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Antidiabetic compounds are a class of emerging contaminants in environment, for which there are no regulations in the world environmental legislation. These compounds are among the most widely used drugs in the world due to the large number of patients with diabetic conditions. The presence of these pollutants in the environment is insufficiently studied, so efficient analytical methods are needed to allow their detection at trace levels (ng/L). For the simultaneously quantification of the five antidiabetics (glyburide, metformin, glipizide, gliclazide, glimepiride) and one bio-degradation product (guanyl urea) in surface water samples a SPE-LC-MS/MS (solid phase extraction -liquid chromatography coupled with mass spectrometry detection) method was validated using real river water samples. The compounds were separated on C18 LC column in 9 minutes at 300C using a gradient of mobile phase of 0.1% formic acid and acetonitrile. Good performance parameters were obtained using the method: low limits of quantification (LOQs 0.1-2.4 ng/L), precision (repeatability 3.5-7.2% and reproducibility 6.5-12.7%) and determination coefficients (higher than 0.99). The most contaminated river was represented by Ialomita, which had a total concentration of antidiabetics of 112.1 ng/L in the downstream point, followed by the Siret and Dambovita rivers, which had a total concentration of antidiabetics of 66.3 ng/L and 57.3 ng/L, respectively, also in the downstream points.

Emerging contaminants are a heterogeneous group of chemicals that include daily personal care products and pharmaceuticals (PPCPs), flame retardants, endocrine-disrupting chemicals (EDCs) and nanoparticles (NPs) present in environment which are unregulated. In this review, we present the methods of analysis conducted by INCD-ECOIND regarding some classes of emerging contaminants (neonicotinoid pesticides, beta-blocker drugs) that are not regulated by the legislation, in different types of environmental samples (wastewater, surface water). The present review presents the selective solid-phase extraction (SPE) methods used for isolation of the targeted compounds from aqueous matrices and also the main instrumental parameters of the separation and detection process. After extraction, the compounds were subjected to liquid phase chromatographic separation with mass spectrometric detection (UHPLC-MS/MS). Finally, the methods were applied in the determination of compounds from different categories of water, carrying out studies on the efficiency of elimination of compounds in several municipal wastewater treatment plants (WWTPs). In addition, the impact of the treatment plants on some receiving surface water used to obtain drinking water was studied.

Antidiabetic drugs are among the most prescribed and consumed pharmaceuticals worldwide. Their occurrence in environment was little investigated due of lack of analytcial methods for their detection in waters. In this work has been developed a selective SPE-UHPLC/MS/MS method for isolation, identification and quantification of some antidiabetic compounds. The 3 selected analytes (glyburide, glimepiride and repaglinide) were separated on Eclipse C18 LC column at 300C using isocrat elution with mobile phase of acetonitrile: 0.04% acetic acid (60/40, v/v %). The optimal flow rate was 0.2 mL/min and the injected volum was 10 µL. The contaminants were detected in negative electropray ionization mode (ESI-) by Multiple Reaction Monitoring (MRM). Collision energy, fragmentor voltages were optimized to obtain high sensitivity. Optimization of SPE-LC-MS/MS parameters gave low quantification limit values between 0.27 and 11.1 ng/L. The organic pollutants were isolated from waste water samples on Strata C18 cartridges. The linear regressions were drawn in the interval of 1-100ng/L with good determination coefficients. Spike recovery rates were between 74.5 and 88.2% for waste water, with satisfactory precisions (RSD

Global population growth is associated with an increase in the amount of water used. A consequence of this increase is the high amount of wastewater volume resulted, which can affect ecosystems balance. For this reason, the authorities are forced to account and improve wastewater treatment processes to minimize environmental impact. The physical-chemical properties of the effluent are unique and depend on the origin of the leakage, the sewer system infrastructure, the level of development of the area, the climatic conditions, and hence the wastewater stream has a unique composition of organic and inorganic loads. For a quick and easy understanding of wastewater quality, two types of water quality indices were developed. This study presents the results of a complex analytical investigation of effluents discharged from six rural WWTP’s situated in southern part of Romania compared with a simplified interpretation of wastewater quality by using a pollution index (PI) and a wastewater quality index (WWQI). Data recorded with a monthly frequency between 2013 and 2017 were used. Regarding the WWQI values calculated in this study, all wastewater analysed from the six WWTP’s, fit to the ‘Marginal’ Designation.

The market expansion due to globalization generated more anthropogenic contaminants, enhancing their negative impact on the environment. In order to prevent and balanced their negative effect, more rapid, sensitive and eco-friendly ecotoxicological studies as risk assessments were developed. Each country developed national programs to ensure the research infrastructure for implementation and development of new testing methodologies, generating new experimental data transferable to governmental authorities, economic agents and academia. In this review, we intend to highlighted the progress of Romanian researchers in the last 10 years in the field of ecotoxicology and aquatic risk assessment. The studies focused on aquatic systems as a non-targeted system to the anthropogenic pollutants impact. The implemented methodologies according with international requirements for chemical control like REACH Regulation, Detergents Regulation, Biocide Products Regulation or the Aquatic Risk Assessment Guidelines were presented. The ecotoxicological effects of various contaminants such as detergents, pharmaceuticals, pesticides, biocides or heavy metals and environmental polluted samples (surface water, sediment or sludge) were provided. Overall, the studies presented in our studies have a nationally novelty through the variety of test substances, the complexity of laboratory experiments and data processing. The research work has a continue applicability in industry and for control authorities. New accredited testing services that providing useful information about the chemicals and their impact on the environmental were introduced. In addition, the ecotoxicology studies and their challenges were a great source for professional training like PhD and master studies and for impact published papers.

Dietary exposure to several heavy metals such as Cd, Cr, Pb, As represents a risk to human health through the consumption of vegetables. Due to the possible risks for the human body, contamination of soils as well as drinking and irrigation water has been the subject of many researches. In this study, the analysis of heavy metals content from soil, water and vegetable samples from households in Ilfov County it was carried out. As a result, no contamination of soil and water with heavy metals was observed. Cadmium content is above the maximum allowable limit for all analyzed vegetables, excepting cabbage and green onion. Two lettuce samples have an alarmingly high content of lead, the values being even 10 times higher than the maximum admissible limit of 0.3 mg/kg. The high values obtained for chromium content in lettuce and radish samples raise serious questions about possible contamination. Arsenic content values ranged between 0.87 and 7.69 mg/kg, which also represents high values. Based on the transfer factor (TF) calculated the strongest accumulation of the metals was in lettuce.

International Symposium "The Environment and the Industry", 26-27 September 2019, Bucharest, Romania, pp. 67-68

The aquatic environment is under increased pressure by pharmaceutically active compounds (PhACs) due to anthropogenic activities. In spite of being found at very low concentrations (ng/L to μg/L) in the environment, PhACs represent a real danger to aquatic ecosystems due to their bioaccumulation and long-term effects. In this study, the presence in the aquatic environment of six non-steroidal anti-inflammatory drugs (ibuprofen, diclofenac, acetaminophen, naproxen, indomethacin, and ketoprofen), caffeine, and carbamazepine were monitored. Moreover, their aquatic risk and ecotoxicity by three biological models were evaluated. The monitoring studies performed in Romania showed that all studied PhACs were naturally present at concentrations >0.01 μg/L, pointing out the necessity to perform further toxicity tests for environmental risk assessment. The toxicity studies were carried out on aquatic organisms or bacteria and they indicated, for most of the tested PhACs, an insignificant or low toxicity effects: lethal concentrations (LC50) on fish Cyprinus carpio ranged from 42.60 mg/L to more than 100 mg/L; effective concentrations (EC50) on planktonic crustacean Daphnia magna ranged from 11.02 mg/L to more than 100 mg/L; inhibitory concentrations (IC50)/microbial toxic concentrations (MTC) on Vibrio fischeri and other bacterial strains ranged from 7.02 mg/L to more than 100 mg/L. The PhAC aquatic risk was assessed by using the ratio between measured environmental concentration (MEC) and predicted no effect concentration (PNEC) calculated for each type of organism. The average of quotient risks (RQs) revealed that the presence of these compounds in Romania's aquatic environment induced a lower or moderate aquatic risk.

A simple, sensitive and reliable HPLC-FLD method for the routine determination of 4-nonylphenol, 4-NP and 4-tert-octylphenol, 4-t-OP content in water samples was developed. The method consists in a liquid–liquid extraction of the target analytes with dichloromethane at pH 3.0–3.5 followed by the HPLC-FLD analysis of the organic extract using a Zorbax Eclipse XDB C8 column, isocratic elution with a mixed solvent acetonitrile/water 65:35, at a flow rate of 1.0 mL/min and applying a column temperature of 40°C. The method was validated and then applied with good results for the determination of 4-NP and 4-t-OP in Ialomiţa River water samples collected each month during 2006. The concentration levels of 4-NP and 4-t-OP vary between 0.08–0.17 μg/L with higher values of 0.24–0.37 μg/L in the summer months for 4-NP, and frequently

Quantitative structure-property relationship models were developed for the prediction of pesticides and some PAH compounds lipophilicity based on a wide set of computational molecular descriptors and a set of experimental chromatographic data. The chromatographic lipophilicity of pesticides has been evaluated by high-performance liquid chromatography (HPLC) using different chemically bonded (C18, C8, CN and Phenyl HPLC columns) stationary phases and two different organic modifiers (methanol and acetonitrile, respectively) in the mobile phase composition. Through a systematic study, by using the classic multivariate analysis, several quantitative structure-property/lipophilicity multi-dimensional models were established. Multiple linear regression and genetic algorithm for the variable subset selection were used. The internal and external statistical evaluation procedures revealed some appropriate models for the chromatographic lipophilicity prediction of pesticides. Moreover, the statistical parameters of regression and those obtained by applying t-test for the intercept (a(0)) and for the slope (a(1)) in order to evaluate relationship between experimental and predicted octanol-water partition coefficients in case of the test set compounds, revealed two statistically valid models that can be successfully used in lipophilicity prediction of pesticides.

Retention in reversed-phase liquid chromatography for some polar and weakly related pesticides (urea derivatives or containing the thiophosphate group), using two types of stationary phases (C8 and C18), was studied for different compositions of mobile phase in order to estimate extrapolated values of capacity factor for entirely aqueous content of mobile phase. Two organic modifiers were used in composition of mobile phase: methanol or acetonitrile. The inter-correlations between extrapolated values for the two types of stationary phase were very high. The extrapolated values for studied pesticides were correlated by linear and multilinear regressions with molecular parameters, computed by means of different theoretical approaches (PM3 quantum chemical model, and DFT computational scheme). The best correlations were obtained for extrapolated values from retention study using acetonitrile as organic modifier in mobile phase composition.

In a study regarding metals concentrations in tap water, more than 250 samples were collected and analyzed using ICP-EOS techniques on a Perkin Elmer Optima 5300 DV spectrometer. Even if the quality of drinking waters provided by one important producer from Romania were situated in the limits imposed by the Romanian Legislation, the data reflected important influences of the material used in the internal distribution system within the customer buildings on the tap waters quality. In 85% of the tap water collected from copper cold water pipes high concentrations of copper were recorded, much more than 100 μg/L, which is the maximum admissible value in the Drinking Water Romanian Law. Another problem observed was related to Fe content, possible leached by the cast iron or unprotected steel pipes. In addition, branch pipe or Pb old pipe included in the internal distribution system has a negative influence on the tap water quality.

13th SGEM GeoConference on Ecology, Economics, Education And Legislation Volume 1 pp. 676-684

13th SGEM GeoConference on Ecology, Economics, Education And Legislation Volume 1 pp. 71-78

The main objective of this paper is to highlight the dynamics of biotic community in terms of spatial and temporal relationship. The biotic community dynamics in St. Gheorghe Branch were discussed based on existing data and the results of our own research during 2003–2009. Surface water and sediment samples have been collected monthly from two control sections, Murighiol and Uzlina. The analyzed parameters were according to the Norm concerning the reference objectives for the surface water quality classification (Romanian Order MEWM no. 161/2006) and also, to the EU Water Framework Directive 2000/60/EC which established a framework for community action in the field of water policy. The variation of parameters during the investigated period along St. Gheorghe Branch was strongly influenced by the climatic conditions (drought, flood). Further studies need to be carried out in this area in order to accomplish a sustainable management and to evaluate the occurrence of persistent organic pollutants and toxic metals in tissues, and to assess the risk of these contaminants on the ecosystem and human health.

The main objective of this paper is to provide data on the Danube River Delta Biosphere (Romania) aquatic ecosystem quality and Vardar – Axios River Valley (FYR Macedonia – Greece) on comparison basis from on the long-term analytical investigation for specific indicators. In particular this paper is focused on the quality assessment of surface water, sediment and biota of the Danube Delta Biosphere Reservation. Information is presented on water and sediment quality variations in heavy metals over a seven-year period (2003 and 2009), from April to October. Samples have been collected monthly from two different locations (Murghiol and Uzlina) situated on St. Gheorghe branch. The presence of some toxic metals was noticed in surface waters and sediments. In both locations in different periods of time high concentrations of Fe, Mn, heptachlor, Lindane, PCBs, phenols, mineral oil in surface water represent an acute problem for the inhabitants of the Danube Delta which use water for household consumption directly from the Danube, without any treatment. This presents a series of disadvantages, such as a high risk of disease for the population, mostly for children and old people. The evolution of the pollution levels of Danube waters was compared with that of Axios/Vardar River, another major transboundary river in the Balkan area.

Quantitative structure-property relationship models were developed for the prediction of pesticides and some PAH compounds lipophilicity based on a wide set of computational molecular descriptors and a set of experimental chromatographic data. The chromatographic lipophilicity of pesticides has been evaluated by high-performance liquid chromatography (HPLC) using different chemically bonded (C18, C8, CN and Phenyl HPLC columns) stationary phases and two different organic modifiers (methanol and acetonitrile, respectively) in the mobile phase composition. Through a systematic study, by using the classic multivariate analysis, several quantitative structure-property/lipophilicity multi-dimensional models were established. Multiple linear regression and genetic algorithm for the variable subset selection were used. The internal and external statistical evaluation procedures revealed some appropriate models for the chromatographic lipophilicity prediction of pesticides. Moreover, the statistical parameters of regression and those obtained by applying t-test for the intercept (a(0)) and for the slope (a(1)) in order to evaluate relationship between experimental and predicted octanol-water partition coefficients in case of the test set compounds, revealed two statistically valid models that can be successfully used in lipophilicity prediction of pesticides.

International Multidisciplinary Scientific GeoConference-SGEM, Geoconference on Science and Technologies in Geology, Ecology, Economics, Education and Legislation, SGEM 2015, vol. II, 2015, pp. 301-308

Occurrence and fate of 6 neonicotinoid insecticides belonging to different chemical classes were investigated in the aqueous phase of surface water at 16 sampling locations along the Romanian side of the Danube River and its three main tributaries (Jiu, Olt, Arges). This is the first report on the neonicotinoid occurrence in the Danube River and three tributaries. It was observed a contamination of Danube River and its tributaries, higher in planting period than pre-or post- planting period, with the next compounds (detection frequency and the concentration range): thiamethoxam (68.7%, 0.9-3.8ng/L), clothianidin (64.6%, 0.84-9.6ng/L), nitenpyram (52.08%, 0.39-11.1ng/L), imidacloprid (31.2%, 0.5-8.2ng/L), acetamiprid (16.6%, 0.84-12.7ng/L). The four main neonicotinoids (clothianidin, thiamethoxam, imidacloprid, nitenpyram) follow the classic pattern in which concentrations and frequency increase during the planting period and that is correlated with seed crop treatment. Total neonicotinoid levels present in investigated Rivers, reaching up to 31.6 ng/L, may affect aquatic invertebrates that are most susceptible to these insecticides. For clothianidin and nitenpyram were obtained positive correlations between the percentage of the area planted with cereals and concentrations of this compound (r= 0.574, r =0.665) which indicate their use in agricultural area. For imidacloprid were obtained positive correlations between percent of permanent cultivated crop in urban land and concentrations of this compound (r =0.264, r =0.877).

International Multidisciplinary Scientific GeoConference-SGEM, Geoconference on Science and Technologies in Geology, Ecology, Economics, Education and Legislation, SGEM 2015, vol. II, 2015, pp. 131-138

A sensitive and precise method for detection of five parabens in sewage sludge was developed based on ultrasonic assistedextraction, SPE clean-up and LC-MS/MS. Most of the parameters that affect the extraction step such as type of solvent and volume, extraction time were optimized. For ultrasonic extraction it was used a mixture of methanol: acetone, then the extract was centrifuged in order to obtain clean supernatant and the extract was purified on polymericSPE cartridges. The parabens were separated on C18 column in 13 min at 18�C using a gradient of mobile phase of 0.01% acetic acid and acetonitrile. Using the method, limit of quantitation (LOQ) were obtained ranging from 0.4 to 2ng/g. All recoveries ranged from 71% to 109% for all compounds. The repeatability and reproducibility between days expressed as RSD (%) were less than 7.4% and 14.5%, respectively. The sum concentrations of all parabens for each sludge sample ranged between 19 ng/g dry weight and 32.7 ng/g dry weight. The study of the profile sample composition shows that the average contribution of each compound of the total parabens concentration was as follow: methyl paraben 62.9%, ethyl paraben 18.6%, iso-propyl paraben 10.9%, propyl paraben 10.8%. This result indicate that methyl paraben is the most used paraben followed by ethyl paraben.