Estimating the contribution of point sources to atmospheric metals using single-particle mass spectrometry

Single-particle mass spectra were collected using an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) during December of 2003 and February of 2004 at an industrially impacted location in East St. Louis, IL. Hourly integrated peak areas for twenty ions were evaluated for their suitability in representing metals/metalloids, particularly those reported in the US EPA Toxic Release Inventory (TRI). Of the initial twenty ions examined, six (Al, As, Cu, Hg, Ti, and V) were found to be unsuitable due to strong isobaric interferences with commonly observed organic fragments, and one (Be) was found to have no significant signal. The usability of three ions (Co, Cr, and Mn) was limited due to suspected isobaric interferences based on temporal comparisons with commonly observed organic fragments. The identity of the remaining ions (Sb, Ba, Cd, Ca, Fe, Ni, Pb, K, Se, and Zn) was substantiated by comparing their signals with the integrated hourly signals of one or more isotope ions. When compared with one-in-six day integrated elemental data as determined by X-ray fluorescence spectroscopy (XRF), the daily integrated ATOFMS signal for several metal ions revealed a semi-quantitative relationship between ATOFMS peak area and XRF concentrations, although in some cases comparison of these measurements were poor at low elemental concentrations/ion signals due to isobaric interferences. A method of estimating the impact of local point sources was developed using hourly integrated ATOFMS peak areas, and this method attributed as much as 85% of the concentration of individual metals observed at the study site to local point sources. Hourly surface wind data were used in conjunction with TRI facility emissions data to reveal likely point sources impacting metal concentrations at the study site and to illustrate the utility of using single-particle mass spectral data to characterize atmospheric metals and identify point sources.     

The shifting sea: from soft space to lively space

It is widely acknowledged that marine spatial planning (MSP) should be responsive to the dynamism of the marine environment and the relatively tenuous human relationship with the sea. However, MSP remains conceptualised within rationalistic terms that limit this potential. This article places MSP within the context of spatial theory that holds greater promise for developing more progressive practice. Firstly, the interrelation of MSP with current notions of soft space (less formal, cross-cutting spatialities) is explored, suggesting that MSP is expressing some of the geographical and institutional freedoms of soft space, and may contribute new insights to this concept. Secondly, a progressive framework is developed that builds upon soft space principles. This draws in, on the one hand, underlying relational understandings of space, and on the other hand, insights from marine contexts. This leads to a picture of marine space-being-planned as lively space, expressing, amongst other things, the sea’s materiality. This concept is illustrated through an application of the framework to a strategic MSP exercise for the Baltic Sea region. Finally, it is suggested that MSP itself should be reconceptualised as immersed into this spatial ontology, with the agents and practices of planning taking their place within the wider assemblage of marine actants and relations.     

Oxidation of bisphenol F (BPF) by manganese dioxide

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO₂ and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺ > Ca²⁺ > Mg²⁺ > Na⁺ and HPO₄²⁻ > Cl⁻ > NO₃⁻ ≈ SO₄²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.     

Removal mechanisms and fate of insecticides in constructed wetlands

Constructed wetlands (CWs), along with other vegetative systems, are increasingly being promoted as a mitigation practice to treat non-point source runoff to reduce contaminants such as pesticides. However, studies so far have mostly focused on demonstrating contaminant removal efficiency. In this study, using two operational CWs located in the Central Valley of California, we explored the mechanisms underlying the removal of pyrethroids and chlorpyrifos from agricultural runoff water, and further evaluated the likelihood for the retained pesticides to accumulate within the CWs over time.In the runoff water passing through the CWs, pyrethroids were associated overwhelmingly with suspended solids >0.7 μm, and the sorbed fraction accounted for 38-100% of the total concentrations. The derived K_d values for the suspended solids were in the order of 10⁴-10⁵, substantially greater than those reported for bulk soils and sediments. Distribution of pyrethroids in the wetland sediments was found to mimic organic carbon distribution, and was enriched in large particles that were partially decomposed plant materials, and clay-size particles (<2 μm). Retention of suspended particles, especially the very large particles (>250 μm) and the very fine particles, is thus essential in removing pyrethroids and chlorpyrifos in CWs. Under flooded and anaerobic conditions, most pyrethroids and chlorpyrifos showed moderate persistence, with DT₅₀ values between 106-353 d. However, the retained pyrethroids were very stable in dry and aerobic sediments between irrigation seasons, suggesting a possibility for accumulation over time. Therefore, the long-term ecological risks of CWs should be further understood before their wide adoption.     

Evaluation of Probes Used for Source Sampling of Hydrogen Fluoride

The body of information presented in this paper is directed to those individuals concerned with methods for the sampling and measurement of fluorides contained in stack gases produced during the manufacture of phosphate fertilizer or aluminum. An air stream containing gaseous hydrogen fluoride (HF), at concentrations of from 87 to 1700 µg F m^-3, was generated and passed through 193 to 198 cm lengths of Pyrex glass, type 316 stainless steel, TFE Teflon, and methyl methacrylate-coated aluminum probes at flow rates of 28 I min^-1. HF passing through the probes was collected in deionized water contained in a Greenburg-Smith impinger. The Teflon probe exhibited no loss of HF and no trend toward increased passage of HF with time. Significant amounts of fluoride were lost in 18 out of 20 tests with the methacrylate probe and in 4 out of 20 tests with the Pyrex and stainless steel probes. Trends toward increased passage of HF with time occurred with the latter three probe materials. The selective ion electrode and semiautomated methods gave equivalent results when samples were made alkaline to avoid sorption of fluoride by Tygon tubing used in the semiautomated method. These results demonstrated that a Teflon probe gave the most representative sample of gaseous HF. However, additional tests are needed before a final recommendation is made for a probe to sample fluorides in stack gases.     

Hg Vapor Emission from Broken Compact Fluorescent Lamps (CFLs) in an Acrylic Chamber

The United States Environmental Protection Agency/Environmental Response Team (US EPA/ERT), in collaboration with St. John's College, Dr. B. R. Ambedkar University, Agra, India, is conducting a study to determine Hg vapor emission rates resulting from broken compact fluorescent lamps (CFLs) in a residential setting. The overall objectives of the study are to determine Hg vapor emission data and provide homeowners with cleanup procedures and disposal options for broken CFLs. Most of the currently available CFLs in the US market are manufactured in China for US companies. Several different types of CFLs were purchased from local stores and their Hg content was determined. Based on previous studies, such as the 2011 study by Singhvi and colleagues, five popular spiral CFLs were selected for emission studies in an acrylic chamber. This study found that Hg vapor emissions from CFLs may be significantly greater than those from beads of liquid Hg with weights comparable to the Hg content of the CFLs. The average 24-hour Hg loss into the atmosphere from CFLs broken on a plastic surface ranged from 0.6% to 22% of the bulb content, while that for CFLs broken on carpet ranged from 2.6% to 28%. Projections for a 12 foot × 9.33 foot × 8 foot (25.4 m³) room based on the chamber measurements in this study indicate that CFL breakage in some household settings may produce 24-hour Hg concentrations above the 2000 Agency for Toxic Substances and Disease Registry (ATSDR) minimum risk level (MRL) of 0.2 μg/m³, for typical air exchange rates. This study also indicates that Hg emission may not be proportional to exposed surface area based on experiments using liquid Hg with different surface areas.     

Persistent organic pollutants in the atmosphere from urban and industrial environments in the Rhine Valley: PCBs, PCDD/Fs

Polychlorinated biphenyls (PCBs) and polychlorinated dibenzodioxin and furan (PCDD/F) concentrations in the atmosphere were analysed using passive air samplers (PAS) close to the Rhine River between France and Germany. Collectors were placed in industrial, urban, rural and remote areas (Vosges Mountains) between March 2009 and August 2010, and the mean PCB concentrations (sum of 22 congeners) were 3.3, 3.9, 4.1 and 1.4 ng?PAS^?1?day^?1, respectively. Two events during the sampling period were observed in April 2009 and February–March 2010 with the highest PCB concentrations found in the industrial area (19.6 ng?PAS^?1?day^?1). PCDD/F level were measured during these periods, and the maximum concentration observed was from 37.5 fg?WHO?PAS^?1?day^?1     

Natural and anthropogenic influences on a red-crowned crane habitat in the Yellow River Delta Natural Reserve, 1992–2008

This study aims to assess the relative importance of natural and anthropogenic variables on the change of the red-crowned crane habitat in the Yellow River Nature Reserve, East China using multitempopral remote sensing and geographic information system. Satellite images were used to detect the change in potential crane habitat, from which suitable crane habitat was determined by excluding fragmented habitat. In this study, a principal component analysis (PCA) with seven variables (channel flow, rainfall, temperature, sediment discharge, number of oil wells, total length of roads, and area of settlements) and linear regression analyses of potential and suitable habitat against the retained principal components were applied to explore the influences of natural and anthropogenic factors on the change of the red-crowned crane habitat. The experimental results indicate that suitable habitat decreased by 5,935 ha despite an increase of 1,409 ha in potential habitat from 1992 to 2008. The area of crane habitat changed caused by natural drivers such as progressive succession, retrogressive succession, and physical fragmentation is almost the same as that caused by anthropogenic forces such as land use change and behavioral fragmentation. The PCA and regression analyses revealed that natural factors (e.g., channel flow, rainfall, temperature, and sediment discharge) play an important role in the crane potential habitat change and human disturbances (e.g., oil wells, roads, and settlements) jointly explain 51.8 % of the variations in suitable habitat area, higher than 48.2 % contributed by natural factors. Thus, it is vital to reduce anthropogenic influences within the reserve in order to reverse the decline in the suitable crane habitat.