Carbon isotope forensics for methane source identification

Methane (CH₄) in ecosystems originates from ancient petroleum formed deep within the earth and/or via microbial fermentation of organic carbon and subsequent reduction of carbon dioxide (CO₂). Given the complexity of different ecosystems, origins of CH₄ present can be difficult to determine. This issue was realized in a situation where an antimethanogenic in situ chemical reduction (ISCR) remedial amendment containing organic carbon plus zero‐valent iron was applied to treat chlorinated solvents in groundwater at a former dry cleaner facility. The technology rapidly and effectively reduced the concentration of tetrachloroethene in groundwater thus meeting project goals without the stoichiometric accumulation of catabolites such as trichloroethene (TCE), cis‐1,2‐dichloroethene, or vinyl chloride and without excessive methanogenesis (e.g., <2 mg/L) in the treated area. However, approximately 9 months after treatment, increased levels of CH₄ (from 5 to 10 mg/L) were observed downgradient from the treated area. The applied remedial amendment contained approximately 60% (weight basis) fermentation organic carbon and was therefore a potential source of this CH₄. However, there was <500 mg/L total organic carbon in groundwater emanating from the upgradient treatment area which was unlikely sufficient to produce that much CH₄. Moreover, the soil gas also contained benzene, toluene, ethylbenzene, and xylenes and other gasoline constituents. These data suggested that the presence of three gasoline/diesel underground storage tanks that were previously closed in place with no active remediation performed could be the source of elevated CH₄. Thirdly, there were sewer lines, utilities, multiple gasoline stations, and industrial activities in the immediate area. With an initial assumption that CH₄ source(s) could include the ISCR amendment over stimulation of production, gasoline sourced CH₄ from nearby leaking lines, or sewage from local fractured pipes, carbon isotope analyses—radiocarbon (Δ¹⁴C) and stable carbon (δ¹³C)—were coupled with CH₄ and CO₂ concentration data from groundwater samples to determine the origin of respired carbon. The δ¹³C range for carbon sources respired in the process would be approximately ?26.5‰ to ?33.0‰ for the ISCR amendment and total petroleum hydrocarbons (TPH) residuals, respectively. Δ¹⁴C is approximately 0‰ and ?999‰ for the ISCR amendment (young carbon) and TPH (old carbon), respectively. The isotopic signature of respired gasses confirmed that elevated CH₄ downgradient of the treated area originated primarily from sewer gasses (or fermentation of liquids released from sewer lines). This study provides an overview of the capability to apply carbon isotope geochemistry to confirmation of remedial protocols and sources of anthropogenic carbon pools that conclusively identify the origin of CH₄ in a complex ecosystem undergoing a remedial action.     

Particulate matter emissions of different brands of mentholated cigarettes

Inhaling particulate matter (PM) in environmental tobacco smoke (ETS) endangers the health of nonsmokers. Menthol, an additive in cigarettes, attenuates respiratory irritation of tobacco smoke. It reduces perceptibility of smoke and therefore passive smokers may inhale ETS unnoticed. To investigate a possible effect of menthol on PM concentrations (PM₁₀, PM_2.5, and PM₁), ETS of four mentholated cigarette brands (Elixyr Menthol, Winston Menthol, Reyno Classic, and Pall Mall Menthol Blast) with varying menthol content was analyzed. ETS was generated in a standardized way using an automatic environmental tobacco smoke emitter (AETSE), followed by laser aerosol spectrometry. This analysis shows that the tested cigarette brands, despite having different menthol concentrations, do not show differences with regard to PM emissions, with the exception of Reyno Classic, which shows an increased emission, although the menthol level ranged in the midfield. More than 90% of the emitted particles had a size smaller than or equal to 1 µm. Regardless of the menthol level, the count median diameter (CMD) and the mass median diameter (MMD) were found to be 0.3 µm and 0.5 µm, respectively. These results point out that there is no effect of menthol on PM emission and that other additives might influence the increased PM emission of Reyno Classic.

Implications: Particulate matter (PM) in ETS endangers the health of nonsmokers and smokers. This study considers the effect of menthol, an additive in cigarettes, on PM emissions. Does menthol increase the amount of PM? Due to the exposure to secondhand smoke nearly 900,000 people die each year worldwide. The aim of the study is to measure the particle concentration (L^?1), mass concentration (µg m^?3), and dust mass fractions shown as PM₁₀, PM_2.5, and PM₁ of five different cigarette brands, including four with different menthol concentrations and one menthol-free reference cigarette, in a well-established standardized system.     

Air quality measurements—From rubber bands to tapping the rainbow

It is axiomatic that good measurements are integral to good public policy for environmental protection. The generalized term for “measurements” includes sampling and quantitation, data integrity, documentation, network design, sponsorship, operations, archiving, and accessing for applications. Each of these components has evolved and advanced over the last 200 years as knowledge of atmospheric chemistry and physics has matured. Air quality was first detected by what people could see and smell in contaminated air. Gaseous pollutants were found to react with certain materials or chemicals, changing the color of dissolved reagents such that their light absorption at selected wavelengths could be related to both the pollutant chemistry and its concentration. Airborne particles have challenged the development of a variety of sensory devices and laboratory assays for characterization of their enormous range of physical and chemical properties. Advanced electronics made possible the sampling, concentration, and detection of gases and particles, both in situ and in laboratory analysis of collected samples. Accurate and precise measurements by these methods have made possible advanced air quality management practices that led to decreasing concentrations over time. New technologies are leading to smaller and cheaper measurement systems that can further expand and enhance current air pollution monitoring networks.

Implications: Ambient air quality measurement systems have a large influence on air quality management by determining compliance, tracking trends, elucidating pollutant transport and transformation, and relating concentrations to adverse effects. These systems consist of more than just instrumentation, and involve extensive support efforts for siting, maintenance, calibration, auditing, data validation, data management and access, and data interpretation. These requirements have largely been attained for criteria pollutants regulated by National Ambient Air Quality Standards, but they are rarely attained for nonroutine measurements and research studies.     

Determination of deployment specific chemical uptake rates for SDB-RPD Empore disk using a passive flow monitor (PFM)

The use of the adsorbent styrenedivinylbenzene-reverse phase sulfonated (SDB-RPD) Empore disk in a chemcatcher type passive sampler is routinely applied in Australia when monitoring herbicides in aquatic environments. One key challenge in the use of passive samplers is mitigating the potentially confounding effects of varying flow conditions on chemical uptake by the passive sampler. Performance reference compounds (PRCs) may be applied to correct sampling rates (R_s) for site specific changed in flow and temperature however evidence suggests the use of PRCs is unreliable when applied to adsorbent passive samplers. The use of the passive flow monitor (PFM) has been introduced for the assessment of site-specific changes in water flow. In the presented study we have demonstrated that the R_s at which both atrazine and prometryn are accumulated within the SDB-RPD-Empore disk is dependent on the flow conditions. Further, the calibration of the measured R_s for chemical uptake by the SDB-RPD-Empore disk to the mass lost from the PFM has shown that the PFM provides an accurate measure of R_s for flow velocities from 0 to 16 cm s⁻¹. Notably, for flow rates >16 cm s⁻¹, a non linear increase in the R_s of both herbicides was observed which indicates that the key resistance to uptake into the SDB-RPD Empore disk is associated with the diffusion through the overlying diffusion limiting membrane. Overall the greatest uncertainty remains at very low flow conditions, which are unlikely to often occur in surface waters. Validation of the PFM use has also been undertaken in a limited field study.     

The performance of passive flow monitors and phosphate accumulating passive samplers when exposed to pulses in external water flow rate and/or external phosphate concentrations

Passive samplers are typically calibrated under constant flow and concentration conditions. This study assessed whether concentration and/or flow pulses could be integrated using a phosphate passive sampler (P-sampler). Assessment involved three 21-day experiments featuring a pulse in flow rate, a pulse of filterable reactive phosphate (FRP) concentration and a simultaneous concentration and flow pulse. FRP concentrations were also determined by parallel grab sampling and the P-sampler calibrated with passive flow monitors (PFMs) and direct measurement of flow rates. The mass lost from the PFM over the deployment periods predicted water velocity to within 5.1, 0.48 and 7.1% when exposed to a flow rate pulse (7.5-50 cm s⁻¹), concentration pulse (5-100 μg P L⁻¹), or both simultaneously. For the P-sampler, good agreement was observed between the grab and passive measurements of FRP concentration when exposed to a pulse in flow (6% overestimation) or concentration (2% underestimation).     

Environmental issues and management strategies for waste electronic and electrical equipment

Issues surrounding the impact and management of discarded or waste electronic and electrical equipment (WEEE) have received increasing attention in recent years. This attention stems from the growing quantity and diversity of electronic and electrical equipment (EEE) used by modern society, the increasingly rapid turnover of EEE with the accompanying burden on the waste stream, and the occurrence of toxic chemicals in many EEE components that can pose a risk to human and environmental health if improperly managed. In addition, public awareness of the WEEE or "e-waste" dilemma has grown in light of popular press features on events such as the transition to digital television and the exportation of WEEE from the United States and other developed countries to Africa, China, and India, where WEEE has often not been managed in a safe manner (e.g., processed with proper safety precautions, disposed of in a sanitary landfill, combusted with proper air quality procedures). This paper critically reviews current published information on the subject of WEEE. The definition, magnitude, and characteristics of this waste stream are summarized, including a detailed review of the chemicals of concern associated with different components and how this has changed and continues to evolve over time. Current and evolving management practices are described (e.g., reuse, recycling, incineration, landfilling). This review discusses the role of regulation and policies developed by governments, institutions, and product manufacturers and how these initiatives are shaping current and future management practices.     

Montana’s Clark Fork River Basin Task Force: A Vehicle for Integrated Water Resources Management?

This article examines what is generally considered to be an unattainable goal in the western United States: integrated water resources management (IWRM). Specifically, we examine an organization that is quite unique in the West, Montana’s Clark Fork River Basin Task Force (Task Force), and we analyze its activities since its formation in 2001 to answer the question: are the activities and contributions of the Task Force working to promote a more strongly integrated approach to water resources management in Montana? After reviewing the concepts underlying IWRM, some of the issues that have been identified for achieving IWRM in the West, and the Montana system of water right allocation and issues it faces, we adapt Mitchell’s IWRM framework and apply it to the analysis of the Task Force’s activities in the context of IWRM. In evaluating the physical, interaction, and protocol/planning/policy components of IWRM, we find that the Task Force has been contributing to the evolution of Montana’s water resources management towards this framework, though several factors will likely continue to prevent its complete realization. The Task Force has been successful in this regard because of its unique nature and charge, and because of the authority and power given it by successive Montana legislatures. Also critical to the success of the organization is its ability to help translate into policy the outcomes of legal and quasi-judicial decisions that have impacted the state’s water resources management agency.     

Persistent organochlorine pesticides in human milk samples from Australia

Human milk has been used as a surrogate for the assessment of body burden and exposure to persistent lipophilic organochlorine pesticides (OCPs). With the exception of restricted use of mirex, the use of persistent, lipophilic OCPs has been banned in Australia since the 1980s. The decline of human body burden of OCPs following their ban in many industrialised countries is well recorded worldwide from the 1970s until the 1990s though little is known on whether these trends are continuing. In this study, 157 human milk samples collected during 2002 and 2003 as well as 24 samples collected in 1993 were analysed as 20 regional pools for 17 OCPs. OCPs were detected in all pooled human milk samples from 2002/03 typically with highest concentrations of p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) (mean+/-standard deviation; median concentration 311+/-174; 279 ng g(-1) lipid) followed by beta-hexachlorocyclohexane (beta-HCH) (80+/-173; 21 ng g(-1) lipid). Other OCPs consistently detected included dieldrin (16+/-6; 17 ng g(-1) lipid), hexachlorobenzene (HCB) (18+/-16; 14 ng g(-1) lipid), transnonachlor (11+/-5; 9 ng g(-1) lipid) and p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) (9+/-6; 7 ng g(-1) lipid). The results from this study indicated that following a substantial decline of OCP concentrations from the early 1980s to the 1990s, little decline could be observed since then. Furthermore the use of multivariate statistics indicated some regional trends with slightly higher levels of the broadly used insecticides DDT and HCH in both historic and recent samples from Melbourne, whereas, sample pools collected from mothers that lived in rural Queensland and New South Wales as well as Adelaide and Sydney showed comparatively higher levels of heptachlor and dieldrin - both of which have been used for termite treatment. These results indicate that even 20 years after the discontinuation of usage, historical use of OCPs rather than exposure via global transport of OCPs is responsible for continuous low exposure in Australia.     

How to consider engineered nanomaterials in major accident regulations?

Major accident regulations aim at protecting the population and the environment from possible accidental releases of chemicals. To achieve this goal, the regulations need to be reassessed in light of the development of new technologies. A currently rapidly growing new technology is nanotechnology, and engineered nanomaterials (ENM) are already produced and used in commercial products. The aim of this work was therefore to evaluate the current knowledge on human and ecotoxicology of ENM and their release and behavior in the environment in the context of major accident prevention. Nano-specific release paths are not to be expected. The established safety standards in the chemical industry are also applicable to ENM, especially the separate storage of flammable solvents and detention reservoirs. The potential of a release to the environment of ENM in powder form is larger than for suspensions; however, it can be minimized by safety measures established for conventional dusts. The considered human toxicology studies show that to date not conclusive enough answers regarding the toxicity of ENM can be made. The effects are dependent not only on the material itself but more on the functionalization, surface reactivity, size, and form. The acute ecotoxicity of ENM seems to be similar to the one of the corresponding microparticles (TiO₂) or the respective dissolved ions (Ag, Zn) with the exception of photocatalytically active nano-TiO₂, which has an increased toxicity. In order to guarantee that all ENM are included in the existing major accident regulations, different classification options are possible and the advantages and disadvantages are discussed. An important step will be the compulsory inclusion of nano-specific data in the Material Safety Data Sheets that serve as the basic medium to transfer information from the manufacturer to downstream users and authorities. We also call for a regular monitoring of the production and uses for ‘high production volume ENM’ that could have the largest implications for major accident regulations.