Polycyclic aromatic hydrocarbons in storm runoff from urban and coastal South Carolina

Stormwater runoff was collected in urbanized areas of South Carolina to investigate the levels and sources of polycyclic aromatic hydrocarbons (PAHs). Mean concentrations of total PAHs in runoff (sum(PAHs), 14 compounds), determined by gas chromatography-mass spectrometry, were 5590 ng/l in the city of Columbia and 282 ng/l in the coastal community of Murrells Inlet. Lower concentrations were found in estuarine water at Murrells Inlet (mean = 35 ng/l) and at undeveloped North Inlet estuary (13 ng/l). The PAH profiles in Columbia and Murrells Inlet runoff were similar to those of atmospheric particulate matter and unlike those in used crankcase oil. Examination of the aliphatic fraction of Columbia runoff samples by gas chromatography with flame ionization detection showed patterns that were more similar to used crankcase oil than to urban aerosols.     

Volatile organic compounds, polycyclic aromatic hydrocarbons and elements in the air of ten urban homes

Ten homes were monitored at regular intervals from June 1994 through April 1995 as part of a Public Health Assessment in Southeast Chicago for exposure to volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and elements. Simultaneous 24-h indoor and outdoor samples were collected. VOCs were and analyzed using USEPA Method TO-14 with Selected Ion Monitoring Mass Spectrometry (GC/MS). PAHs were analyzed using USEPA Method TO-13 with GC/MS. Elements were collected on quartz fiber filters and analyzed by Inductively Coupled Argon Plasma (ICP) spectroscopy or Graphite Furnace Atomic Absorption (GFAA). Continuous measurements of CO2 and temperature were recorded for each indoor sample. Twenty-four h total CO2 emissions were determined from occupancy and estimated gas stove usage and were moderately correlated (R2 = 0.19) with 24 h average indoor CO2 concentrations. Modeled 24-h air exchange rates ranged from 0.04 to 3.76 air changes h-1 (ACH), with mean of 0.52 ACH. Median particle penetration was 0.89. Emission rates were calculated for each pollutant sampled. Using a detailed housing survey and field sampling questionnaires, it was possible to evaluate associations between housing characteristics and source activities, and pollutant source rates. The data indicate that several predictor variables, including mothball storage, air freshner use, and cooking activities, are reasonable predictors for emission rates for specific pollutants in the homes studied.     

Volatile halogenated hydrocarbons in Belgian drinking waters

A comparative study was carried out to determine levels of volatile halogenated hydrocarbons, especially trihalomethanes (THM) in different Belgian drinking waters, prepared from both ground and surface waters. In addition to examining raw and treated water leaving the production plants, changes in haloform concentration during transport in the distribution system were also studied. Only a slight decrease of haloform concentration after decompression in water towers and reservoirs occurred and was rapidly compensated by on going chlorination by residual free chlorine.Despite of the very different conditions used for chlorination in the plants studied, a fairly clear relation was found between total THM content in the finished waters and TOC-values of the raw waters, indicating that the primary organic load was the determining factor for haloform formation.     

Levels of chlorinated hydrocarbons in sediments from the central mediterranean

Levels of PCBs, DDTs and BHCs were measured in sediments taken from the central Mediterranean. BHC was usually < 1 ng g^?1; ΣDDT (sum of DDT, DDE and DDD) ranged from < 1 ng g^?1 to 27.5 ng g^?1; ΣPCBs generally ranged from ca. 1 ng g^?1 to > 80 ng g^?1, but exceptionally high values (130–457 ng g^?1) were observed from stations within Augusta Harbor.     

Volatile disinfection by-product analysis from chlorinated indoor swimming pools

Chlorination of indoor swimming pools is practiced for disinfection and oxidation of reduced compounds that are introduced to water by swimmers. However, there is growing concern associated with formation for chlorinated disinfection by-products (DBPs) in these settings. Volatile DBPs are of particular concern because they may promote respiratory ailments and other adverse health effects among swimmers and patrons of indoor pool facilities. To examine the scope of this issue, water samples were collected from 11 pools over a 6 month period and analyzed for free chlorine and their volatile DBP content. Eleven volatile DBPs were identified: monochloramine (NH₂Cl), dichloramine (NHCl₂), trichloramine (NCl₃), chloroform (CHCl₃), bromoform (CHBr₃), dichlorobromomethane (CHBrCl₂), dibromochloromethane (CHBr₂Cl), cyanogen chloride (CNCl), cyanogen bromide (CNBr), dichloroacetonitrile (CNCHCl₂), and dichloromethylamine (CH₃NCl₂). Of these 11 DBPs, 10 were identified as regularly occurring, with CHBrCl₂ only appearing sporadically. Pool water samples were analyzed for residual chlorine compounds using the DPD colorimetric method and by membrane introduction mass spectrometry (MIMS). These two methods were chosen as complementary measures of residual chlorine, and to allow for comparisons between the methods. The DPD method was demonstrated to consistently overestimate inorganic chloramine content in swimming pools. Pairwise correlations among the measured volatile DBPs allowed identification of dichloromethylamine and dichloroacetonitrile as potential swimming pool water quality indicator compounds.     

Behaviour of self-cleaning glass in urban atmosphere

In order to analyse the self-cleaning mechanism of TiO₂-coated window float glass, a field experiment was conducted in Paris, at a site representative of background urban pollution. Two hydrophilic photocatalytic TiO₂-coated industrial glasses and a traditional float glass (reference) were exposed in unsheltered and sheltered condition for various time duration. The sheltered exposure allowed to study the soiling and self-cleaning mechanism without the disturbing effect of rain washing. In parallel, air filtrations were carried out in order to assess the chemical composition of airborne particulate.     

Degradability of some chlorinated aliphatic hydrocarbons in sea water and sterilized water

The degradability of the substances chloroform, 1.1.2-trichloroethane, 1.1.2-trichloroethene and 1.1.2.2-tetrachloroethene was investigated in sea water and sterilized fresh water. Four different systems were used: (1) daylight, open system; (2) daylight, closed system; (3) darkness, closed system; (4) darkness, 2 atm closed system. The analytical procedure is described The disappearance of the substances was greatest in the aquaria indicating that the substances can escape because of their vapour pressure. In the other systems the decrease within eight days was less than 40%. It is suggested that the closed flask system is to be preferred to other systems.     

Survey of the contamination of Dutch coastal waters by chlorinated hydrocarbons,including the occurrence of methylthio-pentachlorobenzene and di-(methylthio)tetrachlorobenzene

In 1976 contamination of Dutch coastal waters by organochlorine compounds was assessed by analysing mussels, Mytilus edulis, as an indicator-organism. HCB, dieldrin, endrin, p,p′-DDT, p,p′-TDE and PCB's were detected, and also two new compounds previously unknown in the aquatic fauna.Using gas-liquid chromatography, mass spectrometry and ¹³C nuclear magnetic resonance spectrometry these could be identified as methylthiopentachlorobenzene and 1,4-di(methylthio)-2,3,5,6-tetrachlorobenzene. Their concentrations in the mussels ranged from 0.005 to 0.40 mg/kg on a fresh weight basis, depending on sampling site. Their presence is associated with the exposure of mussels to water from the river Rhine. Further work is required to establish the origin of these compounds and their possible precursors.     

Infrared detection of chlorinated hydrocarbons in water at ppb levels of concentrations

Infrared sensor, based on attenuated total reflection phenomenon, for the detection of chlorinated hydrocarbons (CHCs) represents a big advantage compared to chromatographic and mass spectroscopic techniques since it is a one step detector. Pre-concentration and separation take place in the polymer film with simultaneous identification of pollutants by the infrared beam. The analysis is rapid, sample does not require any initial preparation, and can be easily performed in the field. The main default of the latest version of the sensor was a low sensibility (above 1 ppm) compared to the threshold levels of the contaminants. In the present work, it is documented that the response dynamics of the optical sensor and its sensitivity depend strongly on the diffusion of pollutants through a boundary layer formed between polymer film and the monitored solution and in the polymer film. The reduction of thickness of the boundary layer through a controlled high flow rate, and the optimization of thickness (volume) of polymer films result in a tremendous improvement of the response dynamics. It is demonstrated that the sensor can detect simultaneously six CHCs: monochlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chloroform, trichloroethylene, and perchloroethylene in their mixture with a sensitivity as low as a few ppb. This level of detection opens up numerous applications for the optical sensor.     

Chemical and photochemical degradation of polycyclic aromatic hydrocarbons in the atmosphere

Results of studies on chemical and photochemical transformations of polycyclic aromatic hydrocarbons (PAH) are reviewed. Various parameters may modify the kinetics of these reactions, such as light intensity, concentration of gaseous pollutants (NO_x, SO_x, O₃), chemico-physical characteristics of particulates or substrates into which the PAH are adsorbed. Depending on these variables, the half-life of BaP varies from 10 to 104 300 min. The possibility of artefact formation during sampling is discussed. The necessity of clarifying mechanisms for these phenomena, in order to correctly evaluate the risks for exposed populations, is emphasized.     

Photodegradation of chlorinated hydrocarbons in the presence and absence of dissolved oxygen in water

The photodegradation rates of seven chlorinated hydrocarbons; C2Cl4, C2HCl3, C2H4Cl2, 1,1,1-C2H3Cl3, 1,1,2-C2H3Cl3, CHCl3, CCl4 were investigated under the UV bandwidths of 185 and 254 nm in the presence and absence of dissolved oxygen (DO) in water. These hydrocarbons are possible contaminants of groundwater. This study confirms that the degradation rates of all chlorinated hydrocarbons are elevated in the absence of DO. This was especially apparent for chlorinated methane and ethane. Tetrachloroethylene's rate was the highest among the seven hydrocarbons regardless of the DO levels. It was clear that the concentration of intermediate trichloroethylene produced by photodegradation of tetrachloroethylene in the absence of DO was 1/50th of that in the presence of DO. Photodegradation in the presence of DO resulted in the formation of O3 and hydroxyl radicals. Alternatively, the photodegradation in the absence of DO resulted in the formation of organic radicals and a dissociation of the bond. It is discussed that DO acts as an "inner filter" or "scavenger" that reduces the UV light intensity in the photoreactor. Molecular O2 has absorption bands at 185 and 254 nm, the former being stronger. The processes of degradation depend on the degradation rate relative to the presence and absence of DO.     

Distribution and sources of polycyclic aromatic hydrocarbons in the sediment of a sub-tropical coastal wetland

Sediment cores (0-35cm below surface) from twelve sampling stations in the Mai Po and Inner Deep Bay Ramsar Site of Hong Kong were retrieved in the period March-December 1999. Vertical profiles of 15 priority polycyclic aromatic hydrocarbons (PAHs) in each sediment core were determined. Ranges of total PAH concentration, [sigmaPAH], in the wetland sediment were 0.18-0.83 (N = 0.36) microg/g dried sediment (mudflats) and 0.63-0.96 (x = 0.77) microg/g dried sediment (mangroves). A decreasing trend in depth averaged [sigmaPAH] was observed from the landward end towards the seaward end of the Marshes. On the mudflats, vertical profiles of the PAHs were quite uniform. At the fringe of the Mai Po mangroves, significantly higher concentration of all PAHs was observed at the upper 0 to -8 cm layer. No significant difference in the distribution patterns of the 15 priority PAHs in summer and winter was observed. This indicates that distribution of PAHs in the sediment of the Mai Po Marshes is not very sensitive to sub-tropical climatic changes of the region. Two PAH isomer ratios, [Phen]/([Phen] + [Anthra]) and [Pyrene]/([Pyrene] + [Fluoran]), were used to identify potential sources of PAH contamination in the wetland. Results revealed that local deposition is a more important source than long-range atmospheric transportation.     

Human blood samples as indicators of occupational exposure to persistent chlorinated hydrocarbons

The value of using human blood as an indicator of occupational exposure to persistent organochlorine compounds is demonstrated. Blood samples from a total of 35 persons divided into three different groups, with and without exposure to chlorinated hydrocarbons in the work atmosphere, have been investigated by gas chromatography using electron capture detection. It is shown that the group of workers with an occupational exposure to pentachlorobenzene, hexachlorobenzene, heptachlorostyrene and octachlorostyrene had a higher level of these chlorinated hydrocarbons in their blood samples than did the other groups. On the average, the concentration of hexachlorobenzene is about 20 times higher in blood samples from the occupationally exposed workers than from the control group.The level of hexachlorobenzene in blood samples of the control groups is low compared to recent studies of blood samples from the general population in other industrialized countries. Furthermore, the average value obtained for the exposed workers is of the same magnitude as the general population in these industrialized countries.     

The urban coastal zone of Southern California

Every parkland provides habitats for wildlife. Wildlife is frequently recognised as a recreational asset. A few ancient parks are of outstanding national or regional importance for the conservation of invertebrates and epiphytic lichens associated with old trees and dead wood. The perpetuation of suitable habitat is essential if this conservation interest is to be maintained.     

Temporal variations in natural attenuation of chlorinated aliphatic hydrocarbons in eutrophic river sediments impacted by a contaminated groundwater plume

Chlorinated aliphatic hydrocarbons (CAHs) often discharge into rivers as contaminated groundwater baseflow. Biotransformation, sorption and dilution of CAHs in the impacted river sediments have been reported to reduce discharge, but the effect of temporal variations in environmental conditions on the occurrence and extent of those processes in river sediments is largely unknown. We monitored the reduction of CAH discharge into the Zenne River during a 21-month period. Despite a relatively stable influx of CAHs from the groundwater, the total reduction in CAH discharge from 120 to 20 cm depth in the river sediments, on average 74 ± 21%, showed moderate to large temporal variations, depending on the riverbed location. High organic carbon and anaerobic conditions in the river sediments allowed microbial reductive dechlorination of both chlorinated ethenes and chlorinated ethanes. δ¹³C values of the CAHs showed that this biotransformation was remarkably stable over time, despite fluctuating pore water temperatures. Daughter products of the CAHs, however, were not detected in stoichiometric amounts and suggested the co-occurrence of a physical process reducing the concentrations of CAHs in the riverbed. This process was the main process causing temporal variations in natural attenuation of the CAHs and was most likely dilution by surface water-mixing. However, higher spatial resolution monitoring of flow transients in the riverbed is required to prove dilution contributions due to dynamic surface water-groundwater flow exchanges. δ¹³C values and a site-specific isotope enrichment factor for reductive dechlorination of the main groundwater pollutant vinyl chloride (VC) allowed assessment of changes over time in the extent of both biotransformation and dilution of VC for different scenarios in which those processes either occurred consecutively or simultaneously between 120 and 20 cm depth in the riverbed. The extent of reductive dechlorination of VC ranged from 27 to 89% and differed spatially but was remarkably stable over time, whereas the extent of VC reduction by dilution ranged from 6 to 94%, showed large temporal variations, and was often the main process contributing to the reduction of VC discharge into the river.     

The contribution of mercury and chlorinated organics from urban runoff

The concentration of mercury and chlorinated organics in the combined sewer overflows of Rochester, New York (U.S.A.) have been measured. The resulting annual loadings of 0.034 kg ha⁻¹ (0.034 pounds acre⁻¹) and 0.011 kg ha⁻¹ (0.01 pounds acre⁻¹) of mercury and chlorinated organics measured in urban runoff are significant. A high degree of correlation exists between the measured concentration of the toxicants when compared with rainfall intensity, rainfall duration, antecedent number of dry days and the total suspended solids concentration characteristic of the combined wastwater.     

Characterisation of NMHCs in a French urban atmosphere: overview of the main sources

Continuous hourly air quality data involving 37 C2-C9 non-methane hydrocarbons (NMHC) over 4 years are reported for the first time in Lille metropol, northern France, at two urban roadside and background sites. The data have been analysed in two complementary steps: univariate statistics which define the spatial and temporal characteristics of NMHC by constructing the seasonal and daily concentration profiles, and multivariate statistics based on principal component analysis (PCA). A number of important sources have been clearly identified depending on the season: (1) motor vehicle exhaust, which dominates the NMHC distribution and particularly in winter, even for isoprene; (2) wintertime stationary combustion and activities related to fossil fuel consumption in general, such as natural gas leakage of ethane and propane; (3) summertime evaporative emissions from fuel and solvent; and (4) summertime biogenic emissions through isoprene behaviour and their dependence on temperature.     

Modification of soot by volatile species in an urban atmosphere

Aerosol samples in the urban atmosphere of Kumamoto (32 degrees 48'N, 134 degrees 45'E) in southwestern Japan were collected onto aluminum foil strips. Parts of the samples were heated to 550 degrees C in pure helium gas, and oxygen (2%)-helium (98%) mixture gas. Particles in unheated and heated parts were characterized individually by their morphology and elemental composition using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer. There were mainly two types of soot-containing particles according to the morphology: chain-like and sub-round. Chain-like particles were likely young soot particles because such particles in heated specimens showed similar morphology to those in unheated specimen. In contrast, the sub-round particles were composed of volatile species encapsulated with soot. The heating caused partial evaporation of such particles, and the soot inclusions could be identified only after the heating. The volatile species frequently contained sulfur compounds, but sulfur was not detected in the residues, suggesting that the volatile species were mainly produced on soot particles in the atmosphere. The sub-round soot-containing particles were approximately 3 times larger in diameter than the inclusions. These results suggest that soot particles could be substantially modified in size and composition by volatile species in the urban atmosphere.