Water flow plays a key role in determining chemical biodegradation in water-sediment systems.

Before agrochemicals can be registered and sold, the chemical industry is required to perform regulatory tests to assess their environmental persistence, using defined guidelines. Aquatic fate tests (e.g. OECD 308) lack environmental realism as they are conducted under dark conditions and in small-scale static systems, which can affect microbial diversity and functionality. In this study, water-sediment microflumes were used to investigate the impact of these deficiencies in environmental realism on the fate of the fungicide, isopyrazam. Although on a large-scale, these systems aimed to retain the key aspects of OECD 308 tests. Tests were carried out under both a non-UV light-dark cycle and continuous darkness and under both static and flowing water conditions, to investigate how light and water flow affect isopyrazam biodegradation pathways. In static systems, light treatment played a significant role, with faster dissipation in illuminated compared to dark microflumes (DT50s = 20.6 vs. 47.7 days). In flowing systems (DT50s = 16.8 and 15.3 days), light did not play a significant role in dissipation, which was comparable between the two light treatments, and faster than in dark static microflumes. Microbial phototroph biomass was significantly reduced by water flow in the illuminated systems, thereby reducing their contribution to dissipation. Comprehensive analysis of bacterial and eukaryotic community composition identified treatment specific changes following incubation, with light promoting relative abundance of Cyanobacteria and eukaryotic algae, and flow increasing relative abundance of fungi. We conclude that both water velocity and non-UV light increased isopyrazam dissipation, but the contribution of light depended on the flow conditions. These differences may have resulted from impacts on microbial communities and via mixing processes, particularly hyporheic exchange. Inclusion of both light and flow in studies could improve the extent they mimic natural environments and predict chemical environmental persistence, thus bridging the gap between laboratory and field studies.

Chemical composition of essential oil from plants of abandoned mining site of Elba island.

The essential oil composition of three spontaneous species growing in an abandoned mining of Elba island was analyzed by GC-MS. A total of 194 compounds were identified representing 73.7-100% of the whole oil composition. The essential oils of Cistus salvifolius and Dittrichia viscosa from this site showed different profiles in comparison with those from not polluted area, where oxygenated sesquiterpenes were the main class. Volatiles from D. viscosa growing in ex-mining area presented 10-epi-γ-eudesmol and α-eudesmol as main compounds while ß-caryophyllene and limonene were the main ones in not polluted area. Ambroxide and ambrial were the most important compounds in the essential oil from C. salvifolius harvested in polluted area while nonanal and tridecanal were the main compounds in control samples. Oxygenated monoterpenes were the most abundant class from both Lavandula stoechas samples, with fenchone and camphor as main compounds.

Essential oil extraction, chemical analysis and anti-Candida activity of Foeniculum vulgare Miller - new approaches.

A comprehensive study on essential oil samples of Foeniculum vulgare Miller from Tarquinia (Italy) is reported. A 24-h systematic steam distillation was performed on different harvested samples applying different extraction times. The GC-MS analysis of the residue outcome showed o-cymene, α-phellandrene, α-pinene and estragole as the major constituents. The predominance and continued presence of o-cymene makes this fennel oil a rather unique chemotype. An evident correlation between the antifungal activity and phenological stage is demonstrated. The most active fractions were particularly rich in estragole, as well as a significant amount of fenchone that possibly exerts some additive effect in the expression of overall antifungal potency. Pre-fruiting material produced oil particularly rich in o-cymene. With reference to the duration of the extraction, the maximum amount of oil was released within the first 3 h, whereas the reproductive phase material needed at least 6 h for the extraction.

Simultaneous Determination of Isopyrazam and Azoxystrobin in Cucumbers by Liquid Chromatography-Tandem Mass Spectrometry.

A rapid and sensitive analytical method based on high-performance liquid chromatography-tandem mass spectrometry was developed and validated for the determination of isopyrazam (IZM) and azoxystrobin (AZT) in cucumbers. A modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was used as the pretreatment procedure. The samples were extracted with acetonitrile and cleaned up with octadecylsilyl silica (C18) and graphite carbon black. The proposed method resulted in satisfactory recovery of IZM and AZT (91.48 to 114.62%), and relative standard deviations were less than 13.1% at fortification concentrations of 1, 20, and 500 µg kg-1 (n = 3). The limits of quantification for IZM and AZT were 0.498 and 0.499 µg kg-1, respectively, which are far below the maximum residue level (0.5 mg kg-1) established for this type of sample. Matrix effects were also evaluated. This study established a sensitive and fast method for the detection of IZM and AZT in cucumber samples.

Chemical profile, antiproliferative and antioxidant activities of rhizome oil of Zingiber anamalayanum from Western Ghats in India.

Volatile oil from fresh rhizomes of Zingiber anamalayanum was isolated by hydrodistillation and characterised by GC-FID and GC-MS. Twenty-one out of 24 constituents comprising 99.47% of the oil were identified. Major components in Z. anamalayanum rhizome oil were δ-2-carene (52.83%), camphene (9.83%), endo-fenchol (9.42%), iso-dihydrocarveol (6.44%) and cis-p-mentha-2,8-dien-1-ol (5.19%). Monoterpene hydrocarbons in the rhizome oil were 65.81%, followed by oxygenated monoterpenes (23.78%) and sesquiterpene hydrocarbons (9.87%). Physical parameters of rhizome oil were [Formula: see text] 1.4031, [Formula: see text] - 16.097(o) (c = 1, CHCl3) and [Formula: see text] 0.9202. Z. anamalayanum rhizome oil showed significant anti-Dalton's Lymphoma Ascitic activity.

Trace analysis of three fungicides in animal origin foods with a modified QuEChERS method and liquid chromatography-tandem mass spectrometry.

A multi-residue method based on modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS), was developed and validated for the determination of three selected fungicides (propiconazole, pyraclostrobin, and isopyrazam) in seven animal origin foods. The overall recoveries at the three spiking levels of 0.005, 0.05, and 0.5 mg kg(-1) spanned between 72.3 and 101.4% with relative standard deviation (RSD) values between 0.7 and 14.9%. The method shows good linearity in the concentrations between 0.001 and 1 mg L(-1) with the coefficient of determination (R (2)) value >0.99 for each target analyte. The limit of detections (LODs) for target analytes were between 0.04 and 1.26 µg kg(-1), and the limit of quantifications (LOQs) were between 0.13 and 4.20 µg kg(-1). The matrix effect for each individual compound was evaluated through the study of ratios of the areas obtained in solvent and matrix standards. The optimized method provided a negligible matrix effect for propiconazole within 20%, whereas for pyraclostrobin and isopyrazam, the matrix effect was relatively significant with a maximum value of 49.8%. The developed method has been successfully applied to the analysis of 210 animal origin samples obtained from 16 provinces of China. The results suggested that the developed method was satisfactory for trace analysis of three fungicides in animal origin foods.

Persistence assessment of cyclohexyl- and norbornyl-derived ketones and their degradation products in different OECD screening tests.

The persistence of synthetic cyclohexyl- and norbornyl-derived ketones was assessed by using OECD 301F and 301D biodegradation tests. While cyclohexyl-derived ketones either reached or came close to the pass level (60%) after 60 d, the corresponding norbornyl derivatives yielded significantly less biodegradation (<40%). By analyzing extracts at 60 d, the key degradation products of four norbornyl derivatives were identified. Consistently, 2-bicyclo[2.2.1]heptane carboxylic acid was found as a principal degradation product with minor quantities of bicyclo[2.2.1]heptan-2-one and 2-bicyclo[2.2.1]heptane acetic acid. When the three degradation products were re-synthesized and tested individually for biodegradability, the former two were found to be ultimately biodegradable after 60 d in OECD 301D tests, thus proving non-persistence. Similarly, 2-bicyclo[2.2.1]heptane acetic acid was found to be degraded significantly, albeit with long lag phases exceeding 60 d in the case of freshwater inoculum, then ultimately reaching the pass level. On the other hand, norbornyl ketones were still only partially biodegradable in the same test. We conclude that despite the potential for ultimate biodegradation of norbornyl-derived ketones, current screening tests yield an incomplete picture of their biodegradability, particularly when applying strict OECD criteria. The appearance of long lag phases when re-testing norbornyl ketone degradation products underlines the importance of extending tests to well beyond 28 and even 60 d in the case of freshwater inocula.

Lavender (Lavandula stoechas L.) essential oils attenuate hyperglycemia and protect against oxidative stress in alloxan-induced diabetic rats.

BACKGROUND: The present study described the phytochemical profile of Lavandula stoechas essential oils, collected in the area of Ain-Draham (North-West of Tunisia), as well as their protective effects against alloxan-induced diabetes and oxidative stress in rat. METHODS: Essential oils samples were obtained from the aerial parts of the plant by hydrodistillation and analyzed by GC-MS. Rats were divided into four groups: Healthy Control (HC); Diabetic Control (DC); Healthy + Essential Oils (H + EO) and Diabetic + Essential Oils (D + EO).Antidiabetic and antioxidant activities were evaluated after subacute intraperitoneally injection of Lavandula stoechas essential oils (50 mg/kg b.w., i.p.) to rats during 15 days. RESULTS: The principal compounds detected are: D-Fenchone (29.28%), α-pinene (23.18%), Camphor (15.97%), Camphene (7.83%), Eucapur (3.29%), Limonene, (2.71%) Linalool, (2.01%) Endobornyl Acetate (1.03%). The essential oils also contained smaller percentages of Tricyclene, Cymene, Delta-Cadinene, Selina-3,7(11)-diene. Furthermore, we found that Lavandula stoechas essential oils significantly protected against the increase of blood glucose as well as the decrease of antioxidant enzyme activities induced by aloxan treatment. Subacute essential oils treatment induced a decrease of lipoperoxidation as well as an increase of antioxidant enzyme activities. CONCLUSIONS: These findings suggested that lavandula stoechas essential oils protected against diabetes and oxidative stress induced by alloxan treatment. These effects are in partly due to its potent antioxidant properties.

Emerging and historical halogenated flame retardants in fish samples from Iberian rivers.

Forty-eight fish samples from the Llobregat, Ebro, Júcar and Guadalquivir river basins (Spain), were analyzed for polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), pentabromoethylbenzene (PBEB) and halogenated norbornenes (HNs). The most contaminated river basin was the Llobregat, followed by the Ebro, Júcar and Guadalquivir for almost every analyzed contaminant. Most abundant PBDE congener was BDE-47 (BDL-396 ng/g lw) and the most abundant halogenated norbornene was Dechlorane-602 (BQL-174 ng/g lw). Fanti was calculated to determine the different bioaccumulation/biodegradation of syn-DP and anti-DP. Biota to sediment accumulation factor was calculated in order to compare the bioaccumulation capacity of emerging flame retardants with that of "classical" PBDEs. It was found that bioaccumulation of halogenated norbornenes is lower than that of PBDEs. BDE-99, HBB, PBEB and Dechlorane-604 were not detected in any sample.

Distillation time modifies essential oil yield, composition, and antioxidant capacity of fennel (Foeniculum vulgare Mill).

Fennel (Foeniculum vulgare Mill) is an essential oil crop grown worldwide for production of essential oil, as medicinal or as culinary herb. The essential oil is extracted via steam distillation either from the whole aboveground biomass (herb) or from fennel fruits (seed). The hypothesis of this study was that distillation time (DT) can modify fennel oil yield, composition, and antioxidant capacity of the oil. Therefore, the objective of this study was to evaluate the effect of eight DT (1.25, 2.5, 5, 10, 20, 40, 80, and 160 min) on fennel herb essential oil. Fennel essential oil yield (content) reached a maximum of 0.68% at 160 min DT. The concentration of trans-anethole (32.6-59.4% range in the oil) was low at 1.25 min DT, and increased with an increase of the DT. Alpha-phelandrene (0.9-10.5% range) was the lowest at 1.25 min DT and higher at 10, 80, and 160 min DT. Alpha-pinene (7.1-12.4% range) and beta-pinene (0.95-1.64% range) were higher in the shortest DT and the lowest at 80 min DT. Myrcene (0.93-1.95% range), delta-3-carene (2.1-3.7% range), cis-ocimene (0-0.23% range), and gamma-terpinene (0.22-2.67% range) were the lowest at 1.25 min DT and the highest at 160 min DT. In contrast, the concentrations of paracymene (0.68-5.97% range), fenchone (9.8-22.7% range), camphor (0.21-0.51% range), and cis-anethole (0.14-4.66% range) were highest at shorter DT (1.25-5 min DT) and the lowest at the longer DT (80-160 min DT). Fennel oils from the 20 and 160 min DT had higher antioxidant capacity than the fennel oil obtained at 1.25 min DT. DT can be used to obtain fennel essential oil with differential composition. DT must be reported when reporting essential oil content and composition of fennel essential oil. The results from this study may be used to compare reports in which different DT to extract essential oil from fennel biomass were used.

Determination of 5-ethylidene-2-norbornene in industrial emission.

A method to measure the emissive concentration of 5-ethylidene-2-norbornene (ENB), a reactive compound used in industrial synthesis of terpolymers, has been developed. The starting points for the development of the presented method are European and Italian reference methods for the quantification of nonreactive volatile organic compounds in industrial emission. In this study, sampling conditions and desorption solvent have been optimized in laboratory and the method was applied in an industrial plant. The laboratory tests showed a good recovery (88-95%). The concentrations of ENB in industrial emission obtained with the developed method were compared with an online gas chromatography-flame ionization results (R (2) > 0.97). In addition, several manual measurements were performed in parallel, and the resulting %RSD repeatability was <9%. The developed method provides a discontinuous technique to measure reactive volatile organic compounds using easy-to-use instruments and assures a very good accuracy and precision even with high-humidity gas flows. The method could be extended to other reactive compounds of the same class.

[GC-MS analysis of chemical components in seeds oil from Croton tiglium].

OBJECTIVE: To identify the chemical components and their relative content in seeds oil from Croton tiglium. METHODS: The oil obtained by extracting of the seeds of Croton tiglium with petroleum ether was subjected to methyl-esterification or dilution with ethylether. GC-MS were used to identify the components in croton oil,peak area normalization method was used to determine the relative content of these substances in the sample. RESULTS: Seventeen fat acid components were identified from croton oil. The main components were linoleic acid, oleic acid, and eicosenoic acid in methyl-esterified sample, whose quantities accouted for 77.33%. In addition, five aromatic compounds were also found in the sample diluted with ethylether, such as isoborneol, fenchyl alcohol, etc. Phorbol esters, having carcinogenesis and anti-HIV-1 effects, were not been identified. CONCLUSION: There are abundant of linoleic acid, oleic acid and eicosenoic acid in the seeds oil extracted from Chinese Croton tiglium. In contrast, the active component with carcinogenesis and anti-HIV-1 might be very rare in the samples and difficult to be obtained by ordinary separating and extracting methods.

Determination of stimulants using gas chromatography/high-resolution time-of-flight mass spectrometry and a soft ionization source.

RATIONALE: The aim of this study was to investigate the mass spectral fragmentation of a small set of stimulants in a high-resolution time-of-flight mass spectrometer equipped with a soft ionization source using vacuum ultraviolet (VUV) photons emitted from different plasma gases. It was postulated that the use of a plasma gas such as Xe, which emits photons at a lower energy than Kr or Ar, would lead to softer ionization of the test compounds, and thus to less fragmentation. METHODS: A set of nine stimulants: cocaine, codeine, nicotine, methadone, phenmetrazine, pentylenetetrazole, niketamide, fencamfamine, and caffeine, was analyzed by gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) in positive ion mode with this soft ionization source, using either Xe, Kr, or Ar as plasma gases. Working solutions of the test compounds at 0.1 to 100 ng/µL were used to establish instrument sensitivity and linearity. RESULTS: All test compounds, except methadone and pentylenetetrazole, exhibited strong molecular ions and no fragmentation with Xe-microplasma photoionization (MPPI). Methadone exhibited significant fragmentation not only with Xe, but also with Kr and Ar, and pentylenetetrazole could not be ionized with Xe, probably because its ionization energy is above 8.44 eV. The Kr- and Ar-MPPI mass spectra of the test compounds showed that the relative intensity of the molecular ion decreased as the photon energy increased. CONCLUSIONS: When coupled to a TOF mass spectrometer this soft ionization source has demonstrated signal-to-noise (S/N) ratios from 7 to 730 at 100 pg per injection (depending on the compound), and a dynamic range of three orders of magnitude (100 pg to 100 ng) for some of the test compounds.

Chemical composition and antioxidant activities of essential oils and methanol extracts of three wild Lavandula L. species.

A comparative study of essential oil composition, polyphenol content and antioxidant activities of Lavandula coronopifolia, Lavandula multifida and Lavandula stoechas subsp. stoechas were reported. Qualitative and quantitative variations in the composition of oils according to species were shown. Lavandula coronopifolia's oil was characterised by high proportions of trans-ß-ocimene (26.9%), carvacrol (18.5%), ß-bisabolene (13.1%) and myrcene (7.5%). The main components of L. multifida oil are carvacrol (65.1%) and ß-bisabolene (24.7%). Lavandula stoechas oil is rich in fenchone (34.3%) and comphor (27.4%). The total phenolic and flavonoid contents also significantly varied among species. Lavandula coronopifolia exhibits the highest phenolic and flavonoid contents (31.3 mg GAE g(-1) and 16.3 mg RE g(-1), respectively), followed by L. multifida (30.8 mg GAE g(-1) and 12.3 mg RE g(-1)). Methanolic extracts and essential oils displayed significant antioxidant activities. The level of antioxidant capacity varied according to extracts and species.

Historic trends of dechloranes 602, 603, 604, dechlorane plus and other norbornene derivatives and their bioaccumulation potential in lake ontario.

Temporal trends and seasonal variation of Dechloranes (Dec) 602, 603, 604, and Chlordene Plus (CP) in Niagara River suspended sediment, a Lake Ontario sediment core, and Lake Ontario lake trout were investigated, with Mirex and Dechlorane Plus (DP) included for comparison. Temporal concentration trends were generally consistent in each of the media for all compounds with the lowest concentrations observed in or after the late 1990s. In Niagara River suspended sediments, all compounds showed seasonal variation over a year with distinct profiles observed. The relative concentration patterns observed were total DP > Mirex > Dec 602 and Dec 604 > Dec 603 > CP in suspended sediments and sediment cores, whereas Mirex was highest in lake trout, followed by Dec 602 and DP. Dec 602 concentrations were 50 to 380 times greater than those of DP in lake trout, indicating Dec 602 has a greater bioaccumulation potential. The estimated biota-sediment accumulation factor (BSAF) for Dec 602 was much greater than for DP in Lake Ontario, and was greater than those calculated for PBDEs, indicating that assessment of some dechlorane compounds is merited if use is ongoing or planned.

[Analysis on the compositions of volatile oil of Alpinia henryi with GC-MS method].

OBJECTIVE: To study the components of volatile oil of Alpinia henryi. METHODS: The volatile oil was extracted by steam distillation method,used gaseous phase-mass spectrum combination method (GC-MS) to analyze the components of volatile oil. RESULTS: 58 kinds of components were isolated, among them 42 were identified and determined the relative content. CONCLUSION: This study provides a basis for the development and utilization of Alpinia henryi.

Long-term stability of thujone, fenchone, and pinocamphone in vintage preban absinthe.

Research was conducted to ascertain whether analyses of vintage absinthe samples represent their original composition in the early 1900s. Absinthe stored in traditional green glass bottles and irradiated with ultraviolet light for up to 200 h exhibited unchanged composition. Samples stored in clear glass exhibited an 18% reduction in beta-thujone content and a concurrent decoloration. These experiments indicate the stability of thujone in vintage absinthes, as these were stored in green glass bottles. The preserved color of the preban absinthes subjected to analysis indicates that no significant light exposure occurred throughout the duration of storage, and therefore provides indirect proof that no loss of terpenes occurred. The stability of absinthe was further demonstrated through the reanalysis of samples from 2001-2005, which exhibited no changes in thujone content as of 2008. A previous evaluation of preban absinthe was therefore valid and not confounded by significant thujone deterioration over time.

Chemical composition of vintage preban absinthe with special reference to thujone, fenchone, pinocamphone, methanol, copper, and antimony concentrations.

Thirteen samples of authentic absinthe dating from the preban era (i.e., prior to 1915) were analyzed for parameters that were hypothesized as contributing to the toxicity of the spirit, including naturally occurring herbal essences (thujone, pinocamphone, fenchone), methanol, higher alcohols, copper, and antimony. The total thujone content of preban absinthe was found to range between 0.5 and 48.3 mg/L, with an average concentration of 25.4 +/- 20.3 mg/L and a median concentration of 33.3 mg/L. The authors conclude that the thujone concentration of preban absinthe was generally overestimated in the past. The analysis of postban (1915-1988) and modern commercial absinthes (2003-2006) showed that the encompassed thujone ranges of all absinthes are quite similar, disproving the supposition that a fundamental difference exists between preban and modern absinthes manufactured according to historical recipes. Analyses of pinocamphone, fenchone, base spirits, copper, and antimony were inconspicuous. All things considered, nothing besides ethanol was found in the absinthes that was able to explain the syndrome "absinthism".

Comparative essential oil composition and antifungal effect of bitter fennel (Foeniculum vulgare ssp. piperitum) fruit oils obtained during different vegetation.

The chemical composition of the flower and unripe and ripe fruits from fennel (bitter) (Foeniculum vulgare ssp. piperitum) has been examined by gas chromatography and gas chromatography-mass spectrometry. The main identified components of the flower and unripe and ripe fruit oils were estragole (53.08%, 56.11%, and 61.08%), fenchone (13.53%, 19.18%, and 23.46%), and alpha-phellandrene (5.77%, 3.30%, and 0.72%), respectively. Minor qualitative and major quantitative variations for some compounds of essential oils were determined with respect to the different parts of F. vulgare. The oils exerted varying levels of antifungal effects on the experimental mycelial growth of Alternaria alternata, Fusarium oxysporum, and Rhizoctonia solani. The 40 ppm concentrations of fennel oils showed inhibitory effect against mycelial growth of A. alternaria, whereas 10 ppm levels were ineffective. The analyses show that fennel oils exhibited different degrees of fungistatic activity depending on the doses.

Environmental assessment of 5-ethylidene-2-norbornene using modeled and measured fate and effects results.

Several predictive models were used to assess aquatic exposure, persistence (P) and potential for long-range transport (LRT) of 5-ethylidene-2-norbornene (ENB). Such estimations are components of the assessment process for persistent, bioaccumulative and toxic (PBT) substances, which are also referred to as persistent organic pollutants (POPs). An ecological exposure assessment for ENB from manufacturing activities was conducted based on physical/chemical properties, monitoring data, and degradation, transport and distribution estimates. Based on the results of several model predictions, chronic exposure of aquatic organisms is not expected, due to the anticipated residence time of ENB in aquatic ecosystems. These modeled results consistently predict ENB does not present the potential to persist in the environment. Volatilization from water to the air is calculated to occur at a relatively rapid rate for ENB based on its Henry's Law constant. Once in the air, ENB is expected to degrade rapidly due to oxidation by hydroxyl radicals and ozone based on calculated atmospheric half-lives of 57 and 27 min, respectively. Additionally, ENB is not predicted to undergo long-range transport based on the short atmospheric half-life due to oxidation by hydroxyl radicals and ozone. Additionally, based on predicted exposure from site-specific emission using the EPA model EFAST, ENB is not expected to reach concentrations of concern for chronic aquatic toxicity endpoints.