Comprehensive assessment of toxic metals in urban and suburban street deposited sediments (SDSs) in the biggest metropolitan area of China

A set of toxic metals, i.e. As, Hg, Pb, Cd, Cu, Zn, Ni and Cr, in urban and suburban SDSs were investigated comparatively in the biggest metropolitan area of China, Shanghai. Results showed that all of the metals except As were accumulated greatly, much higher than background values. Geo-accumulation index indicated that metal contamination in urban SDSs was generally heavier than that in suburban SDSs. Potential ecological risk index demonstrated that overall risks caused by metals were considerable. Cd contributed 52% to the overall risk. Multivariate statistical analysis revealed that in urban SDSs, Zn, Ni, Cd, Pb, Cu and Cr were related to traffic and industry; coal combustion led to elevated levels of Hg; soil parent materials controlled As contents. In suburban SDSs, Pb, Cu, As and Cd largely originated from traffic pollution; Zn, Ni and Cr were associated with industrial contaminants; Hg was mainly from domestic solid waste.     

A conceptual framework: Redefining forest soil's critical acid loads under a changing climate

Federal agencies of several nations have or are currently developing guidelines for critical forest soil acid loads. These guidelines are used to establish regulations designed to maintain atmospheric acid inputs below levels shown to damage forests and streams. Traditionally, when the critical soil acid load exceeds the amount of acid that the ecosystem can absorb, it is believed to potentially impair forest health. The excess over the critical soil acid load is termed the exceedance, and the larger the exceedance, the greater the risk of ecosystem damage. This definition of critical soil acid load applies to exposure of the soil to a single, long-term pollutant (i.e., acidic deposition). However, ecosystems can be simultaneously under multiple ecosystem stresses and a single critical soil acid load level may not accurately reflect ecosystem health risk when subjected to multiple, episodic environmental stress. For example, the Appalachian Mountains of western North Carolina receive some of the highest rates of acidic deposition in the eastern United States, but these levels are considered to be below the critical acid load (CAL) that would cause forest damage. However, the area experienced a moderate three-year drought from 1999 to 2002, and in 2001 red spruce (Picea rubens Sarg.) trees in the area began to die in large numbers. The initial survey indicated that the affected trees were killed by the southern pine beetle (Dendroctonus frontalis Zimm.). This insect is not normally successful at colonizing these tree species because the trees produce large amounts of oleoresin that exclude the boring beetles. Subsequent investigations revealed that long-term acid deposition may have altered red spruce forest structure and function. There is some evidence that elevated acid deposition (particularly nitrogen) reduced tree water uptake potential, oleoresin production, and caused the trees to become more susceptible to insect colonization during the drought period. While the ecosystem was not in exceedance of the CAL, long-term nitrogen deposition pre-disposed the forest to other ecological stress. In combination, insects, drought, and nitrogen ultimately combined to cause the observed forest mortality. If any one of these factors were not present, the trees would likely not have died. This paper presents a conceptual framework of the ecosystem consequences of these interactions as well as limited plot level data to support this concept. Future assessments of the use of CAL studies need to account for multiple stress impacts to better understand ecosystem response.     

Comparison among model estimates of critical loads of acidic deposition using different sources and scales of input data

The critical load (CL) of acidic atmospheric deposition represents the load of acidity deposited from the atmosphere to the earth’s surface at which harmful acidification effects on sensitive biological receptors are thought to occur. In this study, the CL for forest soils was estimated for 27 watersheds throughout the United States using a steady-state mass balance approach based on both national and site-specific data and using different approaches for estimating base cation weathering. Results suggested that the scale and source of input data can have large effects on the calculated CL and that the most important parameter in the steady-state model used to estimate CL is base cation weathering. These results suggest that the data and approach used to estimate weathering must be robust if the calculated CL is to be useful for its intended purpose.     

Analysis of 3-year observations of CFC-11, CFC-12 and CFC-113 from a semi-rural site in China

In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl₃F), CFC-12 (CCl₂F₂) and CFC-113 (CCl₂F–CClF₂) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10^?12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of ?2.0 ppt yr^?1 for CFC-11, ?2.5 ppt yr^?1 for CFC-12 and ?0.7 ppt yr^?1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.     

Chemical mass balance source apportionment for combined PM2.5 measurements from U.S. non-urban and urban long-term networks

The Minnesota Particulate Matter 2.5 (PM_2.5) Source Apportionment Study was undertaken to explore the utility of PM_2.5 mass, element, ion, and carbon measurements from long-term speciation networks for pollution source attribution. Ambient monitoring data at eight sites across the state were retrieved from the archives of the Interagency Monitoring of Protected Visual Environments (IMPROVE) and the Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and analyzed by an Effective Variance – Chemical Mass Balance (EV-CMB) receptor model with region-specific geological source profiles developed in this study. PM_2.5 was apportioned into contributions of fugitive soil dust, calcium-rich dust, taconite (low grade iron ore) dust, road salt, motor vehicle exhaust, biomass burning, coal-fired utility, and secondary aerosol. Secondary sulfate and nitrate contributed strongly (49–71% of PM_2.5) across all sites and was dominant (≥60%) at IMPROVE sites. Vehicle exhausts accounted for 20–70% of the primary PM_2.5 contribution, largely exceeding the proportion in the primary PM_2.5 emission inventory. The diesel exhaust contribution was separable from the gasoline engine exhaust contribution at the STN sites. Higher detection limits for several marker elements in the STN resulted in non-detectable coal-fired boiler contributions which were detected in the IMPROVE data. Despite the different measured variables, analytical methods, and detection limits, EV-CMB results from a nearby IMPROVE-STN non-urban/urban sites showed similar contributions from regional sources – including fugitive dust and secondary aerosol. Seasonal variations of source contributions were examined and extreme PM_2.5 episodes were explained by both local and regional pollution events.     

Study on ambient concentrations of PM10, PM10–2.5, PM2.5 and gaseous pollutants. Trace elements and chemical speciation of atmospheric particulates

This study provides the first comprehensive report on mass concentrations of particulate matter of various sizes, inorganic and organic gas concentrations monitored at three sampling sites in the city of Palermo (Sicily, Italy). It also provides information on the water-soluble species and trace elements. A total of 2054 PM₁₀ (1333) and PM_2.5 (721) daily measurements were collected from November 2006 to February 2008. The highest mass concentrations were observed at the urban stations, average values being about two times higher than those at the suburban (control) site. Time variations in PM₁₀ and also PM_10–2.5 were observed at the urban stations, the highest concentrations being measured in autumn and winter. CO, NOx, NO₂, benzene, toluene and o-xylene concentrations peaked in autumn and winter, a pattern similar to those recorded for PM₁₀ and PM_10–2.5 mass levels, indicating the importance of traffic emissions in urban air pollution. 91% and 51% of the benzene measurements exceeded the limit of 5 μg m^?3 at the two urban monitoring sites. Trace elements (As, Ba, Cr, Cu, Mo, Pb, Sb) suspected of being introduced into the atmosphere mainly by anthropogenic activities, were highly enriched with respect to local soil. Results indicate that a large fraction of PM₁₀ (31–47% in weight) and PM_2.5 (29% in weight) is made up of water-soluble ions. Ammonium sulphate and nitrate particles accounted for 14–29 wt% of particulate matter mass concentrations. Crustal and marine components, combined, account for 41% and 49% in PM_2.5 and PM₁₀, respectively. The calculated deficits in Cl^- and NH₄⁺ ions suggest that a proportion of these ions are lost, via the formation of gaseous NH₄Cl or HCl and NH₃.     

Air pollution characteristics associated with mesoscale atmospheric patterns in northwest continental Europe

An impact related daily air quality index (DAQx), calculated for 15 air quality monitoring stations (traffic, background, and industry) in Belgium, France, Germany and Luxembourg, was compared to mesoscale atmospheric patterns between 2001 and 2007. Meteorological conditions were described by the Hess and Brezowsky synoptic weather classification system and gridded data of the EU FP6 ENSEMBLES project of total precipitation and mean surface temperature. DAQx values indicate sufficient to poor air quality in the urban area of Brussels and at urban traffic stations, as well as satisfactory air quality at the background stations. The air quality index refers to more than 90% to the presence of high PM₁₀, O₃ and NO₂ concentrations. SO₂ and CO play only a minor role. The investigation of weather regimes indicates that zonal and mixed cyclonic circulation regimes are associated with better air quality than meridional and anticyclonic weather regimes. In general, weather regimes with high daily precipitation lead to better air quality than dryer air masses because of lower contribution of PM₁₀ to the air quality index. A trend analysis of weather regimes from 1978 to 2007 shows significant (α = 0.05) positive trends for weather classes associated with lower PM₁₀ concentrations. The results of a case study at a German station examining the relationship between PM₁₀ concentrations and local meteorological quantities (wind speed and precipitation) confirm the results of the regional analysis.     

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 2. Formation, bioaccumulation and elimination of hydroxylated metabolites

The uptake, elimination and transformation of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, and then depurated over a five-month period. Methoxylated (MeO-) and hydroxylated (OH-) PBDEs were determined in fish plasma exposed to PBDEs and compared to those obtained in control fish. While all MeO- and some OH- congeners identified in fish plasma were found to originate from non-metabolic sources, several OH- congeners, i.e., OH-tetraBDEs and OH-pentaBDEs, were found to originate from fish metabolism. Among these, 4′-OH-BDE-49 was identified as a BDE-47 metabolite. Congener 4′-OH-BDE-101, identified here for the first time, may be the result of BDE-99 metabolic transformation. Our results unequivocally showed that PBDEs are metabolised in juvenile sole via the formation of OH- metabolites. However, this was not a major biotransformation route compared to biotransformation through debromination.     

On-road traffic emissions in a megacity

A new annual bottom–up emission inventory of criteria pollutants and greenhouse gases from on-road mobile sources was developed for 2006 for the metropolitan area of Buenos Aires, Argentina, within a four-year regional project aimed at providing tools for chemical weather forecast in South America. Under the scarcity of local emission factors, we collected data from measuring campaigns performed in Argentina, Brazil, Chile and Colombia and compiled a data set of regional emission factors representative of Latin American fleets and driving conditions. The estimated emissions were validated with respect to downscaled national estimates and the EDGAR global emission database. Our results highlight the role of older technologies accounting in average for almost 80% of the emissions of all species. The area exhibits higher specific emissions than developed countries, with figures two times higher for criteria pollutants. We analyzed the effect on emissions of replacing gasoline by compressed natural gas, occurring in Argentina since 1995. We identified (i) a relationship between number of vehicles and a compound socioeconomic indicator, and (ii) time-lags in vehicle technologies between developed and developing countries, which can be respectively applied for spatial disaggregation and the development of projections for other Latin American cities. The results may also be employed to complement global emission inventories and by local policy makers as an environmental management tool.