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.     

Forest plantations, water availability, and regional climate change: controversies surrounding Acacia mearnsii plantations in the upper Palnis Hills, southern India

Plantation forests not only impact carbon and water cycles, but also affect biodiversity, livelihoods, and shape regional economies. Each of these impacts differs across varying scales of analysis. This paper illustrates how forest, climate change and hydrology debates play out in the context of the forest plantations of Australian black wattle (Acacia mearnsii) in the upper Palni hills of southern India. We outline the contradictory perspectives of different local groups regarding the impact of plantations on catchment hydrology and water availability, and examine these in relation to changes in the regional economy and rainfall patterns. Our analysis indicates that changes in these two factors have played a more significant role than existing wattle plantations in affecting local and regional water availability. We suggest that ongoing debates regarding forest plantation–hydrology–climate change relationships need to broaden their scope to include changes in regional rainfall patterns and shifts in regional economic activity. This approach is likely to provide a more realistic assessment of plantation forests in a dynamic regional context, and offer more resilient strategies for regional landscape and catchment management under conditions of high variability in rainfall patterns.     

Mass transfer coefficients for volatilization of polychlorinated biphenyls from the Hudson River,New York measured using micrometeorological approaches

Air–water exchange is an important process controlling the fate of many organic chemicals in the environment. Modeling this process is hampered by the lack of direct observations. Thus, the purpose of this work was to derive direct measurements of the mass transfer coefficients for air–water exchange (v_aw) of polychlorinated biphenyls (PCBs) that may be used to check the validity of values derived from tracer gas experiments. v_aw values for PCBs were determined using previously published turbulent fluxes divided by the corresponding dissolved phase concentrations. The median v_aw values for each homolog decreased with increasing molecular weight and ranged from 0.29 for hexachlorobiphenyls to 2.2 m d^?1 for monochlorobiphenyls with a propagated uncertainty of about 70%, lower than in previous studies. Due to relatively low wind speeds and possible sorption of PCBs to colloids, these numbers may be biased low. These field measurements of v_aw differ by as much as a factor of 23 from predictions based on the widely-used Whitman two-film model. Therefore a new formulation for the calculation of v_aw based on field measurements is needed. This study demonstrates that micrometeorological approaches are a viable option for the measurement of v_aw for hydrophobic organics such as PCBs and should be used to generate enough field data on the air–water exchange of hydrophobic organics to allow the development of new predictive models.     

The Effect of Nucleating Particulates on Photochemical Aerosol Formation

The role of nucleating particulates in the formation of photochemical aerosols has been studied in a steady, laminar flow of ultrafiltered air containing NO₂ and octene-1 in the concentration range of (30 to 170 ppm) when subjected to intense irradiation under isothermal conditions. The particulates consisted of monodisperse polystyrene latex (d = 0.36 μ.) in concentrations similar to those in the atmosphere (6 × 10¹ to 3 × 10³ cm^–3); the irradiation intensity varied between (6 to 40 × 10³ lumen/liter) and the mean exposure duration between 30 and 180 sec. Samples of the flow prior to and after its photoactivation were withdrawn either by an Aerosol Spectrometer (AS) or by a Royco Aerosol Photometer (PH). While these indications refer thus to the same system, they differ, because the photometric data include all colloidal components in the airborne state, whereas the counts obtained from the AS deposits refer only to the nucleated latex particles. The following pattern becomes evident: The photochemical reaction yields fractional products (less than three percent) which have the tendency to agglomerate (or polymerize) due to their relatively low volatility—independent of the presence or absence of nucleating particulates. In their presence, this reaction becomes kinetically more probable and thus faster, hence the accumulant formation occurs preferably on the nuclei and causes their growth such that, e.g., a 10-fold higher nuclei concentration will produce under the same conditions 10 times the accumulant mass while autonucleation is suppressed. The growth process appears thus principally different from that of fog formation by H₂O-condensation, whereas for identical super saturation it is inversely proportional to the nuclear concentration. In the absence of nuclei autonucleation, i.e., self-agglomeration, occurs at a much lesser reaction rate and higher photon demand. The growth rate of the nuclei, when present, depends on the concentration of the oxidation catalyst (NO₂), its interaction with the nuclei surface is indicated. Under identical conditions the mass of nuclear accumulant is directly proportional to the concentration of the reactive hydrocarbon, while the growth rate depends on the light intensity and the exposure duration. The findings indicate that density and nature of particulate matter present in an air mass prior or during photo-activation are—aside from the chemical reactant levels—of major significance in aerosol formation.     

Characterisation and fingerprinting of PCBs in flue gas and ash from waste incineration and in technical mixtures

Congener patterns of mono- to deca-chlorinated biphenyls (PC1-10B) were evaluated in (a) waste incineration flue gases collected in the post-combustion zone of a laboratory-scale fluidized-bed reactor, (b) ashes from two different MSW incineration plants, and (c) published data of eight Aroclor formulations. The congener patterns of the flue gases, ashes, and Aroclor mixtures clearly differed from each other, likely reflecting differences in formation pathways. The flue gas congener patterns were largely dominated by the least chlorinated congeners, whereas the ashes displayed more evenly distributed patterns. The most abundant congeners indicated a preference for 3,3',4,4'-oriented substitution, which may be related to de novo-type formation involving perylene. Principal component analysis confirmed that congener patterns differed among the three matrices and also distinguished flue gases collected at 200 °C from those collected at 300 °C and 450 °C. This distinction could be partly explained by the degree of chlorination, although the substitution status of the ortho-position, and substitution in the 3,3',4,4'-positions also seemed to be influential. Injecting biphenyl into the post-combustion zone of the reactor did not alter the patterns, indicating that availability of the backbone structure is not a limiting factor for PCB formation.     

Reductive debromination of nonabrominated diphenyl ethers by sodium borohydride and identification of octabrominated diphenyl ether products

A method was developed to study reductive transformation of highly brominated diphenyl ethers (BDEs). The method development is a part of a broader project where it will be used to determine the susceptibility of environmental pollutants to reductive conditions, in an attempt to create a scheme for determination of chemical’s persistence. This paper focuses on identification of octabrominated diphenyl ether transformation products from reductive debromination of the three nonabrominated diphenyl congeners (nonaBDE), BDE-206, -207 and -208. Sodium borohydride was used to explore the reductive debromination of the nonaBDEs. The transformation products were collected at two time-points and identified products were quantified by GC-MS. The reduction of the nonaBDEs lead primarily to debrominated products, mainly octaBDEs. The three nonabrominated DEs gave isomer-related transformation product patterns. BDE-207 and BDE-208 showed a propensity for ortho-debromination in the initial reaction step, while no discrimination between initial debromination positions was seen for BDE-206. All three nonabrominated DEs displayed a preferred initial debromination on the fully brominated DE ring.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.     

Biodegradable chelate enhances the phytoextraction of copper by Oenothera picensis grown in copper-contaminated acid soils

Oenothera picensis plants (Fragrant Evening Primrose) grow in the acid soils contaminated by copper smelting in the coastal region of central Chile. We evaluated the effects of the biodegradable chelate MGDA (methylglycinediacetic acid) on copper extraction by O. picensis and on leaching of copper through the soil profile, using an ex situ experiment with soil columns of varying heights. MGDA was applied in four rates: 0 (control), 2, 6 and 10 mmol plant⁻¹. MGDA application significantly increased biomass production and foliar concentration, permitting an effective increase in copper extraction, from 0.09 mg plant⁻¹ in the control, to 1.3 mg plant⁻¹ in the 6 and 10 mmol plant⁻¹ treatments. With 10 mmol plant⁻¹ rate of MGDA, the copper concentration in the leachate from the 30 cm columns was 20 times higher than in the control. For the 60 cm columns, copper concentration was 2 times higher than the control. It can be concluded that at increased soil depths, copper leaching would be minimal and that MGDA applications at the studied rates would not pose a high risk for leaching into groundwater. It can thus be stated that applications of MGDA are an effective and environmentally safe way to improve copper extraction by O. picensis in these soils.