Simulated use and wash-off release of decamethylcyclopentasiloxane used in anti-perspirants

The cyclic volatile methylsiloxane, decamethylcyclopentasiloxane (D₅) is used in a large variety of personal care products. Based on the physical–chemical properties of D₅, it is likely that losses due to volatilisation may strongly influence the levels entering the aquatic environment. The aim of this study was to quantify the amount of D₅ in waste wash water, after typical application and use in a range of deodorant and anti-perspirant (AP) products. Results implied significant losses after a 24 h period (>99.9%), and suggest that the use of D₅ in leave-on products, such as deodorants/AP is not likely to contribute a significant down-the-drain emission source. An illustrative example is presented, based on data reporting the use of D₅ in a range of personal care products (both wash-off and leave-on), which suggests that the contribution of D₅ used in wash-off products to the aquatic environment may be considerably more significant. Limitations associated with our understanding of the actual D₅ inclusion levels in the products, the market share of the products containing D₅, and the variability of consumer habits, are identified as data gaps that need to be addressed in order to better refine down-the-drain emission estimates.     

Positive vs. false detection: A comparison of analytical methods and performance for analysis of cyclic volatile methylsiloxanes (cVMS) in environmental samples from remote regions

Contamination and analytical variation can significantly hinder trace analysis of cyclic methyl volatile siloxanes (cVMS); potentially resulting in the report of false positives at concentrations approaching detection limits. To assess detection and variation associated with trace cVMS analysis in environmental matrices, a co-operative laboratory comparison for the analysis of octametylcyclotetrasiloxane (D4), decamethylcylcopentasiloxane (D5), and dodecametylcyclohexasiloxane (D6) in sediment and biota from the Svalbard Archipelago was conducted. Two definitions of detection limits were evaluated in this study; method detection limits (MDL, matrix defined) and limits of detection (LOD, solvent defined). D5 was the only cVMS detected above both LOD (0.08–0.81 ng g⁻¹ ww) and MDL (0.47–2.36 ng g⁻¹ ww) within sediment by all laboratories where concentrations ranged from 0.55 to 3.91 ng g⁻¹ ww. The percentage of positive detects for D5 decreased by 80% when MDL was defined as the detection limit. D5 was also detected at the highest frequency among all laboratories in fish liver with concentrations ranging from 0.72 to 345 ng g⁻¹ ww. Similar to sediment, percentage of positive detects for D5 decreased by 60% across all laboratories for fish livers when using MDL (0.68–3.49 ng g⁻¹ ww). Similar observations were seen with both D4 and D6, indicating that sample matrix significantly contributes to analytical response variation. Despite differences in analytical methods used between laboratories, good agreement was obtained when using MDL to define detection limits. This study shows the importance of incorporating variation introduced by sample matrices into detection limit calculations to insure data accuracy of cVMS at low concentrations.     

Exploring the Biodegradation Potential of Polyethylene Through a Simple Chemical Test Method

Oxidatively degradable polyethylene is finding widespread use, particularly in applications such as single use packaging and agriculture. However, the key question which still remains unanswered is the ultimate fate and biodegradability of these polymers. During a short-time frame only the oxidized low molecular weight fraction will be amenable to significant biodegradation. The short-time frame biodegradation potential of different LDPE-transition metal formulations was, thus, explored through a simple chemical extraction of oxidized fraction. In addition the effectiveness of different transitions metals was evaluated by comparing the extractable fractions. Blown LDPE films modified with different transition metal based pro-oxidants were thermo-oxidized at 60 °C over extended periods. The structural changes occurring in the polymer were monitored and the oxidized degradation products formed as a result of the aging process were estimated by extractions with water and acetone. The extractable fraction first increased to approximately 22 % as a result of thermo-oxidative aging and then leveled off. The extractable fraction was approximately two times higher after acetone extraction compared to extraction with water and as expected, it was higher for the samples containing pro-oxidants. Based on our results in combination with existing literature we propose that acetone extractable fraction gives an estimation of the maximum short-term biodegradation potential of the material, while water extractable fraction indicates the part that is easily accessible to microorganisms and rapidly assimilated. The final level of biodegradation under real environmental conditions will of course be highly dependent on the specific environment, material history and degradation time.     

A Visual Basic simulation software tool for performance analysis of a membrane-based advanced water treatment plant

A Visual Basic simulation software (WATTPPA) has been developed to analyse the performance of an advanced wastewater treatment plant. This user-friendly and menu-driven software is based on the dynamic mathematical model for an industrial wastewater treatment scheme that integrates chemical, biological and membrane-based unit operations. The software-predicted results corroborate very well with the experimental findings as indicated in the overall correlation coefficient of the order of 0.99. The software permits pre-analysis and manipulation of input data, helps in optimization and exhibits performance of an integrated plant visually on a graphical platform. It allows quick performance analysis of the whole system as well as the individual units. The software first of its kind in its domain and in the well-known Microsoft Excel environment is likely to be very useful in successful design, optimization and operation of an advanced hybrid treatment plant for hazardous wastewater.     

An assessment of urban vulnerability in the Amazon Delta and Estuary: a multi-criterion index of flood exposure,socio-economic conditions and infrastructure

The Amazon Delta and Estuary (ADE) is a region of continental and global ecological importance. Controversy, many of the basic infrastructure and services essential for quality of life and sustainable development of this delta are absent. Using a conceptual model to define socio-economic vulnerability in the urban ADE, a thorough assessment of indicators including sanitation services, housing conditions, household income, population, flood risk and unplanned settlements was conducted in 41 cities at the census sector scale (n = 2938). A multi criterion index was applied to classify urban vulnerability from three dimensions: flood exposure, socio-economic sensitivity and infrastructure. This is the first study to examine urban vulnerability within and between urban areas of the ADE. Results indicated that most of the urban sectors of the ADE are exposed to potential risks due to a combination of flood hazards, poverty and basic structural deficiencies such as insufficient drinking water or inadequate waste water collection, with several sectors being afflicted by similar problems. The assessment of vulnerability indicates that 60–90 % of the urban population live in conditions of moderate to high degree of vulnerability. The ADE cities presented a pattern where vulnerability increases from city center to their newly developed urban areas. Inadequate planning coupled with rapid urbanization has contributed to the development of unplanned settlements in almost half of the urban sectors of the ADE. Combined, these factors contribute to widespread socio-economic vulnerability along the urban spaces of the ADE, increasing exposure to health risks and more frequent seasonal and stochastic events such as storm surges and high flooding levels.     

Incinerator Conference Covers Emissions Control Aspects

The success of the application of computer modeling to decision-making will depend on the degree to which the scientifically valid “cause-and-effect” features of the air pollution system are represented. For this reason, dynamic simulation models are to be preferred to statistical and empirical models. A digital simulation model based on a stoichiometrically logical chemical mechanism and trajectory estimating routines was constructed, using Los Angeles source, meteorological and geographic input. The basic physical concept underlying the simulation model is the process of evolution of photochemical pollution in a parcel of air as it moves in a dynamic urban emission/meteorological environment along a given urban wind trajectory. Both the photochemical evolution and the trajectory are numerically integrated by a standard linear multistep predictor-corrector method. Concentrations of photochemical reactants and products (i.e., primary and secondary contaminants) are determined by this numerical integration, which also includes appropriate terms for relevant effects. In five preliminary validation runs, simulated NO₂, NO, and O₃ values were within 20% or 0.05 ppm of those observed at air monitoring stations located near the termini of the runs. The trajectories were plotted on the basis of hourly meteorological data for 22 stations. Six control strategy exercises were conducted to illustrate the application of the model to problem-solving situations.     

Characterization of Emissions of Volatile Organic Compounds from Interior Alkyd Paint

ABSTRACT

Alkyd paint continues to be used indoors for application to wood trim, cabinet surfaces, and some kitchen and bathroom walls. Alkyd paint may represent a significant source of volatile organic compounds (VOCs) indoors because of the frequency of use and amount of surface painted. The U.S. Environmental Protection Agency (EPA) is conducting research to characterize VOC emissions from paint and to develop source emission models that can be used for exposure assessment and risk management. The technical approach for this research involves both analysis of the liquid paint to identify and quantify the VOC contents and dynamic small chamber emissions tests to characterize the VOC emissions after application. The predominant constituents of the primer and two alkyd paints selected for testing were straight-chain alkanes (C9–C12); C8–C9 aromatics were minor constituents. Branched chain alkanes were the predominant VOCs in a third paint. A series of tests were performed to evaluate factors that may affect emissions following application of the coatings. The type of substrate (glass, wallboard, or pine board) did not have a substantial impact on the emissions with respect to peak concentrations, the emissions profile, or the amount of VOC mass emitted from the paint. Peak concentrations of total volatile organic compounds (TVOCs) as high as 10,000 mg/m³ were measured during small chamber emissions tests at 0.5 air exchanges per hour (ACH). Over 90% of the VOCs were emitted from the primer and paints during the first 10 hr following application. Emissions were similar from paint applied to bare pine board, a primed board, or a board previously painted with the same paint. The impact of other variables, including film thickness, air velocity at the surface, and air-exchange rate (AER) were consistent with theoretical predictions for gas-phase, mass transfer-controlled emissions. In addition to the alkanes and aromatics, aldehydes were detected in the emissions during paint drying. Hexanal, the predominant aldehyde in the emissions, was not detected in the liquid paint and was apparently an oxidation product formed during drying. This paper summarizes the results of the product analyses and a series of small chamber emissions tests. It also describes the use of a mass balance approach to evaluate the impact of test variables and to assess the quality of the emissions data.     

Indoor Emissions from Conversion Varnishes

ABSTRACT

Conversion varnishes are two-component, acid-catalyzed varnishes that are commonly used to finish cabinets. They are valued for their water and stain resistance, as well as their appearance. They have been found, however, to contribute to indoor emissions of organic compounds. For this project, three commercially available conversion varnish systems were selected. A U.S. Environmental Protection Agency (EPA) Method 24 analysis was performed to determine total volatile content, and a sodium sulfite titration method was used to determine uncombined (free) formaldehyde content of the varnish components. The resin component was also analyzed by gas chromatography/mass spectroscopy (GC/MS) (EPA Method 311 with an MS detector) to identify individual organic compounds. Dynamic small chamber tests were then performed to identify and quantify emissions following application to coupons of typical kitchen cabinet wood substrates, during both curing and aging. Because conversion varnishes cure by chemical reaction, the compounds emitted during curing and aging are not necessarily the same as those in the formulation. Results of small chamber tests showed that the amount of formaldehyde emitted from these coatings was 2.3–8.1 times the amount of free formaldehyde applied in the coatings. A long-term test showed a formaldehyde emission rate of 0.17 mg/m²/hr after 115 days.     

Transport impacts on atmosphere and climate: Shipping

Emissions of exhaust gases and particles from oceangoing ships are a significant and growing contributor to the total emissions from the transportation sector. We present an assessment of the contribution of gaseous and particulate emissions from oceangoing shipping to anthropogenic emissions and air quality. We also assess the degradation in human health and climate change created by these emissions. Regulating ship emissions requires comprehensive knowledge of current fuel consumption and emissions, understanding of their impact on atmospheric composition and climate, and projections of potential future evolutions and mitigation options. Nearly 70% of ship emissions occur within 400 km of coastlines, causing air quality problems through the formation of ground-level ozone, sulphur emissions and particulate matter in coastal areas and harbours with heavy traffic. Furthermore, ozone and aerosol precursor emissions as well as their derivative species from ships may be transported in the atmosphere over several hundreds of kilometres, and thus contribute to air quality problems further inland, even though they are emitted at sea. In addition, ship emissions impact climate. Recent studies indicate that the cooling due to altered clouds far outweighs the warming effects from greenhouse gases such as carbon dioxide (CO₂) or ozone from shipping, overall causing a negative present-day radiative forcing (RF). Current efforts to reduce sulphur and other pollutants from shipping may modify this. However, given the short residence time of sulphate compared to CO₂, the climate response from sulphate is of the order decades while that of CO₂ is centuries. The climatic trade-off between positive and negative radiative forcing is still a topic of scientific research, but from what is currently known, a simple cancellation of global mean forcing components is potentially inappropriate and a more comprehensive assessment metric is required. The CO₂ equivalent emissions using the global temperature change potential (GTP) metric indicate that after 50 years the net global mean effect of current emissions is close to zero through cancellation of warming by CO₂ and cooling by sulphate and nitrogen oxides.