National status and trends mussel watch program: chlordane-related compounds in Gulf of Mexico oysters, 1986-1990

The National Oceanic and Atmospheric Administration's National Status and Trends (NS&T) Program has been monitoring the chemical contamination in bivalve tissues from the US coastal waters since 1986. alpha-Chlordane, trans-nonachlor, heptachlor and heptachlor epoxide, components of technical chlordane, are among the chlorinated pesticides measured. The geographical distribution of these chlordane compounds in oyster samples from the US Gulf of Mexico is well-established. For example, highest residue levels, predominantly alpha-chlordane and trans-nonachlor, were encountered in samples collected near highly populated areas in contrast with the concentrations measured in predominantly agricultural areas. Data collected during 5 years of bivalve sampling are used to evaluate temporal trends in residue concentrations at most NS&T sites. Minor decreases can be observed in the concentrations of alpha-chlordane and trans-nonachlor. Heptachlor and its epoxide concentrations, in contrast, have been increasing since 1987.     

Concentrations, sources and spatial distribution of polycyclic aromatic hydrocarbons in soils from Beijing, Tianjin and surrounding areas, North China

The concentrations, profiles, sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) were determined in 40 surface soil samples collected from Beijing, Tianjin and surrounding areas, North China in 2007, and all sampling sites were far from industrial areas, roadsides and other pollution sources, and across a range of soil types in remote, rural villages and urban areas. The total concentrations of 16 PAHs ranged from 31.6 to 1475.0 ng/g, with an arithmetic average of 336.4 ng/g. The highest PAH concentrations were measured in urban soils, followed by rural village soils and soils from remote locations. The remote-rural village-urban PAH concentration gradient was related to population density, gross domestic product (GDP), long-range atmospheric transport and different types of land use. In addition, the PAH concentration was well correlated with the total organic carbon (TOC) concentration of the soil. The PAH profile suggested that coal combustion and biomass burning were primary PAH sources.     

Variation in PAH inputs and microbial community in surface sediments of Hamilton Harbour: implications to remediation and monitoring

Variations in concentrations of polycyclic aromatic hydrocarbons (PAHs) and microbial community indicators were investigated in representative highly contaminated and less contaminated surface sediment sites of Hamilton Harbour. Inputs of PAH to the upper 3cm of sediments up to four times the average upper sediment concentrations were observed. Associated PAH fingerprint profiles indicated that the source was consistent with the PAH source to the industrial region of the harbour. Increased PAH loadings were associated with decreased bacterial populations as indicated by phospholipid fatty acid (PLFA) concentrations. However, relatively minor impacts on overall community composition were indicated. Porewater methane concentrations and isotopic data indicated a difference in the occurrence of methane oxidation between the two sites. This study confirms temporally limited transport of contaminants from highly impacted regions as a vector for contaminants within the harbour and the impact on microbial carbon cycling and bed stability.     

Source Resolution of Fine Particulate Polycyclic Aromatic Hydrocarbons Using a Receptor Model Modified for Reactivity

This paper provides source contribution estimates from vehicular and meat-cooking emissions to particulate polycyclic aromatic hydrocarbon (PAH) and elemental carbon (EC) concentrations measured at two Los Angeles sites during a field study in 1989. The source concentration matrix for PAH was based on new data for vehicular emissions and literature data for meat-cooking operations. The chemical mass balance (CMB 7.0) receptor model was used, and source profiles were modified to reflect reactive decay of PAH in the atmosphere. The calculations indicate that the Pico Rivera site was dominated by auto emissions, which account for more than 90 percent of all the PAH (except chrysene), carbon monoxide (CO), and 61 percent of the EC concentrations. In contrast, emissions from meat cooking contributed significantly (20 to 75 percent) to the concentrations of four-ring PAH measured at a residential site at Upland. The five-ring and larger PAH were attributed to auto emissions at Upland as well.     

Distribution of polycyclic aromatic hydrocarbons in soils at Guiyu area of China, affected by recycling of electronic waste using primitive technologies

The concentration, distribution, profile and possible source of polycyclic aromatic hydrocarbons (PAHs) in soil were studied in Guiyu, an electronic waste (E-waste) recycling center, using primitive technologies in Southeast China. Sixteen USEPA priority PAHs were analyzed in 49 soil samples (0-10 cm layer) in terms of individual and total concentrations, together with soil organic matter (SOM) concentrations. The concentrations of a sum of 16 PAHs ranged from 44.8 to 3206 microgkg(-1) (dry weight basis), in the descending order of E-waste open burning sites (2065 microgkg(-1))>areas near burning sites (851microgkg(-1))>rice fields (354 microgkg(-1))>reservoir areas (125microgkg(-1)). The dominant PAHs were naphthalene, phenanthrene and fluoranthene, which were mainly derived from incomplete combustion of E-waste (e.g. wire insulations and PVC materials), and partly from coal combustion and motorcycle exhausts. All individual and total PAH concentrations were significantly correlated with SOM except for naphthalene and acenaphthylene. Principal component analysis was performed, which indicated that PAHs were mainly distributed into three groups in accordance with their ring numbers and biological and anthropogenic source. In conclusion, PAH concentrations in the Guiyu soil were affected by the primitive E-waste recycling activities.     

Occurrence of PAH in the seasonal snowpack of the Eastern Italian Alps

PAH concentrations have been determined in 47 seasonal snowpack samples collected in the Valbelluna valley and in the Bellunesi Dolomites National Park, in the Italian North-Eastern Alps, during the winter of 2005. The ΣPAH concentration in high-altitude alpine sites (above 1700 m) was 32 ± 20 ng/kg while in valley bottom urban areas it was 165 ± 54 ng/kg with maximum values of 290 ng/kg. The GIS mapping technique was employed to produce a PAH spatial distribution. The urbanized Valbelluna valley, and in particular the SW part, had the highest accumulation of all PAH, with values an order of magnitude more than those in rural and alpine areas. This behaviour is consistent with urban air quality data, and is due to geo-morphological and meteorological factors such as the deeper shape of the valley at the position of the town of Feltre and the low altitude of the boundary layer during the winter season.     

Butyltin concentrations in oysters from the Gulf of Mexico from 1989 to 1991

Oyster samples from 53 Gulf of Mexico coastal sites were collected and analyzed for butyltins during 1989, 1990, and 1991. The geometric-mean tributylin concentrations were 85, 30, and 43 ng Sn/g for 1989, 1990, and 1991, respectively. The tributyltin concentrations are best represented by a log-normal distribution. A decline in the butyltin concentrations at sites with relatively low butyltin concentrations for 1989 compared with 1990 and 1991 was observed, and, at relatively high butyltin concentrations (> 400 ng Sn/g), there was hardly any difference between 1989 and 1991, but lower concentrations were present in 1990. Continued monitoring is needed in order to determine if butyltin contamination of the coastal marine environment is decreasing in response to use limitations.     

Polycyclic aromatic hydrocarbons in the sediments of the South China Sea

Sixteen sediment samples, collected from the South China Sea, were analyzed for 11 parent polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and gas chromatography-mass spectrometry. Total concentrations of the 11 PAHs studied in the sediments ranged from 24.7 to 275.4 ng/g with a mean of 145.9 ng/g dry sediment. PAH concentrations displayed a consistent distribution trend with the sediment organic carbon content. The linear regression analysis showed that the total concentration of PAHs in the sediment was significantly correlated to the sediment organic carbon content with a correlation coefficient of 0.735 (n=16). Special PAH compound ratios, such as phenanthrene/anthracene and fluoranthene/pyrene, were calculated to evaluate the relative importance of different origins. The collected data showed that pyrolytic input from anthropogenic combustion processes was predominant at almost all the stations investigated. Only one station, located in the proximity of oil wells, appeared to be contaminated predominantly by petrogenic input. Three anthropogenic PAHs, i.e. pyrene, benzo[a]pyrene and benzo[e]pyrene, exhibited similar distribution patterns in the studied area, implying that these compounds possess identical sources. However, perylene did not entirely follow the distribution trend of the three PAHs, suggesting that the sediment perylene probably derived from other sources such as in situ biogenic origins. Dibenzothiophene, a sulfur heterocyclic aromatic compound, was also measured in this study.     

Principal component analysis of trace substance concentrations in rainwater samples

A total of 197 bulk precipitation samples from different rural and suburban stations in Bavaria, F.R.G., were analysed for the following trace substance concentrations: PAH (fluoranthen, benzo-ghiperylene, benzo-a-pyrene), chlorinated hydrocarbons (α- and γ-BHC, HCB, PCB) and trace metals (Zn, Cd, Pb, Cu, Fe). Data analysis was carried out with multivariate principal component analysis separately for suburban and rural sites, and for summer and winter events. The resulting principal component loadings matrices are characterized by typical patterns indicating differences of the emission of the single pollutants in their temporal and spatial distribution. PAH and Pb are concentrations parameters for the interpretation of the data structure of suburban sites. While Pb concentrations are elevated in the rainwater samples of these stations during all seasons, PAH indicate space-heating by showing elevated levels during winter. Rural sites are characterized by a lower interrelation between the various parameters and chlorinated BHC pesticides as further pollution variables. These substances are highly enriched in rainwater samples from spring and summer events.     

Distribution and sources of polycyclic aromatic hydrocarbons from urban to rural soils: a case study in Dalian, China

To estimate the distribution and sources of soil polycyclic aromatic hydrocarbons (PAHs) in metropolitan and adjacent areas, soil samples were collected from urban, suburban and rural locations of Dalian, China, and concentrations of 14 PAHs were determined. The spatial PAH profiles were site-specific and determined by the sources close to the sampling sites. PAH concentrations decreased significantly along the urban-suburban-rural transect. The gradient implied that the fractionation effect influenced PAH distribution. Bivariate plots of selected diagnostic ratios showed general trends of co-variation and allowed to distinguish samples taken from different areas. An improved method, factor analysis (FA) with nonnegative constrains, was used to determine the primary sources and contributions of PAHs in soils. The FA model showed traffic average (74%) and coal related residential emission (26%) were two primary sources to Dalian soils. In addition, the FA model provided reasonable explanations for PAH contributions in soils from different sites. The results suggest that FA with nonnegative constraints is a promising tool for source apportionment of PAHs in soils.     

Particle size distributions of polycyclic aromatic hydrocarbons in rural and urban atmosphere of Tianjin, China

The size distributions of 16 polycyclic aromatic hydrocarbons (PAHs) and particle mass less than 10 microm in aerodynamic diameter (Dp) were measured using a nine-stage low-volume cascade impactor at rural and urban sites in Tianjin, China in the winter of 2003-2004. The particles exhibited the trimodal distribution with the major peaks occurring at 0.43-2.1 and 9.0-10.0 microm for both urban and rural sites. The concentrations of the total PAH (sum of 16 PAH compound) at rural site were generally less than those of urban site. Mean fraction of 76.5% and 63.9% of the total PAH were associated with particles of 0.43-2.1 microm at rural and urban sites, respectively. Precipitation, temperature, wind speed and direction were the important meteorological factors influencing the concentration of PAHs in rural and urban sites. The distributions of PAHs concentration with respect to particle size were similar for rural and urban samples. The PAHs concentrations at the height of 40 m were higher than both of 20 and 60 m at urban site, but the mass median diameter (MMD) of total PAH increased with the increasing height. The mid-high molecular weight (278 >or= MW >or= 202) PAHs were mainly associated with fine particles (Dp or=MW >or=178) PAHs were distributed in both of fine and coarse particle. The fraction of PAHs associated with coarse particles (Dp>2.1 microm) decreased with increasing molecular weight. The relatively consistent distribution of PAHs seemed to indicate the similar combustion source of PAHs at both of rural and urban sites. The fine differences of concentration and distribution of PAHs at different levels at urban site suggested that the different source and transportation path of particulate PAHs.     

Formaldehyde levels in air and wet precipitation at Mexico City, Mexico

Formaldehyde concentrations in ambient air and in rain water were measured at the University of Mexico, Mexico City. Air samples were taken twice a day, from 9:00 to 13:00 h and from 13:00 to 16:00 h local time from July to December 1985. Rain water was collected on daily bases from July to October, i.e. during the rainy season. The ambient air mean value was 24.4 x 10(-3) ppmv for morning hours, while the afternoon mean value was 18.5 x 10(-3) ppmv. The formaldehyde concentration in wet precipitation ranged from 0.10 to 0.80 mg liter(-1) (3.3 to 26.6 micromoles liter(-1)) 0.41 mg liter(-1) (13.7 microoles liter(-1)). A comparison of the results of this study with some measurements made at remote maritime sites, rural and urban areas, indicated that the formaldehyde levels in the atmosphere and rain water of Mexico City are among the highest reported in the literature, including the data reported by Grosjean (1982) for Los Angeles, California, during severe photochemical pollution conditions.     

Temporal variations in PAH concentrations in Quercus ilex L. (holm oak) leaves in an urban area

Temporal variations of polycyclic aromatic hydrocarbon (PAH) concentrations in leaves of a Mediterranean evergreen oak, Quercus ilex L., were investigated in order to assess the suitability of this species to biomonitor PAH air contamination. Leaf samples were collected at six sites of the urban area of Naples (Italy) and at a control site in the Vesuvius National Park, in May and September 2001, and in January and May 2002. PAH extraction was conducted by sonication in dichloromethane-acetone and quantification by GC-MS. In winter, leaf total PAH concentrations showed, at all the urban sites, values 2-fold higher than in all the other samplings, reflecting the temporal trend reported for PAH air contamination in the Naples urban area. Moreover, leaf PAH concentrations showed, at all the urban sites, a decrease in May 2002 after the winter accumulation. At the control site leaf PAH concentrations showed lower values and smaller temporal variations than at the urban sites. The findings support the suitability of Q. ilex leaves to monitor temporal variations in PAH contamination. The highest winter concentrations of total PAHs were due to the medium molecular weight PAHs that increased with respect to both low and high molecular weight PAHs. The medium molecular weight PAHs showed the same temporal trend both at the urban and remote sites.     

The effect of EURO-0 vehicle substitution on polycyclic aromatic hydrocarbon and carbon monoxide concentrations in an urban area

From 1994 to 2003, daily air concentrations of particle-bound polycyclic aromatic hydrocarbons (PAHs) and carbon monoxide (CO) were regularly monitored at two traffic-oriented sampling sites (A and B) in urban Genoa, Italy. The data were used to estimate effects on air quality in real situations due to progressive substitution of EURO-0 vehicles, started in 1993, with less-polluting vehicles (EURO-1, EURO-2), mainly gasoline vehicles with a catalyst. PAH profile classification and diagnostic PAH ratios were used to identify 345 samples of predominantly traffic origin. At both sites, CO and PAH daily concentrations decreased exponentially with time and the apparent half-life values calculated were 6.3 and 5.5 for CO and 3.7 and 3.5 years for PAHs at sites A and B, respectively. At site A, monitored for traffic intensity, multiple regression analyses confirmed that daily PAH and CO concentrations were positively correlated with the number of non-catalytic vehicles estimated to cross this site during sampling and negatively correlated with seasonal variables (air temperature, ozone concentration, relative air humidity). The reduction in air pollution estimated for complete substitution of non-catalytic gasoline vehicles was 89% for BaP, 85% for total PAHs and 69% for CO.     

Polycyclic aromatic hydrocarbons, black carbon, and molecular markers in soils of Switzerland

Polycyclic aromatic hydrocarbons (PAH) were analysed in 23 soil samples (0–10 cm layer) from the Swiss soil monitoring network (NABO) together with total organic carbon (TOC) and black carbon (BC) concentration, as well as some PAH source diagnostic ratios and molecular markers. The concentrations of the sum of 16 EPA priority PAHs ranged from 50 to 619 μg/kg dw. Concentrations increased from arable, permanent and pasture grassland, forest, to urban soils and were 21–89% lower than median numbers reported in the literature for similar Swiss and European soils. NABO soils contained BC in concentrations from 0.4 to 1.8 mg/g dw, except for two sites with markedly higher levels. These numbers corresponded to 1–6% of TOC and were comparable to the limited published BC data in soil and sediments obtained with comparable analytical methods. The various PAH ratios and molecular markers pointed to a domination of pyrogenically formed PAHs in Swiss soils. In concert, the gathered data suggest the following major findings: (1) gas phase PAHs (naphthalene to fluorene) were long-range transported, cold-condensated at higher altitudes, and approaching equilibrium with soil organic matter (OM); (2) (partially) particle-bound PAHs (phenanthrene to benzo[ghi]perylene) were mostly deposited regionally in urban areas, and not equilibrated with soil OM; (3) Diesel combustion appeared to be a major emission source of PAH and BC in urban areas; and (4) wood combustion might have contributed significantly to PAH burdens in some soils of remote/alpine (forest) sites.     

Atmospheric polycyclic aromatic hydrocarbons (PAHs) in Asia: a review from 1999 to 2004

Polycyclic aromatic hydrocarbons (PAHs) are present in both gaseous and particulate phases. These compounds are considered to be atmospheric contaminants and are human carcinogens. Many studies have monitored atmospheric particulate and gaseous phases of PAH in Asia over the past 5 years. This work compares and discusses different sample collection, pretreatment and analytical methods. The main PAH sources are traffic exhausts (AcPy, FL, Flu, PA, Pyr, CHR, BeP) and industrial emissions (BaP, BaA, PER, BeP, COR, CYC). PAH concentrations are highest in areas of traffic, followed by the urban sites, and lowest in rural sites. Meteorological conditions, such as temperature, wind speed and humidity, strongly affect PAH concentrations at all sampling sites. This work elucidates the characteristics, sources and distribution, and the healthy impacts of atmospheric PAH species in Asia.     

Wetlands as principal zones of methylmercury production in southern Louisiana and the Gulf of Mexico region

It is widely recognized that wetlands, especially those rich in organic matter and receiving appreciable atmospheric mercury (Hg) inputs, are important sites of methylmercury (MeHg) production. Extensive wetlands in the southeastern United States have many ecosystem attributes ideal for promoting high MeHg production rates; however, relatively few mercury cycling studies have been conducted in these environments. We conducted a landscape scale study examining Hg cycling in coastal Louisiana (USA) including four field trips conducted between August 2003 and May 2005. Sites were chosen to represent different ecosystem types, including: a large shallow eutrophic estuarine lake (Lake Pontchartrain), three rivers draining into the lake, a cypress-tupelo dominated freshwater swamp, and six emergent marshes ranging from a freshwater marsh dominated by Panicum hemitomon to a Spartina alterniflora dominated salt marsh close to the Gulf of Mexico. We measured MeHg and total Hg (THg) concentrations, and ancillary chemical characteristics, in whole and filtered surface water, and filtered porewater. Overall, MeHg concentrations were greatest in surface water of freshwater wetlands and lowest in the profundal (non-vegetated) regions of the lake and river mainstems. Concentrations of THg and MeHg in filtered surface water were positively correlated with the highly reactive, aromatic (hydrophobic organic acid) fraction of dissolved organic carbon (DOC). These results suggest that DOC plays an important role in promoting the mobility, transport and bioavailability of inorganic Hg in these environments. Further, elevated porewater concentrations in marine and brackish wetlands suggest coastal wetlands along the Gulf Coast are key sites for MeHg production and may be a principal source of MeHg to foodwebs in the Gulf of Mexico. Examining the relationships among MeHg, THg, and DOC across these multiple landscape types is a first step in evaluating possible links between key zones for Hg(II)-methylation and the bioaccumulation of mercury in the biota inhabiting the Gulf of Mexico region.     

Residue level of polycyclic aromatic hydrocarbons in Japanese paddy soils from 1959 to 2002

The residue level of 21 polycyclic aromatic hydrocarbons (PAHs) and the temporal changes in this level were investigated in paddy soils collected from particular experimental sites in Japan from 1959 to 2002. The average total PAH concentration in all the samples was 496 microg kg(-1), and it ranged from 52.9 to 2180 microg kg(-1). The residue level of the PAHs was the highest during the 1960s, rapidly decreased during the 1970s, and remained almost constant thereafter. Relatively high PAH concentrations were observed in soils from areas that experienced heavy snowfall and that had relatively low air temperature. The predominant PAHs were phenanthrene, fluoranthene, naphthalene, and pyrene, and their concentration overall and in relation to that of the total PAHs decreased each year since the 1960s. Similarities in the PAH profiles among the locations were determined using the concentration correlation matrix and cluster analysis, and ratios of the levels of specific PAH pairs were also calculated to determine their origin. The collected data suggested that the origins of soil PAHs changed chronologically from the burning of agricultural wastes such as stubble before the mid-1970s to the combustion of fossil fuel and its secondary products after the mid-1970s.     

Natural attenuation/phytoremediation in the vadose zone of a former industrial sludge basin

The natural attenuation of polyaromatic hydrocarbons (PAHs) in the vadose zone of a naturally revegetated former industrial sludge basin (0.45 ha) was examined. This was accomplished by comparing the concentration of 16 PAH contaminants present in sludge collected below the root zone of plants with contaminants present at 3 shallower depths within the root zone. Chemical analysis of 240 samples from 60 cores showed the average concentration of total and individual PAHs in the 0-30 cm, 30-60 cm, and bottom of the root zone strata were approximately 10, 20, and 50%, respectively, of the 16, 800 ppm average total PAH concentration in deep non-rooted sludge. Statistically significant differences in average PAH concentrations were observed between each strata studied and the non-rooted sludge except for the concentrations of acenaphthene and chrysene present at the bottom of the root zone in comparison to sludge values. The rooting depth of the vegetation growing in the basin was dependent on both vegetation type and plant age. Average rooting depths for trees, forbs (herbaceous non-grasses), and grasses were 90, 60, and 50 cm, respectively. The deepest root systems observed (100-120 cm) were associated with the oldest (12-14 year-old) mulberry trees. Examination of root systems and PAH concentrations at numerous locations and depths within the basin indicated that plant roots and their microbially active rhizospheres fostered PAH disappearance; including water insoluble, low volatility compounds, i.e. benzo(a)pyrene and benzo(ghi)perylene. The reduced concentration of PAHs in the upper strata of this revegetated former sludge basin indicated that natural attenuation had occurred. This observation supports the concept that through appropriate planting and management practices (phytoremediation) it will be possible to accelerate, maximize, and sustain natural processes, whereby even the most recalcitrant PAH contaminants (i.e. benzo(a)pyrene) can be remediated over time.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.