Chemical (polycyclic aromatic hydrocarbon and heavy metal) levels in contaminated stormwater and sediments from a motorway dry detention pond drainage system

Chemical (polycyclic aromatic hydrocarbon - PAH and heavy metal) levels in stormwater and sediment samples collected from the London Orbital (M25) motorway drainage dry detention pond at Oxted, Surrey, UK were determined. Such chemicals are derived from vehicular combustion products and the wear and tear materials deposited onto the motorway surface. Gas chromatography-mass spectrometry (GC-MS) was used for the qualitative and quantitative determination of 16 USEPA priority PAHs in motorway drainage sediments. The GC-MS method, incorporating a solid phase extraction step, provides detection limits ranging from 0.17 to 0.41 mg kg(-1)(dry weight). Almost all of the 16 USEPA listed PAHs were detected. Phenanthrene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(a)pyrene and benzo(g,h,i)perylene (PAH numbers 5, 7, 8, 9, 10, 11, 13 and 16) were among the PAHs found at "higher" levels (ranging from 0.3-10.2 mg kg(-1), dry weight) in the sediment samples. PAH levels show little change along the motorway drainage silt trap (facility for reducing the levels of suspended particulate matter in the stormwater). PAH concentrations are considerably higher in the dry detention pond outflow interceptor. Statistical analysis showed that significant correlation coefficients (based on a t-test at the 95% confidence interval) were obtained between those PAHs found at high concentrations over all of the sampling sites. Several PAHs were dispersed beyond the treatment facility and accumulation in the sediment of the deer park resulted in levels ranging from 0.3-1.6 mg kg(-1), dry weight. These PAHs found beyond the treatment facility (in the local farm deer park) may contribute a serious health threat to farm animals or even fish in the aquatic environment. Heavy metal levels (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Cd, Sb and Pb) of the drainage stormwater and sediments were determined by inductively coupled plasma mass spectrometry (ICP-MS), with quality control evaluation using two certified reference materials. Typical detection limits were found to be below 0.1 [micro sign]g l(-1) for stormwater and 0.005 mg kg(-1) for acid digested sediments. Raised heavy metal levels were found throughout the dry detention pond facility and only decrease when the stormwater is diluted following discharge into the river Eden. Statistical analysis also confirms that some significant correlations exist between various heavy metals and PAHs. However, no overall conclusive trend is found indicating that a particular PAH is deposited in sediment relative to a specific heavy metal/s. These results raise some serious concerns about the dispersion and accumulation of chemicals in the sediments of motorway stormwater drainage systems and the need for maintenance and clean-up of contaminated material from such systems.     

Pulsed redistribution of a contaminant following forest fire: cesium-137 in runoff

Of the natural processes that concentrate dispersed environmental contaminants, landscape fire stands out as having potential to rapidly concentrate contaminants and accelerate their redistribution. This study used rainfall simulation methods to quantify changes in concentration of a widely dispersed environmental contaminant (global fallout 137Cs) in soils and surface water runoff following a major forest fire at Los Alamos, New Mexico, USA. The 137Cs concentrations at the ground surface increased up to 40 times higher in ash deposits and three times higher for the topmost 50 mm of soil compared with pre-fire soils. Average redistribution rates were about one order of magnitude greater for burned plots, 5.96 KBq ha(-1) mm(-1) rainfall, compared with unburned plots, 0.55 KBq ha(-1) mm(-1) rainfall. The greatest surface water transport of 137Cs, 11.6 KBq ha(-1) mm(-1), occurred at the plot with the greatest amount of ground cover removal (80% bare soil) following fire. Concentration increases of 137Cs occurred during surface water erosion, resulting in enrichment of 137Cs levels in sediments by factors of 1.4 to 2.9 compared with parent soils. The elevated concentrations in runoff declined rapidly with time and cumulative precipitation occurrence and approached pre-fire levels after approximately 240 mm of rainfall. Our results provide evidence of order-of-magnitude concentration increases of a fallout radionuclide as a result of forest fire and rapid transport of radionuclides following fire that may have important implications for a wide range of geophysical, ecosystem, fire management, and risk-based issues.     

Assessment of Nonpoint Source Pollution from Inactive Mines Using a Watershed-Based Approach

/ A watershed-based approach for screening-level assessment of nonpoint source pollution from inactive and abandoned metal mines was developed and illustrated. The methodology was designed to use limited stream discharge and chemical data from synoptic surveys to derive key information required for targeting impaired waterbodies and critical source areas for detailed investigation and remediation. The approach was formulated based on the required attributes of an assessment methodology, information goals for targeting, attributes of data that are typical of basins with inactive mines, and data analysis methods that were useful for the case study. The methodology is presented as steps in a framework including evaluation of existing data/information and identification of data gaps; definition of assessment information goals for targeting and monitoring design; data collection, management, and analysis; and information reporting and use for targeting. Information generated includes the type and extent of and critical conditions for water-quality impairment, concentrations in and loadings to streams, differences between concentrations in and loadings to streams, and risks of exceeding target concentrations and loadings. Data from the Cement Creek Basin, located in the San Juan Mountains of southwestern Colorado, USA, were used to help develop and illustrate application of the methodology. The required information was derived for Cement Creek and used for preliminary targeting of locations for detailed investigation and remediation. Application of the approach to Cement Creek was successful in terms of cost-effective generation of information and use for targeting.KEY WORDS: Water quality assessment; Nonpoint source pollution; Inactive mines; Watershed     

Correlates of motivation for competitive or cooperative strategy among employed adults

The degree to which two measures of locus of control (LOC) and two measures of need for achievement (NACH) correlate with the motivations of persons for competitive or cooperative strategy was measured in 191 graduate students who are employed full-time as salaried employees. Results indicated significant correlations between motivation for competitive strategies and LOC, NACH, and the factors of LOC entitled self-confidence, internality, and belief in chance. The motivation to avoid the use of competitive strategies was correlated with belief in control by powerful others and chance. The motivation to use cooperative strategies failed to correlate significantly with either NACH or LOC.     

Genecological variation corresponding to Forest Ecosystem Classification vegetation and soil types for jack pine and black spruce from northwestern Ontario

A preliminary study was undertaken to reveal ecotypic differentiation in jack pine and black spruce corresponding to ecological land classification groups. Seed sources of jack pine (64) and black spruce (68) from northwestern Ontario were classified according to Vegetation Types (V-Types) and Soil Types (S-Types) defined by the Forest Ecosystem Classification (FEC) developed by the Ontario Ministry of Natural Resources and Forestry Canada for northwestern Ontario. Two short-term common garden field trials and a greenhouse trial were established for each species. Significant differences were present among ecological groupings of seed sources for both species. These differences were expressed according to V-Types and S-Types based on first, second, and third year heights as well as needle flushing dates for jack pine and second year growth increments for black spruce. Rank differences among the groups based on FEC V-Types and S-Types were generally consistent for each of the two species although certain groups showed rank reversals at the two field trials. Apparently, selection pressures corresponding to different FEC V-Types and S-Types have resulted in a detectable pattern of adaptive variation for both jack pine and black spruce in northwestern Ontario. However, the management implications for these two species are uncertain since additional tests are required to verify these results.     

Ambient site, home outdoor and home indoor particulate concentrations as proxies of personal exposures

Despite strong longitudinal associations between particle personal exposures and ambient concentrations, previous studies have found considerable inter-personal variability in these associations. Factors contributing to this inter-personal variability are important to identify in order to improve our ability to assess particulate exposures for individuals. This paper examines whether ambient, home outdoor and home indoor particle concentrations can be used as proxies of corresponding personal exposures. We explore the strength of the associations between personal, home indoor, home outdoor and central outdoor monitoring site ("ambient site") concentrations of sulfate, fine particle mass (PM(2.5)) and elemental carbon (EC) by season and subject for 25 individuals living in the Boston, MA, USA area. Ambient sulfate concentrations accounted for approximately 70 to 80% of the variability in personal and indoor sulfate levels. Correlations between ambient and personal sulfate, however, varied by subject (0.1-1.0), with associations between personal and outdoor sulfate concentrations generally mirroring personal-ambient associations (median subject-specific correlations of 0.8 to 0.9). Ambient sulfate concentrations are good indicators of personal exposures for individuals living in the Boston area, even though their levels may differ from actual personal exposures. The strong associations for sulfate indicate that ambient concentrations and housing characteristics are the driving factors determining personal sulfate exposures. Ambient PM(2.5) and EC concentrations were more weakly associated with corresponding personal and indoor levels, as compared to sulfate. For EC and PM(2.5), local traffic, indoor sources and/or personal activities can significantly weaken associations with ambient concentrations. Infiltration was shown to impact the ability of ambient concentrations to reflect exposures with higher exposures to particles from ambient sources during summer. In contrast in the winter, lower infiltration can result in a greater contribution of indoor sources to PM(2.5) and EC exposures. Placing EC monitors closer to participants' homes may reduce exposure error in epidemiological studies of traffic-related particles, but this reduction in exposure error may be greater in winter than summer. It should be noted that approximately 20% of the EC data were below the field limit of detection, making it difficult to determine if the weaker associations with the central site for EC were merely a result of methodological limitations.     

Monitoring of heavy metal levels in roadside dusts of Thessaloniki, Greece in relation to motor vehicle traffic density and flow

In recent years, the level of heavy metal pollution in urban areas has been of considerable concern. The principal source has been attributed to the motor vehicle and increasing inner city congestion, which has lead to a change and enlargement of transport stop-start zones. These areas of high traffic density are associated with an increased release of heavy metals into the adjacent residential or commercial areas. Seventy-five roadside dust samples were collected throughout the inner city and by-pass motorway areas of Thessaloniki, Northern Greece. Samples were taken from arterial, major and minor roads, as well as the ring road, to compare and contrast the levels of heavy metals, namely Cu, Zn, Cd, Mn and Pb. Flame Atomic Absorption Spectroscopy (FAAS) was developed to quantitatively determine concentrations of both total element and geochemical fractionation, within the two dust particulate fraction sizes <75 microm and 75-125 microm. Acid digestion using Aqua Regia (3:1 conc. HCl:HNO(3)) was employed for the total elemental analysis, a method that was validated through the use of certified reference materials (CRM). Fractionation studies involved a three-step sequential extraction method performed on five selected samples (representatives of high, mid and low total elemental concentrations). The resultant solutions were analysed for lead and zinc levels to ascertain fractionation throughout the different geochemical fractions, thus assessing bioavailability.It was found that congestion/stop-start traffic patterns did influence and have led to increased levels of heavy metal deposition along inner city roads compared to levels observed on the new relief ring road. Dust particulate fraction sizes were only found to show statistically significant differences in cadmium and manganese, at the probability P < 0.001 or 99.9% confidence limit. Both Cd and Mn showed higher total levels in the smaller fraction sizes (<75 microm), implying that their major release source is exhaust emissions. There were no significant differences in the other elements, at the P > 0.05 or 95% confidence limit. Road type was seen to have little affect on cadmium and manganese, though lead, copper and zinc were all found to show higher levels on the inner city routes. This can be related back to the wear-and-tear of vehicle components as a result of the stop-start traffic patterns (brake pads etc). Both Pb and Zn have shown to be in chemical forms that are bio available to ecosystems.     

Indoor/ambient residential air toxics results in rural western Montana

Indoor and ambient concentrations of 21 volatile organic compounds (including 14 hazardous air pollutants) were measured in the homes of nearly 80 western Montana (Missoula) high school students as part of the 'Air Toxics Under the Big Sky' program during the 2004/2005 and 2005/2006 school years. Target analytes were measured using low flow air sampling pumps and sorbent tubes, with analysis of the exposed samples by thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). The results reported here present the findings of the first indoor/ambient air toxics monitoring program conducted in a semi-rural valley location located in the Northern Rocky Mountain/Western Montana region. Of all of the air toxics quantified in this study, toluene was found to be the most abundant compound in both the indoor and ambient environments during each of the two school years. Indoor log-transformed mean concentrations were found to be higher when compared with ambient log-transformed mean concentrations at P < 0.001 for the majority of the compounds, supporting the results of previous studies conducted in urban areas. For the air toxics consistently measured throughout this program, concentrations were approximately six times higher inside the student's homes compared to those simultaneously measured directly outside their homes. For the majority of the compounds, there were no significant correlations between indoor and ambient concentrations.     

Variably saturated flow and multicomponent biogeochemical reactive transport modeling of a uranium bioremediation field experiment

Three-dimensional, coupled variably saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport and biogeochemical reactions controlling uranium behavior under pulsed acetate amendment, seasonal water table variation, spatially variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. While the simulation of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado was generally consistent with behaviors identified in previous field experiments at the Rifle IFRC site, the additional process and property detail provided several new insights. A principal conclusion from this work is that uranium bioreduction is most effective when acetate, in excess of the sulfate-reducing bacteria demand, is available to the metal-reducing bacteria. The inclusion of an initially small population of slow growing sulfate-reducing bacteria identified in proteomic analyses led to an additional source of Fe(II) from the dissolution of Fe(III) minerals promoted by biogenic sulfide. The falling water table during the experiment significantly reduced the saturated thickness of the aquifer and resulted in reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP reaction products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions with localized effects of the fine lithofacies having the largest impact on U(VI) surface complexation. The ability to model the comprehensive biogeochemical reaction network, and spatially and temporally variable processes, properties, and conditions controlling uranium behavior during engineered bioremediation in the naturally complex Rifle IFRC subsurface system required a subsurface simulator that could use the large memory and computational performance of a massively parallel computer. In this case, the eSTOMP simulator, operating on 128 processor cores for 12h, was used to simulate the 110-day field experiment and 50 days of post-biostimulation behavior.     

Sources of PCDD/Fs, non-ortho PCBs and PAHs in sediments of high and low impacted transboundary rivers (Belgium-France)

PAHs, PCDD/Fs and non-ortho PCBs have been assessed in Yser and Upper-Scheldt river sediments. Higher contamination levels were observed in the Upper-Scheldt sediments: maximum concentrations for the 16 US-EPA PAHs, PCDD/Fs and non-ortho PCBs respectively amount to 8.9 mg kg⁻¹, 12 ng TEQ kg⁻¹ and 5.1 ng TEQ kg⁻¹. Diagnostic PAH ratios in sediments and atmospheric samples suggest that the PAH compounds are from pyrolytic origin, more specifically combustion processes. The huge consumption of coal in cokes-ovens and smelters and its use for house-heating in Northern France, although decreasing during the last decades, are in support of that suggestion. PCDD/F fingerprints in sediments and deposition material indicate that OCDD is the dominant congener. In addition use of pentachlorophenol (PCP) in the past led to a minor contribution of PCDD/Fs in our sediment samples. Non-ortho PCBs form a substantial fraction of the total TEQ concentrations observed in the sediments. Since the 1980s and 1990s a substantial reduction of the PCDD/F sediment concentrations is observed, but this is not the case for the PAHs.