Quantification of indoor VOCs in twenty mechanically ventilated buildings in Hong Kong

Information of volatile organic compounds (VOCs) in buildings in Hong Kong is relatively scared compared to other countries. Information of how much VOC accumulation comes from occupants themselves, from building materials and other outdoor sources are scarce even on a global basis. This study aimed at collecting information of the levels of individual VOCs using US-EPA Method TO-14. Twenty building premises including offices and public places such as customer service centers, shopping centers, etc. were studied. Samples were taken during the time slots when the mechanical ventilation system was operating. The 43 VOCs were grouped into three categories, i.e. aromatic hydrocarbons, chlorinated hydrocarbons and organohalogen. The most dominant VOCs found in the indoor samples were benzene, toluene, ethylbenzene, xylenes (BETX), chloroform and trichloroethylene as 100% of the samples were found to contain these VOCs. Besides, more than 75% of the samples were found to contain 1,3,5-trimethylbenzene, methylchloride and dichloromethane. The wt% of chlorinated hydrocarbons (48%) and the wt% of aromatic hydrocarbons (38%) only differed by about 10% in the office sector. Organohalogen (14%) contributed to the smallest fraction of the total on all the premises in the office sector on weight basis. A completely different distribution pattern was found in the non-office sector. The most abundant class of VOCs in terms of weight was aromatic hydrocarbons (80%). The second abundant class of VOCs was chlorinated hydrocarbons (14%) and was much less than the level of aromatic hydrocarbons in terms of weight. Organohalogen (6%) contributed to the smallest fraction of the total on all the premises in the non-office sector on weight basis.     

Determination of Volatile Organic Compounds in the Atmosphere Using Two Complementary Analysis Techniques

ABSTRACT

During a preliminary field campaign of volatile organic compound (VOC) measurements carried out in an urban area, two complementary analysis techniques were applied to establish the technical and scientific bases for a strategy to monitor and control VOCs and photochemical oxidants in the Autonomous Community of the Basque Country. Integrated sampling was conducted using Tenax sorbent tubes and laboratory analysis by gas chromatography, and grab sampling and in situ analysis also were conducted using a portable gas chromatograph. With the first technique, monocyclic aromatic hydrocarbons appeared as the compounds with the higher mean concentrations. The second technique allowed the systematic analysis of eight chlorinated and aromatic hydrocarbons. Results of comparing both techniques, as well as the additional information obtained with the second technique, are included.     

Organic compounds and trace metals of anthropogenic origin in sediments from Montego Bay,Jamaica: assessment of sources and distribution pathways

Surface sediments throughout Montego Bay, Jamaica were collected in 1995 and analyzed for their trace metal and trace organic contaminant content. A variety of trace metals, petroleum hydrocarbons, polycyclic aromatic hydrocarbons, coprostanol as well as chlorinated hydrocarbons such as pesticides and polychlorinated biphenyls were detected and provide evidence for several anthropogenic inputs to the bay. Two main sources of these chemicals are the Montego River and the North Gully, the latter being more significant. Particle-associated pollutants were found to be distributed along the Montego River plume, as well as being transported by the prevailing water currents to the South-Western sections of the bay, probably through re-suspension of enriched fine sediments from the North Gully outfall area.     

Prediction of the adsorption capacity for volatile organic compounds onto activated carbons by the Dubinin-Radushkevich-Langmuir model

Prediction of the adsorption capacity for volatile organic compounds (VOCs) onto activated carbons is elucidated in this study. The Dubinin-Radushkevich (D-R) equation was first used to predict the adsorption capacity of nine aromatic and chlorinated VOCs onto two different activated carbons. The two key parameters of the D-R equation were estimated simply from the properties of the VOCs using quantitative structure-activity relationship and from the pore size distribution of the adsorbent. The approach based on the D-R equation predicted well the adsorption capacity at high relative pressures. However, at the relative pressures lower than -1.5 x 10(-3), the D-R approach may significantly overestimate adsorption capacity. To extrapolate the approach to lower relative pressures, the integration of the D-R equation and the Langmuir isotherm, called the D-R-L model, was proposed to predict adsorption capacity over a wide range of relative pressures of VOCs. In this model, the Langmuir isotherm parameters were extracted from the predicted D-R isotherm at high relative pressures. Therefore, no experimental effort was needed to obtain the parameters of the D-R-L model. The model successfully predicted the adsorption capacity of aromatic and chlorinated hydrocarbons tested onto BPL and Sorbonorit B carbons over relative pressures ranging from 7.4 x 10(-5) to 0.03, suggesting that the model is applicable at the low relative pressures of VOCs often observed in many environmental systems. In addition, the molecular size of organic compounds may be an important factor affecting the adsorption capacity of activated carbons. For BPL carbon, an ultramicroporous adsorbent, the limiting pore volume Wo of the D-R equation decreased when the kinetic diameter of the adsorbate was larger than 6 angstroms. However, for Sorbonorit B carbon, no reduction of Wo was found, suggesting that the Wo may be related to the pore size distribution of the adsorbents, as well as to their molecular size. This size exclusion effect may play an important role in predicting the adsorption capacity of VOCs onto microporous adsorbents in the D-R-L model and in the corresponding D-R equation.     

Organic Compounds in Cloud Water and their Deposition at a Remote Continental Site

Some organic compounds (alkylbenzene, chlorinated hydrocarbons and poiycyclic aromatic hydrocarbons) in clouds have been determined from samples collected above the canopy of a coniferous forest. The cloud samples were collected during 1987 and 1988 at Mt. Mitchell State Park, North Carolina, a remote high elevation (～2006 m MSL) continental site. Concentrations of the organic chemicals in clouds were in the range of 0.2 to ～200 ng mL^-1; and their estimated deposition rates via clouds were found to range from 1.58 * 10⁴ to 4.67 * 10⁶ ng m^-2 yr^-1. Great variations in concentrations were found which can best be explained, based on 72 hour back trajectory analysis, by different source locales and moving air masses. The concentration of these chemicals exceeded their water solubility as predicted by Henry's Law, suggesting that clouds are an excellent scavenger of organic chemicals in the ambient environment.     

Personal exposure of graduate students attending the college of natural sciences or social sciences to volatile organic compounds on campus

The present study measured the levels of 24 selected volatile organic compounds (VOCs) in the personal air samples obtained from graduate students attending the college of natural sciences (GSNSs) or social science (GSSSs) during their daily activities on campus along with associated indoor and outdoor air samples. In addition, the sources of their personal exposure were characterized using multivariate statistical models. In the personal samples of GSNSs and GSSSs, 16 and 15 different VOCs were always detected, respectively. The personal exposure of five chlorinated hydrocarbons and six aromatics was significantly higher for GSNSs than for GSSSs. Consistently, the indoor levels of these compounds were higher for GSNSs (in research and laboratory rooms) than for GSSSs (in research rooms). However, the personal exposure of two aromatic VOCs (1,2,4- and 1,3,5-trimethylbenzene) was higher for GSSSs. Moreover, the personal exposure of the five chlorinated and six aromatic compounds was significantly correlated with VOC concentrations both in the research and laboratory rooms of GSNSs and with those in the research rooms of GSSSs. For certain VOCs, outdoor sources were also a major contributor to the personal exposure of both GSNSs and GSSSs. The multivariate models identified five factors that accounted for 81% of the total variance and four factors that explained 76% of the total variance. It was further suggested that multiple indoor sources in research rooms such as office equipment, building finishing materials, and air fresheners were the main source for the personal exposure to VOCs for GSNSs, whereas building finishing materials were the main source for GSSSs.     

Biodegradation of trace gases in simulated landfill soil cover systems

The attenuation of methane and seven volatile organic compounds (VOCs) was investigated in a dynamic methane and oxygen counter gradient system simulating a landfill soil cover. The VOCs investigated were: Tetrachloromethane (TeCM), trichloromethane (TCM), dichloromethane (DCM), trichloroethylene (TCE), vinyl chloride (VC), benzene, and toluene. Soil was sampled at Skellingsted landfill, Denmark. The soil columns showed a high capacity for methane oxidation, with oxidation rates up to 184 g/m2/d corresponding to a 77% reduction of inlet methane. Maximal methane oxidation occurred at 15-20 cm depth, in the upper part of the column where there were overlapping gradients of methane and oxygen. All the chlorinated hydrocarbons were degraded in the active soil columns with removal efficiencies higher than 57%. Soil gas concentration profiles indicated that the removal of the fully chlorinated compound TeCM was because of anaerobic degradation, whereas the degradation of lower chlorinated compounds like VC and DCM was located in the upper oxic part of the column. Benzene and toluene were also removed in the active column. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play an important role in reducing the emission of trace components into the atmosphere.     

Nonylphenols, nonylphenol-ethoxylates, linear alkylbenzenesulfonates (LAS) and bis (4-chlorophenyl)-sulfone in the German Bight of the North Sea.

Nonylphenols and nonylphenol-ethoxylates were detected in the water and sediment samples from the German Bight of the North Sea. Additionally bis (4-chlorophenyl)-sulfone and linear alkylbenzenesulfonates (LAS) were detected in marine waters. Proof of identification is given by comparison of spectral and chromatographic data from the compounds in sample extracts to those obtained from pure standards. In extracts obtained from water samples taken in 1990 and 1995 the concentrations of nonylphenols and bis-(4-chlorophenyl)-sulfone were compared for each year. The concentrations of nonylphenols in seawater varied from 0.7 to 4.4 ng/l while in the Elbe estuary about 33 ng/l were found. In water samples taken in 1998 nonylphenol-polyethoxylates could not be determined, whereas LAS concentrations of 30 ng/l were confirmed by HPLC-MS/MS. The concentrations of bis (4-chlorophenyl)-sulfone ranged from 0.18 to 2.2 ng/l. In sediment samples LAS concentrations of 39-109 ng/g dry weight were determined.     

First study of congener group patterns and concentrations of short- and medium-chain chlorinated paraffins in fish from the North and Baltic Sea

This study presents the first investigation of concentrations and congener group patterns of short- (SCCPs) and medium-chain chlorinated paraffins (MCCPs) in fish from the North and Baltic Sea. North Sea dab, cod and flounder were studied. High resolution gas chromatography (HRGC) coupled to low resolution mass spectrometry (LRMS) in the electron capture negative ionization mode (ECNI) was employed. Good linearity (R2>0.993, 7 measuring points) was achieved between 1 and 100 ng/g of CP mixtures for SCCPs and MCCPs. The limits of detection were 0.5-1 ng/microl of CP mixture for the major congener groups of SCCPs and MCCPs. A clean-up comprising fat extraction, adsorption chromatography on silicagel impregnated with concentrated sulphuric acid and adsorption chromatography on Florisil was employed to avoid interferences from other polychlorinated compounds. Recoveries of CPs in spiked samples ranged between 80% and 100%. Accuracy was controlled with spiked samples and deviated not more than 10% from the expected values. Quantification was performed with standards of an average chlorine content as close as possible to that of the samples (SCCPs: 59-62%, MCCPs: 53-58%). SCCP concentrations ranged between 19 and 286 ng/g liver wet weight (ww), MCCP concentrations were comparable with a range of 25-260 ng/gww. Congener group patterns were also determined and discussed. In samples from the Baltic Sea the SCCP congener pattern was similar to that of commercial SCCP mixtures or C13 congeners were most abundant. In samples from the North Sea a higher relative abundance of C10 congeners was observed.     

Degradation of volatile organic compounds with thermally activated persulfate oxidation

This study investigated the extent and treatability of the degradation of 59 volatile organic compounds (VOCs) listed in the EPA SW-846 Method 8260B with thermally activated persulfate oxidation. Data on the degradation of the 59 VOCs (in mixture) reacted with sodium persulfate in concentrations of 1 g l(-1) and 5 g l(-1) and at temperatures of 20 degrees C, 30 degrees C, and 40 degrees C were obtained. The results indicate that persulfate oxidation mechanisms are effective in degrading many VOCs including chlorinated ethenes (CEs), BTEXs and trichloroethanes that are frequently detected in the subsurface at contaminated sites. Most of the targeted VOCs were rapidly degraded under the experimental conditions while some showed persistence to the persulfate oxidation. Compounds with "CC" bonds or with benzene rings bonded to reactive functional groups were readily degraded. Saturated hydrocarbons and halogenated alkanes were much more stable and difficult to degrade. For those highly persulfate-degradable VOCs, degradation was well fitted with a pseudo first-order decay model. Activation energies of reactions of CEs and BTEXs with persulfate were determined. The degradation rates increased with increasing reaction temperature and oxidant concentration. Nevertheless, to achieve complete degradation of persulfate-degradable compounds, the systems required sufficient amounts of persulfate to sustain the degradation reaction.     

Levels and patterns of persistent organochlorines in minke whale (Balaenoptera acutorostrata) stocks from the North Atlantic and European Arctic

Regional variation in PCBs and organochlorine (OC) pesticide concentrations was examined using the blubber of 155 minke whales (Balaenoptera acutorostrata) sampled in seven regions in the North Atlantic and European Arctic, including western and southeastern Greenland, the Norwegian Sea, the North Sea and the Barents Sea. The levels and relative proportions of OCs were also used to examine the boundaries for North Atlantic minke whale stocks previously defined by the International Whaling Commission (IWC). Concentrations of major OC groups (sigmaPCB, 89.1-22 800 ng/g lipid; sigmaDDT, 65.3-6280 ng/g lipid; sigmaCHL, 33.3-2110 ng/g lipid) generally increased from west to east, while HCH concentrations (sigmaHCH, < 1-497 ng/g lipid) showed the opposite trend. Statistical comparison between six regions using sex-adjusted least squared mean concentrations showed that minke whales from the Barents Sea had significantly higher concentrations of EPCBs than those from the Vestfjorden/Lofoten, the North Sea, and west Svalbard, as well as significantly higher sigmaDDT concentrations compared to west Greenland animals. The differences in concentrations suggest that west and southeast Greenland minkes may represent one group of whales, which are distinct from both the Jan Mayen minkes and those from other IWC defined stocks in northern European waters. Principal components analysis using proportions of 71 PCB congeners and 20 OC pesticides (of total OCs) did not reveal any major differences among groups although minkes from the North Sea were distinguished from those from Greenland waters by higher loadings of more highly chlorinated PCBs and recalcitrant OC pesticides. The general similarity in mean levels of sigmaPCBs, sigmaDDT and sigmaCHL, as well as mean principal components analysis scores, among minkes sampled at Jan Mayen, Svalbard, Vestfjorden/Lofoten, the North Sea and the Barents Sea suggests that the whales are quite mobile and may feed in multiple areas within the northeastern Atlantic.     

An attempt to measure the flow of chlorinated hydrocarbons, such as PCBs, from water to air in the field

A field sampling device to study the transport of aromatic, persistent chlorinated hydrocarbons from water to air was constructed. It was tested in large, outdoor artificial ponds contaminated with polychlorinated biphenyls (PCBs). The PCB compounds volatilised to air at a rate of 0.9 to 9.6 ng m(-2) h(-1) depending on levels of PCBs in the water and water temperature.     

Chlorinated and polycyclic aromatic hydrocarbons in riverine and estuarine sediments from Pearl River Delta, China

Spatial distribution of chlorinated hydrocarbons [chlorinated pesticides (CPs) and polychlorinated biphenyls (PCBs)] and polycyclic aromatic hydrocarbons (PAHs) was measured in riverine and estuarine sediment samples from Pearl River Delta, China, collected in 1997. Concentrations of CPs of the riverine sediment samples range from 12 to 158 ng/g, dry weight, while those of PCBs range from 11 to 486 ng/g. The CPs concentrations of the estuarine sediment samples are in the range 6-1658 ng/g, while concentrations of PCBs are in the range 10-339 ng/g. Total PAH concentration ranges from 1168 to 21,329 ng/g in the riverine sediment samples, whereas the PAH concentration ranges from 323 to 14,812 ng/g in the sediment samples of the Estuary. Sediment samples of the Zhujiang River and Macao harbor around the Estuary show the highest concentrations of CPs, PCBs, and PAHs. Possible factors affecting the distribution patterns are also discussed based on the usage history of the chemicals, hydrologic condition, and land erosion due to urbanization processes. The composition of PAHs is investigated and used to assess petrogenic, combustion and naturally derived PAHs of the sediment samples of the Pearl River Delta. In addition, the concentrations of a number of organic compounds of the Pearl River Delta samples indicate that sediments of the Zhujiang river and Macao harbor are most likely to pose biological impairment.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay

In 1999, the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), the total PAH and polychlorinated biphenyls (PCBs) were measured in sea water, sediment and mussels collected along the coast of Izmit Bay, the most important bay of the Marmara Sea. The total-PAH concentrations, measured by Spectrofluorometry were in the range of 1.16-13.68 microg/l in sea water, in the range of 30.0 1670.0 microg/g dry weight in sediments and in the range from 5.67 to 14.81 microg/g wet weight in edible part of mussel. HPLC revealed Phenanthrene (three rings), chrysene (four rings) and benz[a]antracene (five rings) to be the dominant PAHs in sea water, while 16 different PAHs compounds were observed and measured in mussel samples. The most pollution occured at Dogu Kanali and Dil Deresi where were the main rivers containing wastes fall into the the Izmit Bay. Although the maximum mono-ortho PCB concentrations in sea water were measured in the Dil Deresi River (26.33 ng/l) and the Solventa? (22.19 ng/l) stations, maximum PCB concentrations in mussels were measured in the SEKA (28.11 microg/kg) and the Dil Deresi River (25.68 microg/kg). The dominant congeners of PCBs were from tetra to hexachlorobiphenyls. The toxicity equivalent values were very low in sea water and mussels.     

Chlorinated hydrocarbons in coastal bottom sediments of the Japan Sea

Data on distribution of chlorinated hydrocarbons in coastal bottom sediments of different areas of the Japan Sea are presented. Results obtained during the autumn 1994 expedition in Peter-the-Great Bay were compared with the data of previous surveys in the D.P.R. Korea coastal zone and Tatarsky Strait (Sakhalin Island). Concentrations of DDT metabolites and HCH isomers appear to be related mainly to pesticide usage in agriculture. Mean concentrations of total DDTs decreased from 12.5 ng g(-1) in the D.P.R.K. coastal zone to 2.2 ng g(-1) at Sakhalin Island shelf, whereas total HCH concentrations decreased from 3.4 to 0.4 ng g(-1). Differences in chemical composition of pesticides used in the D.P.R.K. and Russia were evident. The importance of further monitoring of persistent organochlorines in bottom sediments and the need for regulation of wastewater discharges is stressed.     

Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers

The assessment of biodegradation in contaminated aquifers has become an issue of increasing importance in the recent years. To some extent, this can be related to the acceptance of intrinsic bioremediation or monitored natural attenuation as a means to manage contaminated sites. Among the few existing methods to detect biodegradation in the subsurface, stable isotope fractionation analysis (SIFA) is one of the most promising approaches which is pronounced by the drastically increasing number of applications. This review covers the recent laboratory and field studies assessing biodegradation of contaminants via stable isotope analysis. Stable isotope enrichment factors have been found that vary from no fractionation for dioxygenase reactions converting aromatic hydrocarbons over moderate fractionation by monooxygenase reactions (epsilon=-3 per thousand) and some anaerobic studies on microbial degradation of aromatic hydrocarbons (epsilon=-1.7 per thousand) to larger fractionations by anaerobic dehalogenation reactions of chlorinated solvents (epsilon=between -5 per thousand and -30 per thousand). The different isotope enrichment factors can be related to the respective biochemical reactions. Based on that knowledge, we discuss under what circumstances SIFA can be used for a qualitative or even a quantitative assessment of biodegradation in the environment. In a steadily increasing number of cases, it was possible to explain biodegradation processes in the field based on isotope enrichment factors obtained from laboratory experiments with pure cultures and measured isotope values from the field. The review will focus on the aerobic and anaerobic degradation of aromatic hydrocarbons and chlorinated solvents as the major contaminants of groundwater. Advances in the instrumental development for stable isotope analysis are only mentioned if it is important for the understanding of the application.     

Soot sorption of non-ortho and ortho substituted PCBs

Field-observations of distribution coefficients well above expectations from bulk organic-matter partitioning for several chlorinated aromatic compound classes have lead to the hypothesis that enhanced affinity to soot may not be limited to polycyclic aromatic hydrocarbons but may extend as a significant process for a wider range of hydrophobic organic compounds. This suggestion was here tested in soot-column sorption experiments with a series of ortho- and non-ortho substituted polychlorinated biphenyls (PCBs), using diesel particulate matter (NIST standard reference material SRM-1650) as model soot sorbent. For congeners of similar hydrophobicity, considerably higher affinities toward the soot sorbent were observed for the non-ortho substituted PCBs. Mono- to tetra-ortho substituted PCBs exhibited log-based soot-water distribution coefficients (K(sc)) from 5.25 to 5.51 l/kg(sc) at solute concentrations corresponding to 1-13 microg/l. In contrast, biphenyl, mono- and dichloro- non-ortho substituted PCBs yielded logK(sc) values between 5.09 and 6.35 l/kg(sc). These results are 20-50, and 75-110 times higher, respectively, than the corresponding K(ow)-predicted K(oc) numbers. This strong interaction with soot, particularly of non-ortho substituted PCBs, may fundamentally affect their environmental distribution and bioavailable exposure.     

Toxaphene in minke whales (Balaenoptera acutorostrata) from the North Atlantic

Toxaphene contamination of minke whales (Balaenoptera acutorostrata) from North Atlantic waters was examined for the first time. Total toxaphene and SigmaCHB (sum of 11 chlorobornanes) concentrations in blubber samples ranged from 170+/-110 and 41+/-39 ng/g lipid weight (l.w.) for female minke whales from southeastern Greenland to 5800+/-4100 and 1100+/-780 ng/g l.w. for males from the North Sea, respectively. Very large variations in toxaphene concentrations among sampling areas were observed suggesting a spatial segregation of minke whales. However, much of the apparent geographical discrimination was explained by the seasonal fluctuation of animal fat mass. Patterns of CHBs in males revealed that recalcitrant CHBs were in higher proportions in animals from the more easterly areas than in animals from the more westerly areas. This trend may be influenced by the predominance of the US, over the European, input of toxaphene to North Atlantic waters.     

Atmospheric concentrations and air-sea exchanges of nonylphenol, tertiary octylphenol and nonylphenol monoethoxylate in the North Sea

Concentrations of nonylphenol isomers (NP), tertiary octylphenol (t-OP) and nonylphenol monoethoxylate isomers (NP1EO) have been simultaneously determined in the sea water and atmosphere of the North Sea. A decreasing concentration profile appeared following the distance increasing from the coast to the central part of the North Sea. Air-sea exchanges of t-OP and NP were estimated using the two-film resistance model based upon relative air-water concentrations and experimentally derived Henry's law constant. The average of air-sea exchange fluxes was -12+/-6 ng m(-2)day(-1) for t-OP and -39+/-19 ng m(-2)day(-1) for NP, which indicates a net deposition is occurring. These results suggest that the air-sea vapour exchange is an important process that intervenes in the mass balance of alkylphenols in the North Sea.     

Polycyclic aromatic hydrocarbons in rainwater and surface waters of Lake Maggiore, a subalpine lake in Northern Italy

Fourteen polycyclic aromatic hydrocarbons (PAHs) were measured in surface waters and precipitation inputs to Lake Maggiore, a subalpine lake in Northern Italy, from July 2003 to January 2004. Particulate and dissolved phases in surface water and rain samples were determined. Analyses of PAHs were performed using XAD-2 resin to isolate the dissolved PAHs and subsequent extraction by accelerated solvent extraction (ASE). Both the dissolved and particulate phase PAH patterns in surface water and rainwater samples were dominated by the low molecular weight compounds (e.g., phenanthrene, fluoranthene and pyrene). More than 85% of PAHs in surface waters and 72% of PAHs in rainwater were associated to the dissolved phase. The SigmaPAH concentrations in surface waters (particulate and dissolved phases) were 0.584 +/- 0.033 ng l(-1), 2.9 +/- 0.312 ng l(-1) and in rainwater (particulate and dissolved phases) 27.5 +/- 2 ng l(-1), 75.4 +/- 9 ng l(-1), respectively. Temporal variability of PAH concentrations in rain and surface water samples were observed, with higher concentrations in November and December, coinciding with the largest precipitation amounts. The comparison of PAH signatures in rainwater and surface waters seems to indicate that wet deposition (2.5-41 microg m(-2) month(-1)) is the main source of PAH contamination into surface waters of Lake Maggiore.