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Using an LC-MS-MS method for detection of 6 neonicotinoid insecticides (imidacloprid, dinotefuran, acetamiprid, clothianidin, thiamethoxam, nitenpyram) was developed a new performant extraction method based on sonication treatment of soil samples, which were previously dried, grounded, homogenized, sieved (2 mm) and subjected to the selective extraction process with acetonitrile. Then the obtained extracts were diluted with ultrapure water (ratio 1: 100) and subjected to purification by Strata C18 SPE extraction using cartridges loaded with 200 mg/6 mL of octa-dodecyl-silica adsorbent phase. The entire methodology allowed obtaining quantification limits at trace level that varied in the range 0.3-0.9 ng/g and recoveries between 71.4% and 109.6%. In the agricultural soil samples, taken from the lands cultivated with wheat, corn, sunflower, beans, located in Prahova and Giurgiu counties (Romania), only four neonicotinoids out of the total of six were quantified imidacloprid (0.38 ng/g-56.9 ng/g), acetamiprid (1.7-7.2 ng/g), thiamethoxam (1.05-6.7 ng/g), clothianidin (1.1-1.5 ng/g).

Chlorine is widely used in Romania and all over the world as a disinfectant of drinking water. During the chlorination process, the natural organic matter and inorganic ions react with chlorine forming disinfection by-products (DBPs). The predominant organic disinfection by-products are trihalomethanes (THMs) while the main inorganic disinfection by-products are chlorate and chlorite ions. THMs were detected in all investigated drinking water samples from Bucharest distribution system with values from 27.8 µg/L up to 75.1 µg/L, which are below the maximum concentration value admitted by Romanian drinking water legislation of 100 µg/L. Chloroform constitutes the major component in total THMs concentration found in all tested drinking water. Chlorate and chlorite anions were not detected in any of the investigated drinking water samples. THMs concentration was correlated with total organic carbon (TOC), residual chlorine and chloride.

A direct ion chromatographic method for the determination of chlorite, chlorate, and bromate in the presence of fluoride, chloride, nitrate, nitrite, and bromide in treated drinking waters was described. Separation of target analytes was achieved using an AS19-HC analytical column (250 mm x 4 mm), AG 19- HC guard column (50 mm x 4 mm), and KOH 25 mmol/L as mobile phase. Inorganic analytes were eluted using a flow rate of 1 mL/min. The column temperature was set up and maintained at 300C. The analyte ions were quantified using a suppressed conductivity detector.

This study investigated the spatial and temporal distribution of nitrate and nitrite concentration in groundwater from different geographical regions, in Romania. A special emphasis was put on a descriptive statistical analysis of data, namely on the determination of seasonal indices during dry and wet seasons. Nitrate and nitrite concentrations were monitored in 24 groundwater sources situated in different areas, between January 2016 and February 2020. The obtained data showed that the values of nitrate concentrations were situated between 8.03 mg/L in the North-Eastern part of Romania, 6.37 mg/L in the South-Eastern part of the country, and 3.55 mg/L in the Western part towards the center of the country. Nitrite concentration values were situated under the national maximum admitted limit, 0.5 mg/L, in all the investigated areas. The obtained data shows small changes in water quality during the monitoring period, which leads to the conclusion that, in this long interval of time, there were no significant groundwater contaminations with nitrate and nitrite. For adequate control of water pollution and rigorous management of groundwater sources, seasonal indices were calculated.

In the last decade, the use of chemical compounds with a molecular structure similar to that of BPA has been reported more and more as alternatives to BPA in various industrial products. This comes as a result of banning partial or total use of BPA because of its endocrine disrupting properties. However, bisphenol analogues have been shown to have similar or even greater negative properties than BPA. Thus, particular attention has been given to the risks they have for aquatic systems and human health. In this context, the present study aimed to determine the concentration level at which some of the bisphenol analogues (BPS, BPB, BPE, BPC and BPE), BPA and its major metabolite, 4-HAP, are found in surface waters. For this purpose, 11 sampling points were established in the geographical area of the Danube Delta. Among the seven targeted pollutants, only four were detected in the analyzed samples. 4-HAP metabolite was the most abundant compound in the analyzed samples, with concentrations ranging from 3.56 to 30.9 ng/L. BPA concentrations were, in most cases approximately three times lower than those determined for 4-HAP. The next bisphenol analog after 4-HAP, in the decreasing order of concentrations, was BPE, for which the concentration level ranged between LOQ and 12.4 ng/L. Lowest concentrations were detected for BPS, with a maximum level of 1.96 ng/L.

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.

A newly developed direct injection HPLC-DAD method for the simultaneous detection of Brilliant Blue (BB), Sunset Yellow (SY) and Tartrazine (TA) synthetic dyes was validated and applied to surface and wastewater samples. Chromatographic separation was achieved using an Acclaim Surfactant Plus column (150 x 3.0 mm, 3 um) in isocratic elution mode with a mobile phase consisting of 100 mM CH3COONH4 and ACN in the ratio 50/50 (v/v). Linear calibration curves were plotted in the range of 2-100 μg/L (BB) and 6-300 μg/L (SY, TA) respectively with correlation coefficients (R2) higher than 0.99. Low quantitation limit values (LOQ) were obtained for the direct injection HPLC-DAD method, namely: 1.0 �g/L (BB), 5.5 �g/L (SY) and 5.8 �g/L (TA), respectively. The entire sample preparation procedure consisted only in simple filtration using PTFE syringe filters (0.45 �m) without sample extraction or concentration, which improved method accuracy and precision. HPLC-DAD developed method proved to be fast (6 minutes run-time), sensitive and accurate and was succesfully applied for the analysis of the synthetic dyes in surface and wastewater samples. Considering all analyzed samples (8 surface water and 11 wastewater samples), Brilliant Blue was found in influent samples with values between 4.49 � 14.17 �g/L and effluent samples with values between 1.07 � 9.54 �g/L, whereas Sunset Yellow and Tartrazine were not detected in any of the analyzed samples.

A liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method was developed and validated for the simultaneous determination of six organic compounds (2-hydroxy benzophenone, 4-hydroxy benzophenone, 2,2�,4,4�-tetrahydroxy benzophenone, 2,4-dyhydroxy benzophenone, 4,4�-dyhydroxy benzophenone, 2,2�-dyhydroxy-4-methoxy-benzophenone) used as UV filters in personal care products used to protect against UV radiation. The major concern about this type of pollutants is due to their persistence and bioaccumulation potential in the environment and aquatic organisms and for their endocrine disruptor properties. Solid phase extraction was used for sample preparation, followed by liquid chromatography tandem mass spectrometry analysis. Benzophenone derivatives were analyzed on a Phenomenex Luna C18 column (150 x 2.0 mm, 3.0 �m) with the mobile phase run in gradient mode with a mixture of aqueous 0.1% formic acid and acetonitrile as the mobile phase components (at a flow rate of 0.2 mL/min). MS detector response was linear, on the tested concentration domain from 1 to 100 μg/L with correlation coefficient R2 ] 0.998. The recoveries of benzophenone derivatives after solid phase extraction procedure from surface water was found to be ]81% for surface water and higher than 79% for wastewater matrix. The standard deviation values for intra-day precision were situated between 7.67% and 9.88% for lower concentration and 7.27% and 8.86% for higher concentration respectively. The limits of quantitation were calculated for both environmental water matrices (1.6-4.1 ng/L for surface water and 3.3-8.2 ng/L for wastewater). This method can be applied for benzophenone derivatives detection in real environmental samples.

Sewage sludges originating from waste water treatment plants (WWTP) act as a sink for various contaminants including polychlorinated biphenyls (PCBs). The fate of organochlorine compounds in sewage sludge is shaped by their physical-chemical properties and by environmental conditions. The high persistence of polychlorobiphenyls (PCBs) in sewage sludge is given by an extremely reduced degradation rate which varies from months to years (the half-life of PCB 28 is 10.9 years, and PCB 52, 11.2 years). Due to their increased hydrophobicity, these carcinogenic compounds can be easily uptake by plants and transferred to the food chain. The present study investigated the occurrence of these seven PCB congeners in sewage sludge sampled from municipal waste water treatment plants from different geographical areas in Romania for a two-year period (2018 and 2019). For the analyzed PCB congeners a database was created concerning their occurrence levels in sewage sludge from these WWTPs. A total number of 62 sewage sludge samples were collected from different WWTPs between 2018-2019 and analyzed for PCB congener content using a validated GC-ECD method according to SR EN 16167/2013. In all the samples that were analyzed in this study the sum of PCB congeners was situated below the maximum allowable concentration (MAC = 0.8 mg/kg d.w.) stated by the Order 708/2004.

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 fate of organochlorine compounds in soil ecosystem is shaped by their physical-chemical properties and by environmental conditions. The high persistence of polychlorobiphenyls (PCBs) in soil is given by a slow degradation which varies from months to years (the half-life of PCB 28 is 10.9 years, and PCB 52, 11.2 years). Due to high lipophilicity, these carcinogenic compounds can be easily uptaken by plants and transferred to the food chain. The widespread use of medicinal plant, Mentha Piperita, in pharmaceutical and food industry represents a risk of contamination and pollution. Through laboratory studies, we worked to identify the chemical behavior in soil and plants of some PCB congeners: 28, 52, 138, 153 and 180). The compounds mobility from soil to the roots and then through plant was monitored for 5 weeks. By optimizing the analytical method the contaminants were determined from soil and plant with good recoveries and with reduced limit of detection, below 0.01 mg/kg. It was reported that usually are uptaken into the plant high chlorinated PCBs like PCB 153 and PCB 180 but this study shows that after 5 weeks of PCB application, the concentration of PCB 28, a trichlorobiphenyl, is increasing. Fortunately, calculating the bioconcentration factor (BCF) of the selected PCBs in roots, it was shown that is similar to BCF of other plants like poplar and zucchini. The obtained value of 0.2 is assessed as being low.

Herbal drugs are widely used in pharmaceutical industry due to their beneficial effects on human health. The current research was carried out to evaluate the organic pollutant degradation in the flower part of the plant after a foliar application of pesticides. Also, based on the fact that selected pesticides are highly toxic to bees, it is important to monitor the removal rate of the pollutant. Under laboratory conditions, the marigold and French flowers (Calendula Officinalis and Tagetes Patula) were spiked with a mix of organophosphorus insecticide, dimethoate, chlorpyrifos and chlorfenvinphos, where the first two substances are still used on Romanian territory. The samples were extracted at different time moments over 300 min after sprayed treatment in order to evaluate the concentration in flower. The analytes were quantified by using gas chromatography with flame photometric detection (GC-FPD) technique. The developed method ensures the quality and comparability of analytical results, with a good sensitivity in determining the analytes over the concentration range 5-250 �g/L.

Hexabromocyclododecane (HBCD) is a large-scale usage brominated flame retardant consisting of a mixture of diastereoisomers which has been reported as an ubiquitous environmental contaminant. HBCD has attracted much attention due to its toxicity and increasing levels in waste water sewage sludge. Since November 2014, HBCD was added to the Persistent Organic Pollutants list of the Stockholm Convention which generated a higher concern regarding its presence in the environment. A rapid (8 min) and accurate liquid chromatography electrospray ionization tandem mass spectrometry method (LC-ESI-MS/MS) was developed to separate and detect a-, b- and g-HBCD isomers from sewage sludge. Optimization of LC-MS parameters (column temperature, mobile phase composition and flow, collision energy, fragmentor voltage, capillary voltage and drying gas temperature) allowed complete separation of the three isomers and also very good detection sensitivity with instrumental quantitation limits (IQLs) between 0.3 and 0.6 ng/mL. The three isomers were separated on a C18 reversed-phase column, kept at 18�C, using a H2O/ACN/MeOH mobile phase mixture and detected by negative electrospray ionization using MRM mode with two transitions, one for quantitation and one for confirmation. MS detector response was linear in the range 1.0 � 100.0 ng/mL with correlation coefficients (R2) higher than 0.99 for all three isomers. A simple ultrasonic assisted liquid-solid extraction procedure using a solvent mixture was employed to extract HBCD isomers from WWTP sewage sludge. Overall method intra-day and inter-day precision (RSD%) were situated between 7.6 � 9.2% and 10.3 � 14.5%, respectively. LOQs for a-, b- and g-HBCD were 1.4, 0.7 and 1.0 ng/g, comparable and even lower to those reported by similar studies concerning HBCD presence in WWTP sewage sludge. HBCD presence was tested from several WWTP sludge samples. All three isomers were found with 100% detection frequency ranging from 3 to 76 ng/g.

Increasing and widespread use of neonicotinoid insecticides in all world, together with their highly toxicity to invertebrates and environmental persistence mean that surface waters need to be monitored for these compounds. In the 2015, neonicotinoid insecticides have been incorporated in the watch list of substances for a European Union monitoring program (495/2015/ EU). A new method using automated solid phase extraction (SPE) with polymeric cartridges (OASIS HLB) followed by LC-MS/MS provided good separation of the most common neonicotindoid compounds. The method was developed for the determination of four neonicotinoid insecticides (nitenpyram, thiamethoxam, clothianidin, acetamiprid) in surface water with low limit of quantification (0.3-0.9 ng/L, nanograms per liter). Recoveries in surface water samples fortified at 200 ng/L for each compound ranged from 71.4 to 109.9 %; relative standard deviation ranged from 4 to 9%. The method was applied to water samples from four streams in Romania, Danube River and its tributaries (Arges River, Jiu River, and Olt River). The surface water samples were found to be contaminated clothianidin (1.08-6.4 ng/L) and by thiamethoxam (1.1-3.8ng/L). The highest concentrations were recorded in Danube River in Oltenita point (6.4ng/L) and in Gura-Vaii point (5.5ng/L). The concentration of acetamiprid and nitenpyram were situated below limit of quantification in all samples.

The intense industrial exploitation of resources and the continuous degradation of the environment have determined an ecological crisis of care requires a sustainable strategy. The concept of sustainable development permanently determines or re-evaluates the connection between man and nature and is committed to solidarity between the generations as a single viable option for long lung growth. In the article, the theme of the long-term impact in the world terms on the processes developed in Romania is presented and analyzed, a necessary passage for a sustainable economic growth, but there is an existing resource and the possibility to stimulate and capitalize on an economic factor in this the transition to this new stage of use. Keywords: sustainable development, strategies, ecological, perspectives

International Symposium "The Environment and the Industry", 26-27 September 2019, Bucharest, Romania, pp. 50-51

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

A simple, reliable and accurate HPLC/CAD method was developed for the determination of anionic (sodium dioctyl sulfosuccinate and sodium 1-dodecane sulfonate), amphoteric (CHAPS (3-[(3-Cholamidopropyl) dimethylammonium]-1-propanesulfonate hydrate)) and cationic (benzethonium chloride) surfactants mixture from surface water samples. The chromatographic analysis was performed on an Acclaim Surfactant Plus (150 x 3.0 mm, 3 mm d.p.) column acquired from Thermo Scientific, kept at 300C. All experiments were performed in gradient elution conditions at a flow-rate of 0.6 mL/min. Mobile phase composition was a mixture of acetonitrile (A) and 0.1 M ammonium acetate solution acidified to pH 5 with acetic acid (B). The limit of detection (LD) were 20 mg/L for anionic surfactants and 30 mg/L for cationic and amphoteric surfactants. The calibration curves were linear between 15 mg/L � 110 mg/L, with R2 values above 0.992 for all surfactants. Solid phase extraction (SPE) using polymeric (Strata X) cartridges has been applied to extract and concentrate the target analytes from the synthetic samples. Surfactants recoveries after SPE procedure were situated between 91.5�94.6%. Intra-day and inter-day precision (RSD%) were situated between 4.0 � 7.7% and 7.5 � 11.7%, respectively. Limit of quantitation (LQ) was lower than 80 mg/L for anionic surfactants and 90 mg/L for cationic and 100 mg/L for amphoteric surfactants. The new sensitive and selective HPLC/CAD developed method allows simultaneous determination of anionic, amphoteric and cationic surfactants mixture from environmental samples (surface water).