Formation of indoor nitrous acid (HONO) by light-induced NO<Subscript>2</Subscript> heterogeneous reactions with white wall paint

Gaseous nitrogen dioxide (NO₂) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO₂ levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO₂ with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO₂ with selected indoor paint surfaces in the presence of light (300 nm?<?λ?<?400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m^?2), an increase of HONO production rate of up to 8.6?·?10⁹ molecules cm^?2 s^?1 was observed at [NO₂]?=?60 ppb and 50 % relative humidity (RH). At higher light intensity of 10.6 (W m^?2), the HONO production rate increased to 2.1?·?10¹⁰ molecules cm^?2 s^?1. A high NO₂ to HONO conversion yield of up to 84 % was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO₂ heterogeneous reactions.     

Films Made by Blending Poly(ε-Caprolactone) with Starch and Flour from Sagu Rhizome Grown at the Venezuelan Amazons

Starch-based composite films have been proposed as food packaging. In this context, the study of non-conventional starch sources (sagu, Canna edulis Kerr) has worldwide special attention, because these materials can impart different properties as carbohydrate polymers. A thorough study of the matrices used (sagu starch and flour) was carried out. In the same way, thermoplastic starch (TPS)/PCL blend and thermoplastic flour (TFS)/PCL blend were obtained by melt mixing followed by compression moulding containing glycerol as plasticizer. In this study, chemical composition of the matrices and their properties were related with the properties of the developed films. Moisture content, water solubility, X-ray diffraction, thermogravimetric analysis and mechanical and microstructural properties were evaluated in the films. Taking into account the results, the sagu flour has great potential as starchy source for food packaging applications. However, concretely the flour had lower compatibility with the PCL compared to the starch/PCL blend.     

Radical precursors and related species from traffic as observed and modeled at an urban highway junction

Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals and are believed to favor ozone formation significantly. Traffic emission data for both compounds are scarce and mostly outdated. A better knowledge of today's HCHO and HONO emissions related to traffic is needed to refine air quality models. Here the authors report results from continuous ambient air measurements taken at a highway junction in Houston, Texas, from July 15 to October 15, 2009. The observational data were compared with emission estimates from currently available mobile emission models (MOBILE6; MOVES [MOtor Vehicle Emission Simulator]). Observations indicated a molar carbon monoxide (CO) versus nitrogen oxides (NO_x) ratio of 6.01 ± 0.15 (r ² = 0.91), which is in agreement with other field studies. Both MOBILE6 and MOVES overestimate this emission ratio by 92% and 24%, respectively. For HCHO/CO, an overall slope of 3.14 ± 0.14 g HCHO/kg CO was observed. Whereas MOBILE6 largely underestimates this ratio by 77%, MOVES calculates somewhat higher HCHO/CO ratios (1.87) than MOBILE6, but is still significantly lower than the observed ratio. MOVES shows high HCHO/CO ratios during the early morning hours due to heavy-duty diesel off-network emissions. The differences of the modeled CO/NO_x and HCHO/CO ratios are largely due to higher NO_x and HCHO emissions in MOVES (30% and 57%, respectively, increased from MOBILE6 for 2009), as CO emissions were about the same in both models. The observed HONO/NO_x emission ratio is around 0.017 ± 0.0009 kg HONO/kg NO_x which is twice as high as in MOVES. The observed NO₂/NO_x emission ratio is around 0.16 ± 0.01 kg NO₂/kg NO_x, which is a bit more than 50% higher than in MOVES. MOVES overestimates the CO/CO₂ emission ratio by a factor of 3 compared with the observations, which is 0.0033 ± 0.0002 kg CO/kg CO₂. This as well as CO/NO_x overestimation is coming from light-duty gasoline vehicles.

Implications: Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals that ultimately contribute to ozone formation. There still exist uncertainties in emission sources of HONO and HCHO and thus regional air quality modeling still tend to underestimate concentrations of free radicals in the atmosphere. This paper demonstrates that the latest U.S. Environmental Protection Agency (EPA) traffic emission model MOVES still shows significant deviations from observed emission ratios, in particular underestimation of HCHO/CO and HONO/NO_x ratios. Improving the performance of MOVES may improve regional air quality modeling.     

Advances in the recycling of plastic wastes for metallurgical coke production

This paper aims to provide useful knowledge on the use of plastic wastes as additives to coking blends for the production of metallurgical coke. It focuses on the influence that the composition of plastic wastes has upon the development of coal fluidity, the generation of pressure during the coking process and the quality of the cokes produced in a semipilot oven. Several plastic mixtures of two types of thermoplastics, polyolefins (HDPE, LDPE and PP) and aromatic polymers such as PET, were used. The overall addition rate of plastics to a medium-fluid coal blend was 2 wt%. It is shown that polyolefins, weaker modifiers of coal fluidity, may be employed to maintain coke quality but that they have a negative effect on the generation of coking pressure, while plastics of the aromatic type such as PET, a strong modifier of coal fluidity, can be used to counteract the generation of coking pressure. From the results, it is deduced that the protocol developed is useful for determining the optimum amount of each type of polymer (polyolefins and aromatic polymers) that is needed in order to counteract the generation of pressure during the coking process and to maintain the quality of the cokes.     

Temporal and Spatial Trends in Nutrient and Sediment Loading to Lake Tahoe,California‐Nevada,USA

Since 1980, the Lake Tahoe Interagency Monitoring Program (LTIMP) has provided stream‐discharge and water quality data—nitrogen (N), phosphorus (P), and suspended sediment—at more than 20 stations in Lake Tahoe Basin streams. To characterize the temporal and spatial patterns in nutrient and sediment loading to the lake, and improve the usefulness of the program and the existing database, we have (1) identified and corrected for sources of bias in the water quality database; (2) generated synthetic datasets for sediments and nutrients, and resampled to compare the accuracy and precision of different load calculation models; (3) using the best models, recalculated total annual loads over the period of record; (4) regressed total loads against total annual and annual maximum daily discharge, and tested for time trends in the residuals; (5) compared loads for different forms of N and P; and (6) tested constituent loads against land use‐land cover (LULC) variables using multiple regression. The results show (1) N and P loads are dominated by organic N and particulate P; (2) there are significant long‐term downward trends in some constituent loads of some streams; and (3) anthropogenic impervious surface is the most important LULC variable influencing water quality in basin streams. Many of our recommendations for changes in water quality monitoring and load calculation methods have been adopted by the LTIMP.     

Genetic, morphological, and chemical divergence in the sponge genus Latrunculia (Porifera: Demospongiae) from New Zealand

We undertook a comprehensive study of Latrunculia in New Zealand to determine the relationship between taxonomic, environmental, and chemical variation within the genus. Sponges were collected from five locations around New Zealand: Three Kings Islands, Tutukaka, Wellington, Kaikoura, and Doubtful Sound. Allozyme electrophoresis at nine polymorphic loci indicated that sponges from each geographic location were genetically distinct, and that they displayed genetic differences of the magnitude usually associated with reproductively isolated species (Nei's D between locations =0.375-2.476). Additionally, the comparisons revealed that the green and brown colour morphs of Latrunculia that are sympatric at Three Kings Islands and Kaikoura are distinct from each other, and that there are two genetic groups within the green sponges in Doubtful Sound. On the basis of genetic data we conclude that there are at least eight species of Latrunculia in New Zealand waters, not one to four as had been previously thought. Morphological comparisons of the eight genetic species based on skeletal characters (i.e. skeletal organisation of the choanosome, spicule composition, size, and geometry) indicated that the eight Latrunculia species fell into only two morphological groups that could be easily diagnosed on the basis of discorhabd type. Within these two primary morphological groups, skeletal characteristics among the eight species largely overlap and are not diagnostic. These findings emphasise the limitations of traditional taxonomic methods based solely on skeletal characters for distinguishing species of Latrunculia. However, multivariate analysis (MANOVA and CDA) based on six measured skeletal variables did reveal significant morphological variation among the species (Pillai's Trace=3.28, F=6.90, P<0.0001), supporting the division of the genus into eight species. Comparisons of chemical extracts from Latrunculia also showed that the amounts of five different bioactive compounds (discorhabdins A, B, C, D, and J) varied predictably among the eight species. This finding suggests that discorhabdin variation within Latrunculia, previously thought to be associated with intra-specific environmental variability, is more likely to reflect differences among species rather than phenotypic plasticity. Our results also highlight the importance of thorough taxonomic studies associated with marine natural products research to understand fully the variation in bioactive properties among individuals. The potential processes underlying the unusually high speciation rates in New Zealand Latrunculia that are indicated in our study are discussed.     

Reproductive endocrine disruption in smallmouth bass (Micropterus dolomieu) in the Potomac River basin: spatial and temporal comparisons of biological effects

A high prevalence of intersex or testicular oocytes (TO) in male smallmouth bass within the Potomac River drainage has raised concerns as to the health of the river. Studies were conducted to document biomarker responses both temporally and spatially to better understand the influence of normal physiological cycles, as well as water quality and land-use influences. Smallmouth bass were collected over a 2-year period from three tributaries of the Potomac River: the Shenandoah River, the South Branch Potomac and Conococheague Creek, and an out-of-basin reference site on the Gauley River. The prevalence of TO varied seasonally with the lowest prevalence observed in July, post-spawn. Reproductive maturity and/or lack of spawning the previous spring, as well as land-use practices such as application of manure and pesticides, may influence the seasonal observations. Annual, seasonal, and site differences were also observed in the percentage of males with measurable concentrations of plasma vitellogenin, mean concentration of plasma vitellogenin in females, and plasma concentrations of 17β-estradiol and testosterone in both sexes. Bass collected in the South Branch Potomac (moderate to high prevalence of TO) had less sperm per testes mass with a lower percentage of those sperm being motile when compared to those from the Gauley River (low prevalence of TO). An inverse relationship was noted between TO severity and sperm motility. An association between TO severity and wastewater treatment plant flow, percent of agriculture, total number of animal feeding operations, the number of poultry houses, and animal density within the catchment was observed.     

离子色谱法测定PM_(2.5)中硫酸根离子含量不确定度评议

准确测定大气颗粒物中水溶性组份对分析污染物来源及身体健康具有重要意义。本文采用离子色谱法测定PM2.5中硫酸根离子含量,并对测定的不确定度进行分析。分析过程不确定度来源是样品重复性测量引入不确定度,样品测量准确性引入不确定度和标准曲线的不确定度。应用不确定度评定理论,计算硫酸根离子的合成不确定度。结果表明,滤膜中硫酸根离子本底浓度高低与剪裁滤膜环节是不确定度的主要来源。为了提高分析的准确性,建议使用本底低的滤膜,并取整张滤膜进行分析。     

An attempt to determine growth and hatching dates of juvenile sardine,Sardina pilchardus,in the Western Mediterranean Sea

Juvenile sardine, Sardina pilchardus Walbaum, 1792, were collected off Mallorca, Balearic Islands, during April–July 1989, and were aged by means of daily otolith increments. Growth rates were in the range of values reported for other clupeoids, although lower than those for larvae of the Mediterranean anchovy Engraulis encrasicolus. Hatching dates were back-calculated from the age in days and the date of capture. The data indicated that hatching was continuous, but revealed a low peak in the last half of November 1988 and a second, higher peak in the first half of March of the following year, in accordance with the general cycle of secondary production in this oligotrophic area.