represents a preliminary numerical evaluation of the effect of steam dilution and hydrogen addition on the oxidation of formaldehyde and benzene, chosen as representative of the volatile organic compounds (VOC), in mild condition by evaluating the autoignition time and the steady state attainment. These parameters are important in the design of thermal VOC destruction plants since they influence the abatement efficiency and, therefore, the plant dimension. It has come out that, in comparison with the system diluted in nitrogen, steam induces lower autoignition times and, on the other hand, longer times for the attainment of the steady state. In contrast, for very high water content the autoignition time slightly increases. In particular results have shown that is possible to identify an optimum value of steam content that allows for the attainment of the steady state condition by the lowest residence time. Hydrogen addition to systems diluted in nitrogen promotes the oxidation reactions and anticipates the steady state condition. In steam diluted systems hydrogen delays the autoignition of the mixtures even though anticipates the attainment of the complete destruction of the VOC. The rate of production analysis has showed that the H(2)/O(2) reactions, that promote the ignition and the destruction of VOC, are sensibly modified by the presence of water and hydrogen.