Urinary arsenic and spontaneous pregnancy loss - a hypothesis-generating case-control investigation in western Romania.

Arsenic occurs as a natural contaminant of drinking water supplies in arsenic endemic areas, posing a threat to public health. Our aim was to evaluate the relationship between urinary arsenic concentrations and spontaneous pregnancy loss in a population with low-moderate level drinking water arsenic exposure (mostly <10 µg/L). We enrolled 150 women with incident spontaneous pregnancy losses and 150 controls with ongoing pregnancies matched by gestational age. We measured arsenic species in urine using high performance liquid chromatography paired to inductively coupled plasma mass spectrometry. Urinary arsenic was not related to spontaneous pregnancy loss in conditional logistic regression models adjusted for confounding factors. However, a 10 µg/L increase in urinary arsenic (III + V) salt concentrations was associated with 8.00-fold (95% CI: 0.68, 3.35 × 105) greater odds of spontaneous loss among women using prenatal vitamins in an interaction model (P for interaction = 0.07), although the effect estimate was imprecise. In an additional interaction model, prenatal vitamin use was associated with lower odds of loss (OR = 0.30; 95% CI: 0.13, 0.66), although the association was diminished in the presence of a 10 µg/L increase in urinary inorganic arsenic (OR = 0.44; 95% CI: 0.70, 3.22). Total urinary arsenic was associated with 1.48-fold (95% CI: 0.20, 11.35) greater odds for loss among women with urinary cotinine >50 µg/L in another interaction model (P for interaction = 0.07). These results suggest a potential modest increase in the odds of pregnancy loss associated with increased total urinary arsenic among women smoking during pregnancy (urinary cotinine >50 µg/L). Prenatal vitamin use may act as a protective factor for arsenic exposure associated pregnancy loss, but appears to be less protective with increasing urinary inorganic arsenic concentrations.

Bridging the Chemical Profile and Biological Activities of a New Variety of Agastache foeniculum (Pursh) Kuntze Extracts and Essential Oil.

This study investigated the phytochemical content of alcoholic extracts and essential oil of a new variety of medicinal plants, Agastache foeniculum (Pursh), which Kuntze adapted for cultivation in Romania, namely "Aromat de Buzau". The essential oil was investigated by GC-MS, while the identification and quantification of various compounds from alcoholic extracts were performed by HPLC-DAD. The total phenol and flavonoid contents of the extracts were evaluated by using standard phytochemical methods. The antioxidant activities of ethanol, methanol extracts, and essential oil of the plant were also assessed against 2,2'-diphenyl-1-picrylhydrazyl (DPPH•), 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS•+), and by ferric reducing power (FRAP) using spectroscopic methods. Cyclic voltammetry was used to evaluate the antioxidant capacity of the essential oil. The concentrations of phenolic compounds were higher in methanolic extract compared to ethanolic extract. A significant correlation was found between total phenol and total flavonoid contents (r = 0.9087). Significant high correlations were also found between the total phenolic compounds and the antioxidant activities of the extracts (r ≥ 0.8600, p < 0.05). In addition, the extracts and essential oil showed good antioxidant and xanthine oxidase inhibitory activities. Estragole was detected as the major constituent of the essential oil (94.89%). The cytotoxic activity of the essential oil was evaluated by the MTT assay. At lower concentrations (1 µg/mL) high cytotoxicity against MCF-7 breast cancer cells was observed but not on the non-tumoral dermal fibroblasts (HDF) which indicated selectivity for cancer cells and suggests the presence of biologically active components that contribute to the observed high cytotoxic effect. Findings from the present study offer new perspectives on the use of A. foeniculum as a potential source of bioactive compounds and a good candidate for pharmaceutical plant-based products.

Differentiation of tomatoes based on isotopic, elemental and organic markers.

In this study, 41 tomato samples were investigated by means of stable isotope ratios (δ13C, δ18O and δ2H), elemental content, phenolic compounds and pesticides in order to classify them, according to growing conditions and geographical origin. Using investigated parameters, stepwise linear discriminant analysis was applied and the differences that occurred between tomato samples grown in greenhouses compared to those grown on field, and also between Romanian and abroad purchased samples were pointed out. It was shown that Ti, Ga, Te, δ2H and δ13C content were able to differentiate Romanian tomato samples from foreign samples, whereas Al, Sc, Se, Dy, Pb, δ18O, 4,4'-DDT could be used as markers for growing regime (open field vs. greenhouse). For the discrimination of different tomato varieties (six cherry samples and fourteen common sorts) grown in greenhouse, phenolic compounds of 20 samples were determined. In this regard, dihydroquercetin, caffeic acid, chlorogenic acid, rutin, rosmarinic acid, quercetin and naringin were the major phenolic compounds detected in our samples. The phenolic profile showed significant differences between cherry tomato and common tomato. The contents of the chlorogenic acid and rutin were significantly higher in the cherry samples (90.27-243.00 µg/g DW and 160.60-433.99 µg/g DW respectively) as compared to common tomatoes (21.30-88.72 µg/g DW and 24.84-110.99 µg/g DW respectively). The identification of dihydroquercetin is of particular interest, as it had not been reported previously in tomato fruit.

Environmental exposure of anthropogenic micropollutants in the Prut River at the Romanian-Moldavian border: a snapshot in the lower Danube river basin.

The Prut River, the second longest tributary of the Danube river, was investigated for a wide range of anthropogenic organic pollutants to fill the data gap on environmental contamination in eastern European surface waters. In this study, the occurrence of a wide range of organic pollutants was measured along the transboundary Prut River, between Sculeni and Branza in 2010-2012. Using two different analytical methods, gas chromatography coupled to mass spectrometry and liquid chromatography coupled to high-resolution mass spectrometry, over 300 compounds were screened for and 88 compounds were determined in the Prut River. In general, the chemicals occurred at low levels. At the last sampling site upstream of the confluence with the Danube river at Branza, the highest average concentrations (≥ 100 ng L-1) were determined for the artificial sweetener acesulfame, the pharmaceuticals metformin, 4-acetamidoantipyrene, and 4,4,5,8-tetramethylchroman-2-ol, the antioxidants 2,4-di-tert-butylphenol, 3-tert-butyl-4-hydroxyanisol, and 3,5-di-tert-butyl-4-hydroxy-toluene, the personal care products HHCB (galaxolide), 4-phenyl-benzophenone, and octyl dimethyl-p-aminobenzoic acid, the industrial chemical diphenylsulfone, and the sterol cholesterol. Low concentrations of agricultural pesticides occurred in the catchment. At Branza, the total accumulated load of all measured compounds was calculated to be almost 19 kg day-1. In comparison to the Rhine River, the loads in the Prut, determined with same LC-HRMS method for the same set of analytes, were two orders of magnitude lower. Discharge of wastewater without proper treatment from the city of Iasi in the Jijia catchment (Romania) as well as from the city of Cahul (Moldova) revealed a distinct increase in concentrations and loads in the Prut at Frasinesti and Branza. Thus, an implementation of wastewater treatment capacities in the Prut River basin would considerably reduce the loads of micropollutants from urban point sources.

HCH phytoremediation potential of native plant species from a contaminated urban site in Turda, Romania.

Current physical or chemical methods used for remediation of soils contaminated with hexachlocyclohexane (HCH), leave behind significant levels of pollutants. Given the compound's volatility and persistence in the environment, sites contaminated with HCH remain a concern for the population living in nearby areas. By making use of both the recovery capacity and the pollutant uptake ability of spontaneously growing vegetation, our study aimed to identify native plant species able to cover and moreover take up the HCH left at a former lindane production unit in Turda, Romania. The results showed that dominant species across the study site like Lotus tenuis, Artemisia vulgaris or Tanacetum vulgare, were capable of taking up HCH in their tissues, according to different patterns that combined at the scale of the plant community. Regardless of the proximity of the HCH contamination hotspots, the development of the plant cover was characteristic for vegetation succession on disturbed soils of the Central European region. Finally, we conclude that plant species which grow spontaneously at the HCH contaminated site in Turda and are capable of taking up the pollutant, represent a self-sustainable and low maintenance phytomanagement approach that would allow for the reintegration of the site in the urban or industrial circuit and nevertheless would reduce the toxicity risk to the neighboring human inhabitants.

Isotopic and elemental markers for geographical origin and organically grown carrots discrimination.

This study proposes different markers associations for the discrimination of organically and conventionally grown carrots, as well as for the geographical origin differentiation. It was shown that one of the most powerful differentiation markers proved to be Mn content. Along with manganese concentrations, isotope ratios of nitrogen and a high number of Rare Earth-Elements (REEs) were able to differentiate the organically grown carrots samples in a percent of 83.3% (initial classification) and 81% (cross-validation), respectively. It was observed that some of the obtained discrimination markers were interlinked, for instance Mn content being positively correlated with some REEs (i.e. Sc, La, Ce, Pr, Nd, Lu, Th). One of the best markers that could differentiate the carrot samples grown in Transylvania, Romania, from those either grown in other side of the country or foreign samples is represented by Mn content along with another REE, particularly terbium (Tb).

Optimized and validated method for simultaneous extraction, identification and quantification of flavonoids and capsaicin, along with isotopic composition, in hot peppers from different regions.

Nineteen hot pepper (Capsicum annuum L.) samples from five countries and twenty samples from Romanian producers were analyzed. Concentrations of flavonoids and capsaicin were simultaneously quantified for the first time with the method developed and validated in the present paper. δ13C, δ2H, and δ18O isotopic values were also measured. Maximum concentrations of studied compounds were detected in methanol extracts, after 12 h incubation of the samples assisted by ultrasound, at the 1:8 ratio of sample to solvent. The extraction recovery ranged from 90.60% to 115.05%. Capsaicin and four flavonoids were quantified in studied samples at different concentration ranges: capsaicin (28.23-2322.35 µg/g), vitexin (2.93-33.46 µg/g), isoquercetin (3.19-155.58 µg/g), kaempferol-3-glucoside (2.31-2462.25 µg/g) and myricetin (1.55-78.79 µg/g). The association between these analytical techniques and chemometric tools proved that kaempferol-3-glucoside is one of the strongest markers for country and maturity stage discrimination.

Sorption of biocides, triazine and phenylurea herbicides, and UV-filters onto secondary sludge.

The sludge-water distribution of a total of 41 organic micropollutants (9 phenylurea herbicides, 11 triazines, 16 biocides and 5 UV-filters) was investigated in laboratory batch experiments with fresh secondary sludge taken from a municipal WWTP. Sorption kinetics as well as sorption isotherms were examined by analyzing the compound concentration in the aqueous and solid phase for mass balance control and quality assurance. The sorption kinetic experiments revealed a sorption equilibrium time of <2 h and adverse effects of sodium azide on the sludge-water distribution of several compounds. Sorption isotherms were constructed for 6 different spiking levels spanning 3 orders of magnitude (100 ng L(-1)-30,000 ng L(-1)) and were well described by the Freundlich model. For some compounds non-linear sorption with Freundlich exponents n < 1 revealed a decreased sorption affinity to the sludge flocs with increasing aqueous phase concentration. Therefore, sludge-water distribution coefficients (K(d,sec)) were calculated from the isotherm data for a constant concentration level of 1 µg L(-1). Based on the sludge dry weight (dw), the K(d,sec) values of phenylurea herbicides ranged from 9 L kg(dw sludge)(-1) (isoproturon) to 320 L kg(dw sludge)(-1) (neburon), those of triazines from 5 L kg(dw sludge)(-1) (atrazine) to 190 L kg(dw sludge)(-1) (terbutryn), those of biocides from 10 L kg(dw sludge)(-1) (N,N-dimethyl-N'-p-tolylsulfamide) to 40,000 L kg(dw sludge)(-1) (triclocarban) and those of UV-filters from 9 L kg(dw sludge)(-1) (phenylbenzimidazole sulfonic acid) to 720 L kg(dw sludge)(-1) (benzophenone-3). For most compounds K(d,sec) values were below 500 L kg(dw sludge)(-1) and thus removal in WWTPs by the withdrawal of excess sludge is expected to be negligible (<10%) except for the biocides triclocarban (80-95%), triclosan (55-85%), chlorophene (30-60%), imazalil (25-55%) and fenpropimorph (15-40%) as well as the UV-filter benzophenone-3 (5-20%). A simple linear free-energy relationship (LFER) approach using the logarithmized octanol-water partition coefficient log K(OW) as single descriptor is discussed for a rough classification of nonionic compounds regarding their potential removal in WWTPs by sorption.

The determination of the linear alkylbenzene sulfonate isomers in water samples by gas-chromatography/mass spectrometry.

A number of 20 compounds of linear alkylbenzene sulfonates (LASs) family were identified by electron impact mass spectrometry (EI-MS) in water samples collected from wastewater treatment plants (WWTP). This paper presents the mass spectra of 20 compounds, the proposed mechanism of formation of the diagnostic ions obtained by EI-MS and the distribution of individual isomers in water samples collected from compartments of WWTP. The individual isomers from four homolog series C(10)-, C(11)-, C(12)- and C(13)-LAS were analyzed as methyl derivatives.