Estrogenic and dioxin-like compounds in sediment from Zierikzee harbour identified with CALUX assay-directed fractionation combined with one and two dimensional gas chromatography analyses

The identity of compounds responsible for estrogenic and dioxin-like activities in sediment from the harbour of the small town Zierikzee in Zeeland, The Netherlands, was investigated using a bioassay directed fractionation approach with the in vitro estrogen and dioxin responsive reporter gene assays ER- and DR-CALUX. For identification of compounds exhibiting activity in the bioassays, either one or two-dimensional GC in combination with quadrupole (MSD), ion trap (ITD) or time-of-flight mass spectrometric detection (ToF-MS) was used, depending on the biological and chemical characteristics and the complexity of the fractions. The natural estrogenic hormone 17-β-estradiol and its metabolite estrone were identified with GC–ITD as the main contributors to the estrogenic activity. After successive rounds of fractionation, the dioxin-like activity could be explained by the presence of various polycyclic aromatic hydrocarbons identified with GC–MSD and two-dimensional comprehensive GC × GC–ToF-MS. Some estrogenic activity of a relatively non-polar nature remained unidentified.     

GC × GC—A New Analytical Tool For Environmental Forensics

Comprehensive two-dimensional gas chromatography, GC × GC, is a new analytical tool with a tremendous capability to separate and identify organic compounds in complex environmental samples. GC × GC uses two different chromatography columns coupled serially by a modulator to produce a volatility by polarity separation and distribute compound peaks across a two-dimensional retention time plane. The two-dimensional separation produces an order of magnitude more resolved peaks than traditional GC methods. The grouping or ordering of the peaks in the GC × GC chromatogram facilitates the identification of unknown compounds and the comparison of complex environmental samples. When a mass spectrometer detector is used, each resolved GC × GC peak yields a single-component, interference-free mass spectrum that leads to accurate matching with mass spectral libraries. GC × GC examination of marine sediment extracts identified a wide variety of chemical contaminants including polychlorinated biphenyls, p -nonylphenol isomers, polycyclic aromatic hydrocarbons, benzotriazoles, and the alkane, cycloalkane, alkylbenzene, alkylnaphthalene, and biomarker fractions of petroleum. The two-dimensional GC × GC chromatogram image permits rapid screening of the sediment extracts for these and other unknown contaminants.     

Bioanalytical and instrumental analysis of estrogenic activities in drinking water sources from Yangtze River Delta

The estrogenic activities of source water from Yangtze River, Huaihe River, Taihu Lake and groundwater in Yangtze River Delta in the dry and wet season were determined by use of reporter gene assays based on African green monkey kidney (CV-1) cell lines. Higher estrogenic activities were observed in the dry season, and the estrogenic potentials in water samples from Taihu Lake were greater than other river basins. None of the samples from groundwater showed estrogen receptor (ER) agonist activity. The 17β-Estradiol (E2) equivalents (EEQs) of water samples in the dry season ranged from 9.41 × 10^?1 to 1.20 × 10¹ ng E2 L^?1. In the wet season, EEQs of all the water samples were below the detection limit as 9.00 × 10^?1 ng E2 L^?1 except for one sample from Huaihe River. The highest contribution of E2 was detected in Yangtze River as 99% of estrogenic activity. Nonylphenol (NP, 100% detection rate) and octylphenol (OP, 100% detection rate) might also be responsible for the estrogenic activities in water sources. Potential health risk induced by the estrogenic chemicals in source water may be posed to the residents through water drinking.     

Identification,abundance and seasonal variation of anthropogenic organic aerosols from a mega-city in China

PM_2.5 aerosols were collected in Nanjing, a typical mega-city in China, during summer and winter 2004 and were characterized for aromatic and cyclic compounds using a GC/MS technique to understand the air pollution problem. They include polycyclic aromatic hydrocarbons (PAHs), hopanes, phthalates and hydroxy-PAHs (OH-PAHs). PAHs, hopanes and OH-PAHs presented higher concentrations in winter (26–178, 3.0–18, and 0.013–0.421 ng m⁻³, respectively) than in summer (12–96, 1.6–11, and 0.029–0.171 ng m⁻³, respectively) due to an enhanced coal burning for house heating and atmospheric inversion layers developed in the cold season. In contrast, phthalates are more abundant in summer (109–368 ng m⁻³, average 230 ng m⁻³) than in winter (33–390 ng m⁻³, average 170 ng m⁻³) due to an enhanced evaporation from plastics during the hot season and the subsequent deposition on the pre-existing particles. Generally, all the identified compounds showed higher concentrations in nighttime than in daytime due to inversion layers and increased emissions from heavy-duty trucks at night. PAHs, hopanes and phthalates in Nanjing aerosols are 5–100 times more abundant than those in Los Angeles, USA, indicating a serious air pollution problem in the city. Concentrations of OH-PAHs are 1–3 orders of magnitude less than their parent PAHs and comparable to those reported from other international cities. Source identification using diagnostic ratios of the organic tracers suggests that PAHs in Nanjing urban area are mainly derived from coal burning, whereas hopanes are more attributable to traffic emissions.     

Use of thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) on identification of odorant emission focus by volatile organic compounds characterisation

Volatile organic compounds (VOCs) from several different municipal solid wastes’ treatment plants in Mallorca (Spain) have been analysed by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified.The linear fit for all 93 external standard calibration, from 10 mg L⁻¹ to 150 mg L⁻¹ (n = 4), was within the range 0.974 < r² < 0.998. Limits of detection of the method (LOD) for all the standards were within the range 1.1–4,213 pg, as the absolute standard amount spiked into sorbent tubes in 1 μL standard mixture (dissolved in methanol).Overall results stated systematic correlation between waste’s nature and VOCs’ air composition. Organic wastes show main contribution of terpenes, waste water sludge residues’ of reduced sulphured compounds (RSCs) and municipal solid wastes show contribution of a wide sort of VOCs. The use of a chemometric approach for variable’s reduction to 12 principal components enables evaluation of similarities and dissimilarities between facilities. PCA clearly related samples to its corresponding facility on the basis of their VOCs composition and the ambient temperature.     

The composition and sources of PM2.5 organic aerosol in two urban areas of Chile

Fine particle (PM_2.5) samples were collected, using a charcoal diffusion denuder, in two urban areas of Chile, Santiago and Temuco, during the winter and spring season of 1998. Molecular markers of the organic aerosol were determined using GC/MS. Diagnostic ratios and molecular tracers were used to investigate the origin of carbonaceous aerosols. As main sources, road and non-road engine emissions in Santiago, and wood burning in Temuco were identified. Cluster analysis was used to compare the chemical characteristics of carbonaceous aerosols between the two urban environments. Distinct differences between Santiago and Temuco samples were observed. High concentrations of isoprenoid (30–69 ng m⁻³) and unresolved complex mixture (UCM) of hydrocarbons (839–1369 ng m⁻³) were found in Santiago. High concentrations of polynuclear aromatic hydrocarbons (751±304 ng m⁻³) and their oxygenated derivatives (4±2 ng m⁻³), and of n-alk-1-enes (16±13 ng m⁻³) were observed in Temuco.     

Investigations into a novel method for atmospheric polycyclic aromatic hydrocarbon monitoring

A novel analytical method for atmospheric polycyclic aromatic hydrocarbons (PAHs) was developed based on laser induced fluorescence (LIF) of samples on quartz multi-channel polydimethylsiloxane traps. A tunable dye laser with a frequency doubling crystal provided the excitation radiation, and a double monochromator with a photomultiplier tube detected emitted fluorescence. The method allowed for the rapid (<5 min), cost effective analysis of samples. Those yielding interesting results could be further analysed by direct thermal desorption-gas chromatography–mass spectrometry (TD–GC–MS, with limits of detection of ～0.3 ng m^?3), as photodegradation was minimal (<10% over 5 min irradiation). Small amounts of naphthalene photodegradation products identified by TD–GC–MS after >15 min irradiation, included phenol, benzyl alcohol and phthalic anhydride. Without any signal optimization, a LIF detection limit of ～1 μg m^?3 was established for naphthalene using a diffusion tube (diffusion rate of 2 ng s^?1) and 292 nm excitation.     

Isocyanatocyclohexane and isothiocyanatocyclohexane levels in urban and industrial areas and possible emission-related activities

Isocyanatocyclohexane and isothiocyanatocyclohexane are becoming relevant compounds in urban and industrial air, as they are used in important amounts in automobile industry and building insulation, as well as in the manufacture of foams, rubber, paints and varnishes. Glass multi-sorbent tubes (Carbotrap, Carbopack, Carboxen) were connected to LCMA-UPC pump samplers for the retention of iso- and isothiocyanatocyclohexanes. The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detector (MSD). TD-GC/MS was chosen as analytical method due to its versatility and the possibility of analysis of a wide range of volatility and polarity VOC in air samples. The method was satisfactory sensitive, selective and reproducible for the studied compounds. The concentrations of iso- and isothioisocyanatocyclohexanes were evaluated in different urban, residential and industrial locations from extensive VOC air quality and odour episode studies in several cities in the Northeastern edge of Spain. Around 200–300 VOC were determined qualitatively in each sample. Higher values of iso- and isothiocyanatocyclohexane were found in industrial areas than in urban or residential locations. The concentrations ranged between n.d.−246 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively, for industrial areas. On the other hand, urban and residential locations showed concentrations ranging between n.d.−164 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively. The site location (urban or industrial), the kind and nearness of possible iso- and isothiocyanatocyclohexane emission activities (industrial or building construction) and the changes of wind regimes throughout the year have been found the most important factors influencing the concentrations of these compounds in the different places.     

Urban roadside aromatic hydrocarbons in three cities of the Pearl River Delta,People's Republic of China

Urban roadside levels of benzene, toluene, ethylbenzene and xylenes (BTEX) were investigated in three typical cities (Guangzhou, Macau and Nanhai) in the Pearl River Delta Region of south China. Air samples were collected at typical ground level microenvironments by multi-bed adsorbent tubes. The BTEX concentrations were determined by thermal desorption–gas chromatography–mass selective detector (TD–GC–MSD) technique. The mean concentrations of benzene, toluene, ethylbenzene and xylenes were, respectively, 51.5, 77.3, 17.8 and 81.6 μg/m³ in Guangzhou, 34.9, 85.9, 24.1, 95.6 μg/m³ in Macau, and 20.0, 39.1, 3.0 and 14.2 μg/m³ in Nanhai. The relative concentration distribution pattern and mutual correlation analysis indicated that in Macau BTEX were predominantly traffic-related while in Guangzhou benzene had sources other than vehicle emission. In Nanhai, both benzene and toluene had different sources other than vehicle emission. The samples collected from Guangzhou showed that BTEX had significant higher concentrations in November than those in July.     

Emissions of volatile fatty acids from feed at dairy facilities

Recent studies suggest that dairy operations may be a major source of non-methane volatile organic compounds in dairy-intensive regions such as Central California, with short chain carboxylic acids (volatile fatty acids or VFAs) as the major components. Emissions of four VFAs (acetic acid, propanoic acid, butanoic acid and hexanoic acid) were measured from two feed sources (silage and total mixed rations (TMR)) at six Central California Dairies over a fifteen-month period. Measurements were made using a combination of flux chambers, solid phase micro-extraction fibers coupled to gas chromatography mass spectrometry (SPME/GC–MS) and infra-red photoaccoustic detection (IR-PAD for acetic acid only). The relationship between acetic acid emissions, source surface temperature and four sample composition factors (acetic acid content, ammonia-nitrogen content, water content and pH) was also investigated. As observed previously, acetic acid dominates the VFA emissions. Fluxes measured by IR-PAD were systematically lower than SPME/GC–MS measurements by a factor of two. High signals in field blanks prevented emissions from animal waste sources (flush lane, bedding, open lot) from being quantified. Acetic acid emissions from feed sources are positively correlated with surface temperature and acetic acid content. The measurements were used to derive a relationship between surface temperature, acetic acid content and the acetic acid flux. The equation derived from SPME/GC–MS measurements predicts estimated annual average acetic acid emissions of (0.7 + 1/?0.4) g m^?2 h^?1 from silage and (0.2 + 0.3/?0.1) g m^?2 h^?1 from TMR using annually averaged acetic acid content and meteorological data. However, during the summer months, fluxes may be several times higher than these values.     

Seasonal characteristics of ambient volatile organic compounds in Seoul,Korea

The measurements of C₂–C₉ volatile organic compounds (VOC) were carried out at a site in Seoul, the capital of Korea from August 1998 to July 1999. Air samples were collected for 24 h in 6 l SUMMA canisters every 6 days. The canister samples were quantitatively analyzed by a GC/FID and GC/MS. The species with the highest mean concentration among the 70 identified was propane (7.8 ppb), followed by toluene (6.4 ppb) and ethylene (5.9 ppb). The high concentration of propane was mainly attributed to the emissions by liquefied petroleum gas (LPG) usage for cooking and heating, and butane fuel for transportation. The general trend of the seasonal variation shows higher concentrations in winter and lower ones in summer. This behavior was mainly caused by the variations of temperature, and resultant VOC source strengths, coupled with the variations of the mixing depth. According to the analysis of concentration ratios, the seasonal contributions of the major emission sources to the VOC concentrations were influenced by ambient temperature. Further, it was identified that the contributions by the use of solvents, natural gas, LPG, and butane fuel were closely related to the variations of consumption pattern according to seasons. Through the analysis of the concentration correlations between less reactive compound and highly reactive ones for summer and winter months, it was found that photochemical reactivity affects relative concentration of reactive compound.     

Reactions between ozone and building products: Impact on primary and secondary emissions

Reactions of ozone on common building products were studied in a dedicated emission test chamber system. Fourteen new and unused products were exposed to 100–160 ppb of ozone at 23 °C and 50% RH during 48 h experiments. Ozone deposition velocities calculated at steady state were between 0.003 cm s⁻¹ (alkyd paint on polyester film) and 0.108 cm s⁻¹ (pine wood board). All tested product showed modified emissions when exposed to ozone and secondary emissions of several aldehydes were identified. Carpets and wall coverings emitted mainly C₅–C₁₀ n-aldehydes, typical by-products of surface reactions. Linoleum, polystyrene tiles and pine wood boards also showed increased emissions of formaldehyde, benzaldehyde and hexanal associated with reduced emissions of unsaturated compounds suggesting the occurrence of gas-phase reactions. The ozone removal on the different tested products was primarily associated with surface reactions. The relative contribution of gas-phase reactions to the total ozone removal was estimated to be between 5% and 30% for pine wood boards depending on relative humidity (RH) and on the incoming ozone concentration and 2% for polystyrene tiles. On pine wood board, decreasing ozone deposition velocities were measured with increasing ozone concentrations and with RH increasing in the range 30–50%.     

Heterogeneous reactivity of pyrene and 1-nitropyrene with NO2: Kinetics,product yields and mechanism

The heterogeneous reactivity of nitrogen dioxide with pyrene and 1-nitropyrene (1NP) adsorbed on silica particles has been investigated using a fast-flow-tube in the absence of light. Reactants and products were extracted from particles using pressurised fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different NO₂ concentrations and second order rate constants were calculated considering the oxidant concentration. The following rate constant values were obtained at room temperature: k(NO₂ + pyrene) = (9.3 ± 2.3) × 10^?17 cm³ molecule^?1 s^?1 and k(NO₂ + 1NP) = (6.2 ± 1.5) × 10^?18 cm³ molecule^?1 s^?1, showing that the reactivity of 1NP was slower by a factor of 15 than that of pyrene. 1NP was identified as the only NO₂-initiated oxidation product of pyrene and all the three dinitropyrenes were identified in the case of the 1NP reaction. The product quantification allowed showing that the kinetics of oxidation product formation was equal to that measured for parent compounds degradation, within uncertainties, confirming the validity of the reaction kinetics measurements.     

Risks from sediments contaminated with organochlorine pesticides in Hangzhou,China

In September 2009, we investigated the residues, enantiomer fractions (EFs) and biological risks of organochlorine pesticides (OCPs), including dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs), in three different depth ranges (0–5 cm, 5–10 cm and 10–15 cm) of sediments from 15 sites in Hangzhou, China. The concentration (ng g^?1 dry weight) ranges of HCHs and DDTs in surface sediments were 0.74–5.8 and 0.76–17, respectively. The vertical distribution of mean OCP concentrations was in the order of 10–15 cm > 5–10 cm > 0–5 cm and implied that the residues of HCHs and DDTs gradually decreased after they were banned. The residues of OCPs in the study area mainly originated from the historical OCP use. The isomer ratios of <alpha>-HCH (α-HCH)/<gamma>-HCH (γ-HCH) (0.10–7.6) implied that HCH residues were derived not only from historical technical HCH use but also from additional use of lindane in this area. The isomer ratios of o,p′-DDT/p,p′-DDT (51% of samples were in the range of 0.3–1.3) suggested that both dicofol-type DDT and technical DDT applications may be present in most study areas. The (+)-enantiomers of α-HCH and o,p′-DDT were more prevalent than (?)-enantiomer in most samples with the fractions contain different enantiomers greater than 0.5. DDTs, especially p,p′-DDE, are the main OCP species of more ecotoxicological concern in Hangzhou.     

Estimation of ecotoxicity of petroleum hydrocarbon mixtures in soil based on HPLC–GCXGC analysis

Detailed HPLC–GCXGC/FID (high performance liquid chromatography followed by comprehensive two-dimensional gas chromatography with flame-ionization detection) analysis of oil-contaminated soils was performed to interpret results of selected acute ecotoxicity assays. For the five ecotoxicity assays tested, plant seed germination and Microtox^® were selected as most sensitive for evaluating ecotoxicity of the oil in the soil phase and in the leaching water, respectively. The measured toxicity for cress when testing the soil samples did not correspond to TPH concentration in the soil. A detailed chemical composition analysis of the oil contamination using HPLC–GCXGC/FID allows to better predict the ecotoxicological risk and leaching potential of petroleum hydrocarbons in soil. Cress biomass production per plant was well correlated to the total aromatic hydrocarbon concentration (R² = 0.79, n = 6), while cress seed germination was correlated (R² = 0.82, n = 6) with total concentration of “highly water-soluble aromatic hydrocarbons” (HSaromatics). The observed ecotoxicity of the leaching water for Microtox-bacteria related well to calculated (based on the HPLC–GCXGC/FID results) petroleum hydrocarbon equilibrium concentrations in water.     

Analysis of particulate polycyclic aromatic hydrocarbons by on-line coupled supercritical fluid extraction–liquid chromatography–gas chromatography–mass spectrometry

An on-line supercritical fluid extraction–liquid chromatography–gas chromatography–mass spectrometry (SFE–LC–GC–MS) method was developed for the analysis of the particulate polycyclic aromatic hydrocarbons (PAHs). The limits of detection of the system for the quantification standards were in the range of 0.25–0.57 ng, while the limits of determinations for filter samples varied from 0.02 to 0.04 ng m⁻³ (24 h sampling). The linearity was excellent from 5 to 300 ng (R²>0.967). The analysis could be carried out in a closed system without tedious manual sample pretreatment and with no risk of errors by contamination or loss of the analytes. The results of the SFE–LC–GC–MS method were comparable with those for Soxhlet and shake-flask extractions with GC–MS. The new method was applied to the analysis of PAHs collected by high-volume filter in the Helsinki area to study the seasonal trend of the concentrations. The individual PAH concentrations varied from 0.015 to more than 1 ng m⁻³, while total PAH concentrations varied from 0.81 to 5.68 ng m⁻³. The concentrations were generally higher in winter than in summer. The mass percentage of the total PAHs in total suspended particulates ranged from 2.85×10⁻³% in July to 15.0×10⁻³% in December. Increased emissions in winter, meteorological conditions, and more serious artefacts during the sampling in summer season may explain the concentration profiles.     

Carbon mineralization,microbial activity and metal dynamics in tailing ponds amended with pig slurry and marble waste

A field experiment was set up in Cartagena-La Unión Mining District, SE Spain, aimed at evaluating the short-term effects of pig slurry (PS) amendment alone and together with marble waste (MW) on organic matter mineralization, microbial activity and stabilization of heavy metals in two tailing ponds. These structures pose environmental risk owing to high metals contents, low organic matter and nutrients, and null vegetation. Carbon mineralization, exchangeable metals and microbiological properties were monitored during 67 d. The application of amendments led to a rapid decrease of exchangeable metals concentrations, except for Cu, with decreases up to 98%, 75% and 97% for Cd, Pb and Zn, respectively. The combined addition of MW + PS was the treatment with greater reduction in metals concentrations. The addition of PS caused a significant increase in respiration rates, although in MW + PS plots respiration was lower than in PS plots. The mineralized C from the pig slurry was low, approximately 25–30% and 4–12% for PS and MW + PS treatments, respectively. Soluble carbon (Csol), microbial biomass carbon (MBC) and β-galactosidase and β-glucosidase activities increased after the application of the organic amendment. However, after 3 d these parameters started a decreasing trend reaching similar values than control from approximately day 25 for Csol and MBC. The PS treatment promoted highest values in enzyme activities, which remained high upon time. Arylesterase activity increased in the MW + PS treatment. Thus, the remediation techniques used improved soil microbiological status and reduced metal availability. The combined application of PS + MW reduced the degradability of the organic compounds.     

An insight into the influence of low dose irradiation pretreatment on the microbial decolouration and degradation of Reactive Red-120 dye

The influence of low dose irradiation pretreatment on the microbial decolouration and degradation of Reactive Red-120 (RR-120) dye was investigated in detail by using Pseudomonas sp. SUK1. About 27%, 56% and 66% decolouration of 150 ppm RR-120 dye solution was observed by applying 0, 0.5 and 1 kGy doses, respectively, in the first step followed by microbial treatment for 24 h under static condition. Similarly, about 70%, 88% and 90% TOC removal was observed by applying 0, 0.5 and 1 kGy doses, respectively, in the first step followed by the microbial treatment for 96 h under static condition. The radiation induced fragmented products of RR-120 at doses of 0.5 and 1 kGy were investigated by FTIR and electrospray ionization-MS analysis. The induction of the enzymes viz. laccase, tyrosinase, azoreductase and NADH-2,6-dichlorophenol indophenol reductase was studied in the decolourised solution obtained after irradiating 150 ppm RR-120 dye solution with 0 and 1 kGy doses followed by the microbial treatment for 96 h under static condition. The enzymatic degradation products were studied by FTIR, HPLC and GC–MS. The toxicity study of the treated dye solution on plants revealed the degradation of RR-120 into non-toxic products by combined radiation-microbial treatment. This study explores a reliable and promising way to use industrially viable dose (?1 kGy) and microbial strain viz. Pseudomonas sp. SUK1 for permissible safe disposal of dye solutions from textile industries.