Polynuclear aromatic hydrocarbons in diesel emission particulates

A preliminary characterization of polynuclear aromatic hydrocarbons (PAH) in dichloromethane extracts of diesel exhaust particulates is described. Acid-base liquid-liquid partitioning followed by adsorption chromatography was used to isolate the PAH fraction. Compounds were identified primarily by the mass spectra of high-resolution gas chromatographic effluents. Three four-ring PAHs and their alkyl-substituted homologues were the predominant constituents. In addition, ultraviolet spectra of four high performance liquid chromatography-separated PAHs were superimposable with those of reference compounds leading to their unambiguous identification. These results show the advantage of using several complementary techniques for characterization rather than gas chromatrographapy-mass spectrometry alone.     

Ultraviolet irradiation of municipal wastewater: Evaluation of effects on organic constituents

A comparison of chromatograms derived from the UV-absorbing and oxidizable constituents present in primary and secondary municipal wastewater effluents indicates that exposure to UV irradiation at disinfection levels results in only slight chemical changes. The most pronounced chemical effects to nonvolatile organic constituents in wastewater effluents have been observed at irradiation levels in excess of those necessary for disinfection. Aliquots of effluents before and after exposure to varying levels of UV irradiation were concentrated by lyophilization prior to liquid chromatographic (LC) analysis. Anion-exchange chromatographic techniques utilizing a modified ultraviolet detector coupled in series with a cerate oxidative monitor provided excellent resolution and sensitivity in the determination of chemical changes occurring in the effluents as a result of exposure to different irradiation levels. The total coliform counts for each irradiated effluent were determined by the membrane-filter technique to evaluate the effectiveness of UV irradiation as a disinfection process for municipal wastewaters. Changes in biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC), and total Kjeldahl nitrogen (TKN) at different levels of exposure to UV irradiation are presented. The results of these determinations and the gas chromatography/mass spectrometry data characterizing the observed chemical changes are discussed.     

Presence and behavior of organic pollutants in an aqueous environment surrounded by an industrialized area

Water and sediment samples in a bay surrounded by heavily industrialized areas were analyzed by a combined gas chromatography/mass spectrometry/computer system, and a number of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAH), and polar oxygenated compounds were found. Behavior of PAH in the bay and its surroundings was traced by gas chromatographic fingerprint by using a glass capillary column. Water and sediment, dust fall, and airborne particulate samples were used as environmental samples. It was emphatically suggested that the major origin of sedimentary PAH was airborne dust.     

Validation of the new passive monitor without a membrane in indoor air

A series of experiments were conducted to investigate the suitability of activated carbon cloth (ACC) strips for diffusive sampling of volatile organic compounds in air without using a membrane. Experiments were carried out in an environmental chamber and in an indoor air environment. The monitors were analyzed qualitatively by liquid extraction and gas chromatography-mass spectrometry and quantitatively by gas chromatography with a flame ionization detector. It was shown that ACC monitors can provide satisfactory quantitative data for a wide variety of volatile organic compounds in indoor air ranging in concentration from 1 mg/m³ to 0.02 g/m³. It was also observed that the absence of a membrane does not affect the linearity of the sampling rate. In addition, a packaging system has been developed that allows samples to be sent out and returned to the laboratory for analysis by mail. Recycling, a convenient procedure of exposure, delivery, and return by postal service, as well as simple analysis all show that this passive sampler substantially reduces the cost of monitoring, thus demonstrating its benefits in the determination of contamination sources within both large industrial sites or any other building where such an analysis may be required.     

Characterization of hydrocarbon pollutant burdens in petrochemical and refinery process streams

This paper describes techniques which provide for both qualitative and quantitative identification of major components in a process stream. The techniques and instrumentation have been deliberately chosen so as to be within the technical and financial reach of all but the smallecompany laboratory. The sample preparation steps consist of an initial series of extractions which isolate compounds into organic acid, base, and neutral compounds and a totally water soluble phase. Each fraction is then concentrated and subjected to thin-layer chromatography, gas chromatography, infrared spectroscopy or ultraviolet spectroscopy as appropriate. Results are given for laboratory samples, one a mixture of aniline, phenol, benzoic acid, m-nitrobenzaldehyde, 1-butanol, 2-hexanone, nonane, and cyclohexane, and the other a mixture of benzene, ethylbenzene, and styrene. Also, a qualitative analysis of a petroleum refinery desalter water is presented.     

Possible influence of lipid content on levels of organochlorine compounds in mussels from Galicia coast (Northwestern, Spain). Spatial and temporal distribution patterns

Influence of lipid content of mussel on levels of organochlorine compounds (polychlorinated biphenyls [PCBs] and OC pesticides) has been studied. Mussel samples coming from three sites in Galicia coast (Northwestern, Spain), Moa?a and Cangas C from Ría de Vigo and Barallobre from Ría de Ferrol, collected monthly in the period from November 2000 to October 2001, have been analysed. Organochlorine compounds, PCBs (IUPAC nos. 31, 28, 52, 101, 118, 153, 105, 138, 156 and 180) and OC pesticides (pp'-DDE, op'-DDT, pp'-DDT, aldrin, isodrin and endrin) have been extracted by means of Soxhlet and determined by using gas chromatography (electron capture detector [ECD]) and gas chromatography-mass spectrometry. Statistical analysis has been performed using the SPSS statistical package. Few compounds were correlated with lipid content (Pearson product-moment correlation); for samples coming from Barallobre, only the individual PCBs 31, 28, 52 (tri- and tetrachlorinated biphenyls) and 180 (heptachlorinated biphenyl) presented a significant correlation; for Moa?a samples, two cyclodiene pesticides, endrin and isodrin, presented a slight significant correlation with lipid content. From these results, it is deduced that the normalization of the concentration of organochlorine compounds to the lipid content is not necessary, in this way, avoiding possible error sources associated to the analytical determination of the lipid contentor reproductive status of mussel. Multivariate techniques (PCA) have been employed in order to study spatial and temporal distribution patterns of organochlorine compounds. The great differences found in studied samples are mainly related to spatial distribution: separations between estuarine bays (samples coming from Ría de Vigo and Ría de Ferrol) and between rural and urban zones (samples coming from Moa?a and Cangas C and samples from Barallobre, respectively).     

Identification of nonvolatile neutral organic compounds in tap water

Nonvolatile neutral organic compounds in tap water were examined by high-pressure liquid chromatography, infrared spectrometry, ¹H- and ¹³C-FT-NMR, gel permeation chromatography, elementary analysis, and field desorption mass spectrometry. Neutral organic compounds in 10 m³ of tap water were continuously extracted by the Amberlite XAD-2 resin column, and separated into four fractions by silica-gel column chromatography. Removal of volatile compounds in fraction 3 including polar oxygenated compounds was carried out with microdistillation column under high vacuum by using a diffusion pump. Nonvolatile organic compounds isolated from tap water were identified as poly(vinyl acetate) derivatives with molecular weights ranging from 300 to 1300.     

Chlorinated paraffins in indoor air and dust: concentrations, congener patterns, and human exposure

Chlorinated paraffins (CPs) are large production volume chemicals used in a wide variety of commercial applications. They are ubiquitous in the environment and humans. Human exposure via the indoor environment has, however, been barely investigated. In the present study 44 indoor air and six dust samples from apartments in Stockholm, Sweden, were analyzed for CPs, and indoor air concentrations are reported for the first time. The sumCP concentration (short chain CPs (SCCPs) and medium chain CPs (MCCPs)) in air ranged from <5-210 ng m(-3) as quantified by gas chromatography coupled to electron ionization tandem mass spectrometry (GC/EI-MS/MS). Congener group patterns were studied using GC with electron capture negative ionization MS (GC/ECNI-MS). The air samples were dominated by the more volatile SCCPs compared to MCCPs. SumCPs were quantified by GC/EI-MS/MS in the dust samples at low μg g(-1) levels, with a chromatographic pattern suggesting the prevalence of longer chain CPs compared to air. The median exposure to sumCPs via the indoor environment was estimated to be ~1 μg day(-1) for both adults and toddlers. Adult exposure was dominated by inhalation, while dust ingestion was suggested to be more important for toddlers. Comparing these results to literature data on dietary intake indicates that human exposure to CPs from the indoor environment is not negligible.     

Determination of non-steroidal anti-inflammatory drug (NSAIDs) residues in water samples

Pharmacologically active substances used to treat human and animal illnesses can enter the aquatic environment via effluents from wastewater treatment plants or in the case of veterinary drugs directly through liquid manure discharge. Some of these substances enter the environment either as the parent compound or as active/inactive metabolites. Due to their pharmacological activity, their determination and understanding their behavior and fate in the environment are important. The scope of this paper was to develop an analytical procedure to determine common pharmaceutical residues in wastewaters. Pharmacologically active substances were chosen according to their wide spread application in Slovenia and Central Europe and are members of analgesics, e.g., non-steroidal anti-inflammatory drugs: ibuprofen, naproxen, ketoprofen and diclofenac. Selected compounds were isolated from synthetic water using a novel SPE sorbent Strata X. Due to the non-volatile nature of these compounds they were first silylised prior to gas chromatographic-mass spectrometric detection. The developed procedure was tested with synthetic wastewaters and their extraction efficiency (>84%) and method limits of detection (2-6 ng L(-1)) were determined. Our procedure has been adopted and optimised for "real" water samples and applied to eleven drinking and ten river water samples from Slovenia. The results showed no traces of NSAIDs in all potable water samples and low-range contamination (ng L(-1)) of Slovene rivers. These results show that NSAIDs contamination of Slovene waters is comparable with published results of water contamination in Central Europe.     

Monitoring of the benzene and toluene contents in human milk

Twenty-three samples of human milk collected from the milk bank of a children's hospital were analysed with a view to monitoring the possible presence of some of the most common aromatic hydrocarbons (benzene and toluene) and to quantify their concentrations. The analysis was carried out by the "purge and trap" technique combined with gas chromatography and with the use of the mass spectrometer as detector. The hydrocarbons themselves were used in a deuterated form as internal standards. The analysis of the data showed the presence of both hydrocarbons, even though their quantity was much lower than that detected in other foods.     

Characteristics of the PAH emissions from the incineration of livestock wastes with/without APCD

This study was conducted on two batch-type livestock waste incinerators, including the one with an air-pollution control device (APCD)-one wet scrubber (WSB) and the other without APCD for the disposal of livestock wastes. The concentration and composition of 21 individual polycyclic aromatic hydrocarbons (PAHs) in the stack flue gas (gas and particle phases), bottom ash, and effluent of WSB were determined. Stack flue gas samples were collected by a PAH stack-sampling system. Twenty-one individual PAHs were analyzed by a gas chromatography/mass spectrometer (GC/MS). Due to the low combustion temperature, a remarkable and significant increase in the total-PAH concentration of emission from the stack with APCD was observed when compared with the case without APCD. Measured total-PAH emission factors were 285 and 2.86 mg/kg waste for the incineration with and without APCD, respectively, while BaP (the most carcinogenic PAH) emission factors were 0.79 and 0.12 mg/kg waste for the incineration with and without APCD. The total-PAH output/input mass ratios averaged 0.011 and 0.004 with and without APCD, respectively. The result reveals that the PAH content in the auxiliary fuel during the incinerating process could affect the emission of PAH.     

Morphology,spatial distribution,and concentration of flame retardants in consumer products and environmental dusts using scanning electron microscopy and Raman micro-spectroscopy

We characterized flame retardant (FR) morphologies and spatial distributions in 7 consumer products and 7 environmental dusts to determine their implications for transfer mechanisms, human exposure, and the reproducibility of gas chromatography–mass spectrometry (GC–MS) dust measurements. We characterized individual particles using scanning electron microscopy/energy dispersive x-ray spectroscopy (SEM/EDS) and Raman micro-spectroscopy (RMS). Samples were screened for the presence of 3 FR constituents (bromine, phosphorous, non-salt chlorine) and 2 metal synergists (antimony and bismuth). Subsequent analyses of select samples by RMS enabled molecular identification of the FR compounds and matrix materials. The consumer products and dust samples possessed FR elemental weight percents of up to 36% and 31%, respectively. We identified 24 FR-containing particles in the dust samples and classified them into 9 types based on morphology and composition. We observed a broad range of morphologies for these FR-containing particles, suggesting FR transfer to dust via multiple mechanisms. We developed an equation to describe the heterogeneity of FR-containing particles in environmental dust samples. The number of individual FR-containing particles expected in a 1-mg dust sample with a FR concentration of 100 ppm ranged from < 1 to > 1000 particles. The presence of rare, high-concentration bromine particles was correlated with decabromodiphenyl ether concentrations obtained via GC–MS. When FRs are distributed heterogeneously in highly concentrated dust particles, human exposure to FRs may be characterized by high transient exposures interspersed by periods of low exposure, and GC–MS FR concentrations may exhibit large variability in replicate subsamples. Current limitations of this SEM/EDS technique include potential false negatives for volatile and chlorinated FRs and greater quantitation uncertainty for brominated FR in aluminum-rich matrices.     

Determination of potentially bioaccumulating complex mixtures of organochlorine compounds in wastewater: a review

Organic chlorine compounds can be persistent environmental contaminants and may be accumulated through the food chain to the aquatic organisms, to fish and humans, depending basically on their hydrophobic properties. Consequently, there is an interest to measure these organic compounds from both the scientific and regulatory communities. The analytical essays have been improved for measuring specific organic chlorine compounds that present the most toxicological potential (polychlorinated biphenyls [PCBs], certain pesticides and dioxins), although they are tedious and time-consuming procedures. The existing tests to measure adsorbable organic halogens (AOX) or extractable organic halogens (EOX) do not distinguish the more hydrophobic organic chlorine matter. The intention of this paper is to make a review of the existing methods to measure the potentially bioaccumulating organochlorine compounds (OCs) from wastewater and propose a methodology to a standardisation procedure for complex mixtures of OCs in wastewater, such as pulp mill effluents. A new method has been proposed for determining the most hydrophobic part of the extractable organic halogens (EOX(fob)), the lowest reported value is 0.6 microg/l, expressed as chloride, and the relative standard deviation at 20 microg/l is 7% on laboratory samples and 30% on real effluents. This new procedure could be a valuable tool to complement environmental risk assessment studies of wastewater discharges.     

High levels of dioxin-like PCBs found in organic-farmed eggs caused by coating materials of asbestos-cement fiber plates: A case study

During a regional monitoring project of organic-farmed, free-range and cage-free eggs, high levels of dioxin-like compounds were detected in organic-farmed eggs, using the dioxin responsive chemical-activated luciferase gene expression (DR-CALUX®) bioassay. Further evaluations performed with GC–HRMS (gas chromatography in combination with high resolution mass spectrometry) revealed elevated amounts of non-dioxin-like (non-dl) polychlorinated biphenyls (PCBs) dominated by most lipophilic congeners like PCB 138, 153 and 180 and of dioxin-like (dl) PCBs, with a congener pattern in the descending order of PCB 118, 156, 167, 105, 189, 157, 105, 126 and PCB 77. Contaminations with polychlorinated dibenzo-p-dioxins (PCDDs) appeared of minor priority, with only hepta- and octa-substituted dioxins above their limits of quantification (LOQs). The pattern of polychlorinated dibenzofurans (PCDFs) was dominated by low amounts of tetra- and penta-chlorinated congeners. To identify the source of contamination, several samples of organic-farmed eggs, soil, laying hens, feedstuff, corrugated asbestos-cement cover plates (ACPs), stable dust and debris collected in the gutter of the stable, were analyzed. Comparing PCB congener-pattern of individual samples, the source was traced back to the coating of ACPs, which covered roof and sidewalls of the stable. Because coating materials probably have been used for roofing and cladding in many countries worldwide, there is a high probability that the presented case report is not a local incident but rather describes a new source of PCB contamination, yet widely unknown or underestimated.     

Gas chromatographic/mass spectrometric analysis of partially dechlorinated 1,1-diphenyl ethane and ethylene

Gas chromatographic relative retention time data and 70 eV electron impact mass spectra of partially dechlorinated derivatives of 1,1-bis-p-chlorophenyl-2,2,2-trichloroethane (DDT), and the corresponding, 2,2-dichloroethylene (DDE) are presented.The mass spectra of all partially dechlorinated ethane intermediates are characterized by fragmentation across the aliphatic CC bond, whereas the mass spectra of the corresponding olefins are characterized principally by CCl bond rupture. The mass spectral data, coupled with the observed systematic decrease in relative retention time that is a function of aromatic chlorine substitution, provides an almost complete set of relative retention time data for the homologous series of compounds between both DDT and 1,1-diphenylethane and DDE and 1,1,-diphenylethylene.     

Basic characterization of Norwegian NOM samples — Similarities and differences

NOM (natural organic matter) samples, isolated by reverse osmosis (RO), and nine NOM samples, concentrated by low-pressure, low-temperature evaporation (EVA) from various origin in Norway, were characterized by different methods. The methods included elemental content of the freeze-dried samples (C, H, N, and O), elemental content of the redissolved samples (DOC, Na, Ca, Cu, Fe, and Mn), specific spectral absorbance at λ = 254 nm (A(254 nm)/DOC) and at λ = 436 nm (A(436 nm)/DOC), UV/Vis-spectra, specific fluorescence (excitation and emission spectra), proton capacity, Cu-complexation capacity, and content of hydrolysable amino acids and carbohydrates. In addition, chromatographic characterization by gel chromatography and reversed-phase chromatography was done. Studies on adsorption and flocculation abilities and the formation of trihalomethanes (THM) and organic halogens adsorbable on activated carbon (AOX) upon chlorination were also investigated. Comparison of the results showed that the samples were different according to the origin of the sample, isolation procedure, and time of sampling. The differences are not the same for all parameters used. Standardized procedures have to be applied to redissolve the organic material in water in order to compare data. For the samples investigated, it was shown that parameters like elemental analysis (H/C ratio), the specific spectral absorption in the UV range, proton capacity, complexation capacity and anionic particle charge, amount of hydrolysable amino acids and carbohydrates, adsorption behaviour on activated carbon, and the THM-FP are sensitive parameters to show differences concerning origin and isolation procedure.     

Analysis of phytoestrogens,progestogens and estrogens in environmental waters from Rio de Janeiro (Brazil)

The environment is currently exposed to a large variety of man-made chemicals (e.g. for industrial, medicinal use) which have potential adverse effects to its ecological status. In addition, the densely populated areas represent local high emissions of those chemicals leading to more aggravating consequences. Estrogenic compounds that end-up in environmental water directly affect living organisms by interfering with their endocrine metabolism. The assessment of their presence in the environment requires sensitive and selective analytical methods. Nineteen estrogenic compounds belonging to different classes (5 free estrogens, 6 conjugated estrogens, 3 progestogens and 5 phytoestrogens) have been studied. The analytical methodology developed is based on solid phase extraction followed by liquid chromatography tandem mass spectrometry and has been applied to study the occurrence of the above mentioned analytes in environmental waters from the state of Rio de Janeiro (Brazil). Due to insufficient infra-structure in this region, waste waters are released onto the environment without or with incomplete previous treatment. The results show that high levels of the phytoestrogens daidzein, coumestrol and genistein of up to 366 ng/L and progesterone of up to 47 ng/L could be found in river water. Estrogens and their conjugated derivatives were detected in the lower ng/L range up to 7 ng/L. The main estrogens estrone, estradiol and the synthetic ethinyl estradiol could not be detected. The developed method showed overall good performance with recoveries above 80% (with one exception), limits of detection ≤ 2 ng/L, good linearity and reproducibility.     

Distribution and temporal trends of butyltins monitored by molluscs along the Chinese Bohai coast from 2002 to 2005

Thirteen areas around the Chinese Bohai coast, individuals including ten kinds of bivalves and two kinds of snails were collected during the period of 2002-2005 for the investigation of spatial distribution and temporal variations of butyltin compounds (BTs). BTs including tributyltin (TBT) and its derivates, dibutyltin (DBT) and monobutyltin (MBT) were quantified by gas chromatography/flame photometric detection after extraction and Grignard derivatization. BTs compounds were widely existed in the samples and TBT was the dominant composition, indicating recent TBT input along Bohai coast. As a whole, BTs concentration remained high during the sampling years except a slightly decreased in samples from several sites in 2005. The contamination characteristics of BTs in different sampling sites were analyzed using principal component analysis (PCA) method, and the species specific bioaccumulation of BTs was also identified using cluster analysis.     

The use of extraction chromatography resins to concentrate actinides and strontium from soil for radiochromatographic analyses

An analytical technique utilizing selective extractant resins to concentrate strontium and actinides from soil followed by separation with radiochromatography was evaluated. The technique was tested using uncontaminated soil samples spiked with a radionuclide tracer solution that were either microwave-aided acid digested or leached with a strong acid. Extraction of the strontium and actinides from the acidified solution was accomplished using a serial arrangement of Sr-Resin and TRU-Resin columns. The combined eluate solutions from the extraction resins were treated with HNO(3) and H(2)O(2) to oxidize residual extractant and eluates prior to separation and analysis of the radionuclides by radiochromatography. Chromatograms obtained with larger soil mass loadings resulted in either incomplete peak resolution of the tracers or had highly variable peak elution times, indicative of an ionic interfering constituent(s). Better separations (e.g., chromatograms that resolved all radioactive constituents) were obtained when the sample mass loading was decreased, but with a concurrent decreased sensitivity for the radionuclides. Elemental analyses of the soil were conducted to provide data on the ionic constituents in unprocessed soil and post-processed soil samples. These results identified aluminum as an interfering contributor to the poor performance exhibited by the radiochromatographic separations.     

High concentrations of polybrominated diphenylethers (PBDEs) in breast adipose tissue of California women

We measured major PBDEs and PCBs in breast adipose tissues of California women participating in a breast cancer study in the late 1990s. Samples were analyzed using gas chromatography with electron impact ionization and tandem mass spectrometry detection. The congener profile observed was: BDE47>BDE99>BDE153>BDE100>BDE154 and PCB153>PCB180>PCB138>PCB118. Whereas high correlations were observed within each chemical class, very weak correlations appeared between classes, pointing to different exposure pathways. Weak negative associations were observed for PBDE congeners and age. Our PBDE data are among the highest reported, exceeding data from the National Health and Nutrition Examination Survey and consistent with the high use of PBDEs in California. These data may be helpful in establishing a baseline for PBDE body burdens to gauge changes over time as a result of restrictions in the use of PBDE formulations.