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 Traffic emission data for both compounds are scarce and mostly outdated.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.     

宝钢厂区植被碳储量及其固碳效益评价

以著名钢铁企业上海宝钢为例,基于厂区植被调查、航片数字化解释、优势种生物量测定及模型建立,对宝钢厂区植被碳储量和固碳能力进行估算,并通过碳税法对其固碳效益进行评价,以期为城市工业区绿地群落配置和绿化树种选择、企业绿化建设的费用效益分析提供更为科学的依据。结果表明:宝钢厂区植被总碳储量为3992.99～4736.17 t,固碳效益为13507.33～16185.85万元;平均碳密度为45.82～53.27 t/hm2,固碳能力为5.91～6.87t/(hm2.a),高于上海城市森林平均值,但小于中国森林平均值,一定程度上受平均胸径、郁闭度及群落密度等因素影响。厂区在进行绿化建设时,应考虑选择防污且固碳能力强的植物,构建防污固碳兼有型群落,发挥植被的多元功能。     

Homogenous catalyzed ozonation of simazine. Effect of Mn(II) and Fe(II).

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide typically found in surface and ground water was ozonised by using catalytic amounts of Mn(II) and Fe(II). An optimum value for metal concentration was found in the process. Some inhibition of the simazine degradation rate was observed when these metals were added above the optimum concentration. The pH of the reaction media played a significant role in the simazine oxidation rate. Thus, an increase in simazine conversion was observed when the pH was raised from 5 to 9. However, the catalytic effect of added manganese was negligible at the highest pH used in this study (pH 9). The beneficial influence of Fe(II) was also observed when utilising the combination of ozone and hydrogen peroxide. Contrarily, Mn(II) presented a negative influence on simazine conversion when using this oxidation technology.     

Sequential removal of heavy metals ions and organic pollutants using an algal-bacterial consortium

The residual algal-bacterial biomass from photosynthetically supported, organic pollutant biodegradation processes, in enclosed photobioreactors, was tested for its ability to accumulate Cu(II), Ni(II), Cd(II), and Zn(II). Salicylate was chosen as a model contaminant. The algal-bacterial biomass combined the high adsorption capacity of microalgae with the low cost of the residual biomass, which makes it an attractive biosorbent for environmental applications. Cu(II) was preferentially taken-up from the medium when the metals were present both separately and in combination. There was no observed competition for adsorption sites, which suggested that Cu(II), Ni(II), Cd(II), and Zn(II) bind to different sites and that active Ni(II), Cd(II) and Zn(II) binding groups were present at very low concentrations. Therefore, special focus was given to Cu(II) biosorption. Cu(II) biosorption by the algal-bacterial biomass was characterized by an initial fast cell surface adsorption followed by a slower metabolically driven uptake. pH, Cu(II), and algal-bacterial concentration significantly affected the biosorption capacity for Cu(II). Maximum Cu(II) adsorption capacities of 8.5+/-0.4 mg g-1 were achieved at an initial Cu(II) concentration of 20 mg l-1 and at pH 5 for the tested algal-bacterial biomass. These are consistent with values reported for other microbial sorbents under similar conditions. The desorption of Cu(II) from saturated biomass was feasible by elution with a 0.0125 M HCl solution. Simultaneous Cu(II) and salicylate removal in a continuous stirred tank photobioreactor was not feasible due to the high toxicity of Cu(II) towards the microbial culture. The introduction of an adsorption column, packed with the algal-bacterial biomass, prior to the photobioreactor reduced Cu(II) concentration, thereby allowing the subsequent salicylate biodegradation in the photobioreactor.     

Water Remediation: PVA-Based Magnetic Gels as Efficient Devices to Heavy Metal Removal

Scientific and technological researches are devoted to obtain materials capable of retaining different kinds of pollutants, contributing to contamination solutions. In this context, hydrogels have emerged as great candidates because of their excellent absorption properties as well as good mechanical, thermal and chemical properties. More specifically, ferrogels (magnetic gels) present the extra advantage of being easily manipulated by a permanent magnet. Here, we present the results derived from the application of ferrogels as efficient tools to extract heavy metal pollutants from wastewater samples. The gels were prepared following the method of freezing and thawing of a polyvinyl alcohol aqueous solution with magnetic nanoparticles coated with polyacrylic acid. Ferrogels were fully characterized and their ability to retain Cu²⁺ and Cd²⁺, as model heavy metals, was studied. Thus kinetics and mechanisms of adsorption were evaluated and modeled. The concentration of MNPs on the PVA matrix was key to improve the adsorption capability (approximately the double of retention is improved by the MNPs addition). The adsorption kinetics was determined as pseudo-second order model, whereas the Langmuir model was the most appropriate to explain the behavior of the gels. Finally reuse ability was evaluated to determine the real potential of these materials, the ferrogels demonstrated high efficiency up to about five cycles, retaining about 80–90% of their initial adsorption capability. All the results indicated that the materials are promising candidates able to compete with the commercial technology regarding to water remediation.     

Allozyme variation in European populations of the oyster Ostrea edulis

Variations at 22 enzyme coding loci were surveyed in 11 populations of the oyster Ostrea edulis L., which were sampled between 1988 and 1990 along the Atlantic and Mediterranean coasts of Europe. Atlantic oyster beds suffered a steady decline during the last century, and restocking of beds with oysters of foreign origin has probably resulted in a high degree of interbreeding of natural oyster stocks from all Atlantic Europe. Our study confirms the low levels of genetic variability previously reported for the oyster populations from the Atlantic coasts, and extends it to the Mediterranean coasts. The locus arginine-kinase (ARK ^*) exhibited a high degree of interpopulation differentiation (F _ST=0.289), resulting from extensive variation in gene frequencies along a geographical cline. However, the overall genetic differentiation between populations was slight, and similar to that reported for other local populations of bivalves (mean genetic distance between populations is 0.010, mean F _ST=0.062). A general pattern of increasing differentiation along the coastline in an Atlantic-mediterranean direction emerged; but genetic differentiation among the Atlantic populations was not significantly lower than that observed among the Mediterranean populations. This and other results suggest that the effects of extensive transplantation of oysters among various areas in Europe are detectable only in some particular localities. The geographical distribution of low-frequency alleles suggests a restriction to gene flow outwards from the Mediterranean Sea, across the Straits of Gibraltar.     

Geographical patterns of variability at allozyme loci in the European oyster Ostrea edulis

The variability of 14 enzyme-coding genes has been analysed in samples from 19 populations of the oyster Ostrea edulis L., collected along the Atlantic and Mediterranean coasts of Europe. We found an abundance of clines, which appeared at 8 loci, including the most polymorphic (AP-2 ^*, ARK ^*, EST-4 ^*, MDH-2 ^*, ME-1 ^*, 6PGH ^*, PGI ^* and PGM ^*). Another 6 loci (ALDH ^*, EST-3 ^*, EST-5 ^*, IDH-2 ^*, MDH-1 ^*, ME-2 ^*) exhibited V-shaped patterns of gene-frequency variation, with clines at one or both sides of the Straits of Gibraltar. The observation of coincident clines at many loci can be explained by a model of secondary intergradation. The geographical location of the midpoints of the clines and V-shaped patterns suggests the existence of two ancient Atlantic and Mediterranean oyster stocks which became differentiated in allopatry and subsequently merged. Clines observed along Atlantic and/or Mediterranean coasts at the loci with V-shaped patterns must have arisen independently. The large heterogeneity observed in the levels of gene differentiation (G _ST ) across loci (G _ST ranged from 0.008 to 0.290) and important differences in estimates of gene flow obtained by different methods suggest that the populations of O. edulis are not in genetic equilibrium. Lack of population equilibrium can be due to natural selection and/or restrictions to gene flow. The average among-population variability was higher than in other oyster species that do not show incubatory habits, and represented 8.8% of the total heterozygosity. Levels of intrapopulation variability were lowest in populations from the North Atlantic, suggesting low population sizes in that area.     

Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream

Four water samples collected using standard depth and width water-column sampling methodology were compared to an innovative passive, in situ, sampler (the polar organic chemical integrative sampler or POCIS) for the detection of 96 organic wastewater-related contaminants (OWCs) in a stream that receives agricultural, municipal, and industrial wastewaters. Thirty-two OWCs were identified in POCIS extracts whereas 9-24 were identified in individual water-column samples demonstrating the utility of POCIS for identifying contaminants whose occurrence are transient or whose concentrations are below routine analytical detection limits. Overall, 10 OWCs were identified exclusively in the POCIS extracts and only six solely identified in the water-column samples, however, repetitive water samples taken using the standard method during the POCIS deployment period required multiple trips to the sampling site and an increased number of samples to store, process, and analyze. Due to the greater number of OWCs detected in the POCIS extracts as compared to individual water-column samples, the ease of performing a single deployment as compared to collecting and processing multiple water samples, the greater mass of chemical residues sequestered, and the ability to detect chemicals which dissipate quickly, the passive sampling technique offers an efficient and effective alternative for detecting OWCs in our waterways for wastewater contaminants.