Gas chromatographic analysis of organic marker compounds in fine particulate matter using solid-phase microextraction

A gas chromatographic method that uses solid-phase microextraction for analysis of organic marker compounds in fine particulate matter (PM2.5) is reported. The target marker compounds were selected for specificity toward emission from wood smoke, diesel or gasoline combustion, or meat cooking. Temperature-programmed volatilization analysis was used to characterize the thermal stabilities and volatile properties of the compounds of interest. The compounds were thermally evaporated from a quartz filter, sorbed to a solid phase microextraction (SPME) fiber, and thermally desorbed at 280 degrees C in a gas chromatograph injection port connected via a DB 1701 capillary separating column. Various experimental parameters (fiber type, time, and temperature of sorption) were optimized. It was found that high extraction yield could be achieved using a polyacrylate fiber for polar substances, such as levoglucosan, and a 7-microm polydimethylsiloxane (PDMS)-coated fiber for nonpolar compounds, such as hopanes and polyaromatic hydrocarbon. A compromise was made by selecting a carboxen/PDMS fiber, which can simultaneously extract all of the analytes of interest with moderate-to-high efficiency at 180 degrees C within a 30-min accumulation period. The optimized method was applied to the determination of levoglucosan in pine wood combustion emissions. The simplicity, rapidity, and selectivity of sample collection with a polymer-coated SPME coupled to capillary gas chromatography (GC) made this method potentially useful for atmospheric chemistry studies.     

Global-scale environmental transport of persistent organic pollutants

In order to realistically simulate both chemistry and transport of atmospheric organic pollutants, it is indispensable that the applied models explicitly include coupling between different components of the global environment such as atmosphere, hydrosphere, cryosphere and soil system. A model with such properties is presented.

The atmospheric part of the model is based on the equations in a general contravariant form which permits easy changes of the coordinate system by redefining the metric tensor of a specifically employed coordinate system. Considering a need to include explicitly the terrain effects, the terrain following spherical coordinate system is chosen from among many possible coordinate systems. This particular system is a combination of the Gal-Chen coordinates, commonly employed in mesoscale meteorological models, and the spherical coordinates, typical for global atmospheric models.

In addition to atmospheric transport, the model also simulates the exchange between air and different types of underlying surfaces such as water, soil, snow, and ice. This approach permits a realistic representation of absorption and delayed re-emission of pollutants from the surface to the atmosphere and, consequently, allows to capture hysteresis-like effects of the exchange between the atmosphere and the other components of the system. In this model, the most comprehensive numerical representation of the exchange is that for soil. In particular, the model includes a realistic soil module which simulates both diffusion and convection of a tracer driven by evaporation from the soil, precipitation, and gravity.

The model is applied to a long-term simulation of the transport of pesticides (hexachlorocyclohexanes in particular). Emission fluxes from the soil are rigorously computed on the basis of the realistic data of the agricultural application. All four modelled systems, i.e. atmosphere, soil, hydrosphere and cryosphere, are driven by objectively analysed meteorological data supplemented, when necessary, by climatological information. Therefore, the verification against the observed data is possible. The comparison of the model results and the observations taken at remote stations in the Arctic indicates that the presented global modelling system is able to capture both trends and short-term components in the observed time series of the concentrations, and therefore, provides a useful tool for the evaluation of the source–receptor relationships.     

Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.     

Sorption of organic pollutants by marine sediments: implication for the role of particulate organic matter

The objective of this study was to quantify sorption properties for kerogen/black carbon (BC)-bearing sediments. Single-solute sorption isotherms were measured for five pristine marine sediments using phenanthrene, naphthalene, 1,3,5-trichlorobenzene, and 1,4-dichlorobenzene as the sorbates. The results showed that the sorption isotherms were nonlinear and that the organic carbon normalized single point K_OC values were comparable to those reported in the literature for the purified keorgen and BC, but are much higher than the data reported for HA and kerogen/BC-containing terrestrial soils and sediments. It is likely that koergen and BC associated with these pristine marine sediments may not be encapsulated with humic acids or Fe and Mn oxides and hydroxides as often do in terrestrial soils and sediments. As a result, they may be fully accessible to sorbing molecules, exhibiting higher sorption capacities. The study suggests that competition from background HOCs and reduced accessibility when kerogen and BC are associated with terrestrial sediments may dramatically increase variability of sorption reactivities of geosorbents. Such variability may lead to large uncertainties in the prediction of sorption from the contents of kerogen and/or BC along with TOC.     

Cosorption study of organic pollutants and dissolved organic matter in a soil

In this study we have evaluated the effects of dissolved organic matter (DOM) on sorption of imidacloprid, 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on a typical calcareous soil (Luvic Xerosol) from south-eastern Spain. Two different types of DOM were used, that is to say, dissolved natural organic matter extracts from a commercial peat (DNOM) and a high-purity tannic acid (TA) solution. The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results indicated that the presence of both DNOM and TA, over a concentration range of 15-100 mg L(-1), produced an increase in the amount of 3,4-DCA and 4-BA sorbed and a decrease in the amount of imidacloprid retained on the soil studied. A modified distribution coefficient, K(doc), has been proposed as a safer parameter for soil sorption predictions of organic pollutants and it could be of help to model the fate of these in the environment.     

Assessment of commercially available polymeric materials for sorptive microextraction of priority and emerging nonpolar organic pollutants in environmental water samples

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978?r ²?r ²?-1 level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.     

Relationships between organic matter, black carbon and persistent organic pollutants in European background soils: Implications for sources and environmental fate

Black carbon (BC) and total organic carbon (TOC) contents of UK and Norwegian background soils were determined and their relationships with persistent organic pollutants (HCB, PAHs, PCBs, co-planar PCBs, PBDEs and PCDD/Fs) investigated by correlation and regression analyses, to assess their roles in influencing compound partitioning/retention in soils. The 52 soils used were high in TOC (range 54-460 mg/g (mean 256)), while BC only constituted 0.24-1.8% (0.88%) of the TOC. TOC was strongly correlated (p < 0.001) with HCB, PCBs, co-PCBs and PBDEs, but less so with PCDD/Fs (p < 0.05) and PAHs. TOC explained variability in soil content, as follows: HCB, 80%; PCBs, 44%; co-PCBs, 40%; PBDEs, 27%. BC also gave statistically significant correlations with PBDEs (p < 0.001), co-PCBs (p < 0.01) and PCBs, HCB, PCDD/F (p < 0.05); TOC and BC were correlated with each other (p < 0.01). Inferences are made about possible combustion-derived sources, atmospheric transport and air-surface exchange processes for these compounds.     

Clear effects of soil organic matter chemistry, as determined by NMR spectroscopy, on the sorption of diuron

Organic matter has long been recognized as the main sorbent phase in soils for hydrophobic organic compounds (HOCs). In recent times, there has been an increasing realization that not only the amount, but also the chemical composition, of organic matter can influence the sorption properties of a soil. Here, we show that the organic carbon-normalized sorption coefficient (K(OC)) for diuron is 27-81% higher in 10 A11 horizons than in 10 matching A12 horizons for soils collected from a small (2ha) field. K(OC) was generally greater for the deeper (B) horizons, although these values may be inflated by sorption of diuron to clays. Organic matter chemistry of the A11 and A12 horizons was determined using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. K(OC) was positively correlated with aryl C (r2=0.59, significance level 0.001) and negatively correlated with O-alkyl C (r2=0.84, significance level <0.001). This is only the second report of correlations between whole soil K(OC) and NMR-derived measures of organic matter chemistry. We suggest that this success may be a consequence of limiting this study to a very small area (a single field). There is growing evidence that interactions between organic matter and clay minerals strongly affect K(OC). However, because the soil mineralogy varies little across the field, the influence of these interactions is greatly diminished, allowing the effect of organic matter chemistry on K(OC) to be seen clearly. This study in some way reconciles studies that show strong correlations between K(OC) and the chemistry of purified organic materials and the general lack of such correlations for whole soils.     

Analysis of marine sediment, water and biota for selected organic pollutants

The concentrations of various organic pollutants (benzo(a)pyrene (BaP), hexachlorobenzene (HCB) and pentachlorophenol (PCP)) were determined in samples of water, sediment and biota (flounder, killifish, shrimp, crabs and squid) from San Luis Pass, Texas. Sediment was also analyzed for polychlorinated biphenyls (PCBs), phthalic acid esters (PAEs) and various pesticides. Only PCP was detectable in water. In sediment, the relative concentrations were PAEs > BaP > (PCBs HCB) > PCP. In biota, BaP was not detectable in any animal; HCB was highest in crabs and PCP was highest in all others (flounder, killifish, shrimp and squid). The relative concentrations of HCB and PCP were different in the different organisms. The differences between the relative concentrations in the biota and in sediment are discussed. The results of this study are compared to values measured at other sites. This study is part of a larger effort to identify and quantitate pollutants in various Texas estuaries and to serve as a basis for monitoring marine pollution.     

The development of soil organic matter in restored biodiverse Jarrah forests of South-Western Australia as determined by ASE and GCMS

Background, aim and scope  

Soil organic matter (SOM) is known to increase with time as landscapes recover after a major disturbance; however, little is known about the evolution of the chemistry of SOM in reconstructed ecosystems. In this study, we assessed the development of SOM chemistry in a chronosequence (space for time substitution) of restored Jarrah forest sites in Western Australia.     

Partitioning and photodegradation of ciprofloxacin in aqueous systems in the presence of organic matter

Ciprofloxacin is an extensively used antibiotic that has been reported to occur in surface water. Previous studies have indicated that ciprofloxacin photodegrades and sorbs to particulate organic material within aquatic systems. The first objective of the current study was to evaluate the influence of organic material on photodegradation rates of ciprofloxacin. Using a bench top experimental design, ciprofloxacin was added to experimental chambers that contained only water or water and fine particulate organic matter (FPOM) followed by exposure to ultraviolet light. Sorption to FPOM was rapid, reducing the amount of ciprofloxacin that was available for photodegradation. Thus, the presence of FPOM initially decreased the ciprofloxacin concentration in the aqueous compartment. However by the end of the 16 h test, 42% of the ciprofloxacin was recovered from the test system with FPOM present, while only 2% of the ciprofloxacin was recovered in systems that did not contain FPOM. The second objective of this study was to compare the sorption coefficients for ciprofloxacin between two types of organic material: FPOM, classified as amphipod processed leaves, and coarse particulate organic matter (CPOM), represented by intact leaf disks. Sorption to FPOM (log Kd of 4.54+/-0.09 l kg(-1)) was 1.6 orders of magnitude greater than sorption to CPOM (log Kd of 2.92+/-0.10 l kg(-1)) potentially resulting in differential toxicity among similar organisms that occupy these different niches and leading to different estimates of environmental fate and effects.     

Hair-biomonitoring of organic pollutants

This report reviews past research on hair analysis development for organic contaminants from the point of view of analytical procedures, successful applications and their limitations. For the past 20 years, hair analysis for organic pollutants has received more and more attention, since it is non-invasive, easily available and ethically not prioritized. New methods such as SFE, SPME and INAA have been developed to make the analysis more accurate and reliable. Furthermore, the correlation of contamination levels between hair samples and ambient air or internal tissues has been found by hair analysis and short-term and long-term exposure assessment in combination. However, there are still some limitations of hair analysis to be a validated risk assessment tool for many compounds. Some limitations had been of the past, some have not been fully investigated and need still further study. In this way, hair analysis can be the key to successfully biomonitor organic contaminations.     

Persistent organic pollutants and sedimentary organic matter properties: a case study in the Kishon River, Israel

The Kishon River, the second largest coastal river in Israel, has been severely polluted for several decades. Sediments from upstream and downstream sites of the river were analyzed, lipid-extracted and evaluated for phenanthrene uptake. Total polycyclic aromatic hydrocarbon (PAH) concentration in downstream sediments was 299 microg kg(-1), consisting mostly of petrogenic-derived PAHs. Downstream sedimentary lipids were found to be dominated by fresh and decomposed petroleum-derived n-alkanes. The total PAH concentration in upstream sediments was 173 microg kg(-1), consisting mostly of pyrogenic-derived PAHs, whereas lipids from these sediments were mostly vegetation-derived. Spectroscopic data suggested an exceptionally high aromatic content in downstream humic acid, which originated from PAHs attached to its structure. Sorption data suggested that upstream sedimentary cuticle-derived lipids function as a sorption domain, while downstream sedimentary lipids, consisting of shorter-chain-length petroleum-derived alkanes, compete with phenanthrene for sorption sites.     

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk: A literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.     

环境中有机污染物的半导体光催化降解研究进展

应用半导体二氧化钛光催化剂促进氧化降解环境中常见有机污染物是一种有效的清洁处理技术,对光催化活性的半导体的必要性质,影响光催化效率的内在因素以及反应器,反应条件等方面的因素进行了讨论。     

Analysis of volatile and semivolatile organic compounds in municipal wastewater using headspace solid-phase microextraction and gas chromatography.

The aim of this work was to develop a simple and fast analytical method for the determination of a wide range of organic compounds (volatile and semivolatile compounds) in municipal wastewater. The headspace-solid-phase microextraction (HS-SPME) and gas chromatography (with mass spectroscopy) was used for determination of the organic compounds. In this study, 39 organic compounds were determined, including 3 sulfur compounds, 28 substituted benzenes, and 8 substituted phenols. The extraction parameters, such as types of SPME fiber, extraction temperature, extraction time, desorption time, salt effect, and magnetic stirring, were investigated. The method had very good repeatability, because the relative standard deviations ranged from 0.5 to 12%. The detection limit of each compound was at or below the microgram-per-liter level. This method was applied for determination of the organic compounds in raw wastewater, primary effluent, secondary effluent, and chlorinated secondary effluent samples from the Chania Municipal Wastewater Treatment Plant (Crete, Greece).     

Extractability of water-soluble soil organic matter as monitored by spectroscopic and chromatographic analyses

Purpose

Cold and hot water processes have been intensively used to recover soil organic matter, but the effect of extraction conditions on the composition of the extracts were not well investigated. Our objective was to optimize the extraction conditions (time and temperature) to increase the extracted carbon efficiency while minimizing the possible alteration of water extractable organic matter of soil (WEOM).

Method

WEOM were extracted at 20°C, 60°C, or 80°C for 24?h, 10?C60?min, and 20?min, respectively. The different processes were compared in terms of pH of suspensions, yield of organic carbon, spectroscopic properties (ultraviolet?Cvisible absorption and fluorescence), and by chromatographic analyses.

Results

For extraction at 60°C, the time 30?min was optimal in terms of yield of organic carbon extracted and concentration of absorbing and fluorescent species. The comparison of WEOM 20°C, 24?h; 60°C, 30?min; and 80°C, 20?min highlighted significant differences. The content of total organic carbon, the value of specific ultraviolet absorbance (SUVA₂₅₄), the absorbance ratio at 254 and 365?nm (E ₂/E ₃), and the humification index varied in the order: WEOM (20°C, 24?h)?Conclusions For the soil chosen, extraction at 60°C for 30?min is the best procedure for enrichment in organic chemicals and minimal alteration of the organic matter.     

Biosorption of hydrophobic organic pollutants by mixed microbial populations

In recognition of the need to estimate biosorption for natural microbial populations, the variability of partition coefficients for two hydrophobic pollutants to natural populations from a variety of aquatic systems was investigated. Biosorption partition coefficents for pyrene [2.46(±0.6) × 10⁴] and phenanthrene [6.34(±1) × 10³] were nearly constant over 14 different microbial sources, consisting of sediments and soils from eight states. For these condensed ring aromatics, semi-empirical equations were developed relating biosorption partition coefficients to octanol/water partition coefficients and to water solubility and melting point. Concepts and relationships developed for these materials should extend to other families of hydrophobic compounds.     

Partitioning microbial respiration between jet fuel and native organic matter in an organic-rich long time-contaminated aquifer

The relative importance of jet fuel biodegradation relative to the respiration of natural organic matter in a contaminated organic-rich aquifer underlying a fire training area at Tyndall Air Force Base, Florida, USA was determined with isotopic measurements. Thirteen wells were sampled and analyzed for BTX (benzene, toluene, xylene), dissolved inorganic carbon (DIC) and CH4 concentrations, and delta13C and 14C of DIC. Results range from non-detectable to 3790 ppb, 1.4-24 mM, 0.2-776 microM, +5.8 per thousand to -22 per thousand, and from 52 to 99 pmc, respectively. Residual fuel was confined to two center wells underlying the fire training area. DIC and CH4 concentrations were elevated down-gradient of the contamination, but also at sites that were not in the apparent flow path of the contaminated groundwater. DIC exhibited greatest delta13C enrichment at highest DIC and CH4 concentrations indicating that CH4 production was an important respiration mode. Radiocarbon-depleted DIC was observed at sites with high hydrocarbon concentrations and down-gradient of the site. The results indicate that while natural attenuation was not rapidly reducing the quantity of free product overlying the aquifer at the site of contamination, it was at least constraining its flow away from the spill site. Apparently under the conditions of this study, BTX was degraded as rapidly as it was dissolved.     

Behavior of selected priority organic pollutants in horizontal subsurface flow constructed wetlands: a preliminary screening

A discrete injection experiment was carried out in a constructed wetland to evaluate the behavior of selected priority pollutants. A horizontal subsurface flow pilot plant located in the NE of Spain was selected for this study. A total of eight European Priority Pollutants listed in the Water Framework Directive were considered, including a commonly used herbicide (mecoprop). The pollutants encompassed a variety of chemical classes and physicochemical properties. They included organochlorine, organophosphorus, phenols, chloroacetanilides, triazine, phenoxycarboxylic acid and phenylurea pesticides. A time series of composite effluent samples and discrete gravel bed samples from the wetland were analyzed. Response curves for all the pollutants injected from effluent concentrations were obtained and compared with the tracer (clofibric acid). On the basis of an analysis of the samples taken 21 days after the injection, priority pollutants were classified into four groups according to their removal efficiency. These groups were (i) the highly efficiently removed (>90%), namely lindane, pentachlorophenol, endosulfan and pentachlorobenzene; (ii) the efficiently removed (80-90%), namely alachlor and chlorpyriphos; (iii) poorly removed (20%), namely mecoprop and simazine; and (iv) recalcitrant to elimination, namely clofibric acid and diuron. Taking into account the poor accumulation of the injected contaminants in the gravel bed (0-20%), biodegradation and plant uptake are postulated as the most likely elimination pathways for the pollutants.