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 Traffic emission data for both compounds are scarce and mostly outdated.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

Survey of phthalates, alkylphenols, bisphenol A and herbicides in Spanish source waters intended for bottling

Background, aim and scope

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination.

Materials and methods

Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed.

Results and discussion

Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77?C124?%) and limits of quantification were between 0.0004 and 0.029???g/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018???g/L for octylphenol to 0.970???g/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115???g/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds.

Conclusions

Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

Growth,photosynthesis and removal responses of the cyanobacteria Chroococcus sp. to malathion and malaoxon

Abstract

Malathion is an organophosphorus pesticide widely used in agricultural crops, despite its toxicity. In addition, malaoxon occurs by oxidation of malathion being more toxic. The toxic effects of malathion and malaoxon in humans include hepatoxicity, breast cancer, genetic damage and endocrine disruption. The aim of this study involved assessing the effect of malathion commercial grade on Chroococcus sp., and its potential as an alternative to the removal of this pesticide and its transformation product such as malaoxon. We evaluated the effect of malathion at different concentrations (1, 25, 50, 75 and 100?ppm) on the biomass of the cyanobacteria Chroococcus sp. grown in medium BG-11; also, we analyse its ability to degrade both malathion and malaoxon into a temperature of 28?±?2?°C and at pH 6. The results showed that 50?ppm of malathion the cyanobacteria Chroococcus sp. reached the highest removal efficiency of malathion and malaoxon (69 and 65%, respectively); also, the growth rate of Chroococcus sp. increased without inhibiting the production of chlorophyll “a”, this can be explained by the hormesis phenomenon. Therefore, we consider that the cyanobacteria Chroococcus sp. may be a good candidate for bioremediation of aquatic systems contaminated with organophosphorus pesticides such as malathion and its transformation product such as malaoxon.     

Mortality due to haematological cancer in cities close to petroleum refineries in Spain

Controversy exists as to whether working or living in the vicinity of a petroleum refinery (RF) increases the risk of haematological cancer (HC). The European Pollutant Release and Transfer Register obliges petroleum refineries to notify their emissions of toxic substances which include carcinogenic substances. Our objective is to determine if living in the proximity of an RF is associated with a greater risk of mortality due to HC in the census tracts (CTs) of the Spanish cities of Bilbao, Cartagena, Castellón, La Coruña, Huelva, and Santa Cruz de Tenerife. This is an ecological study of mortality in the years 1996–2007 which includes 968 CTs with 1,263,371 inhabitants. Exposure has been measured as the distance from the centroid of each CT to the RF. The Besag–York–Mollié autoregressive spatial model has been fitted by R-INLA to estimate the relative risk (RR) and 95 % credible intervals (95 % CrI) for distance in quintiles. The most distant quintile has been taken as the reference. A total of 2,574 persons died of HC. The distances from the CTs to RFs ranged from 0.5 to 22.5 km (median?=?7.6 km). All of the RRs for the quintiles of distances in Huelva were greater than 1. Statistically significant excess risk was shown in Cartagena in the nearest CT (1.8 to 6.8 km; RR?=?1.43, 95 % CrI 1.02 to 2.02). Radial effects have not been detected between the CT of residence and the petroleum RF in mortality due to HC in any of the cities.     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

Linking Salmon Aquaculture Synergies and Trade-Offs on Ecosystem Services to Human Wellbeing Constituents

Salmon aquaculture has emerged as a successful economic industry generating high economic revenues to invest in the development of Chiloe region, Southern Chile. However, salmon aquaculture also consumes a substantial amount of ecosystem services, and the direct and indirect impacts on human wellbeing are still unknown and unexplored. This paper identifies the synergies and trade-offs caused by the salmon industry on a range of ecosystem services. The results show that large economic benefits due to the increase of provisioning ecosystem services are also causing a reduction on regulating and cultural services. Despite the improvement on average income and poverty levels experienced in communities closely associated with the sector, this progress is not large enough and social welfare did not improve substantially over the last decade. The rest of human wellbeing constituents in Chiloe region have not changed significantly compared to the development in the rest of the country.     

Effect of liquid swine manure rate, incorporation, and timing of rainfall on phosphorus loss with surface runoff

Excessive manure phosphorus (P) application increases risk of P loss from fields. This study assessed total runoff P (TPR), bioavailable P (BAP), and dissolved reactive P (DRP) concentrations and loads in surface runoff after liquid swine (Sus scrofa domesticus) manure application with or without incorporation into soil and different timing of rainfall. Four replicated manure P treatments were applied in 2002 and in 2003 to two Iowa soils testing low in P managed with corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] rotations. Total P applied each time was 0 to 80 kg P ha(-1) at one site and 0 to 108 kg P ha(-1) at the other. Simulated rainfall was applied within 24 h of P application or after 10 to 16 d and 5 to 6 mo. Nonincorporated manure P increased DRP, BAP, and TPR concentrations and loads linearly or exponentially for 24-h and 10- to 16-d runoff events. On average for the 24-h events, DRP, BAP, and TPR concentrations were 5.4, 4.7, and 2.2 times higher, respectively, for nonincorporated manure than for incorporated manure; P loads were 3.8, 7.7, and 3.6 times higher; and DRP and BAP concentrations were 54% of TPR for nonincorporated manure and 22 to 25% for incorporated manure. A 10- to 16-d rainfall delay resulted in DRP, BAP, and TPR concentrations that were 3.1, 2.7, and 1.1 times lower, respectively, than for 24-h events across all nonincorporated P rates, sites, and years, whereas runoff P loads were 3.8, 3.6, and 1.6 times lower, respectively. A 5- to 6-mo simulated rainfall delay reduced runoff P to levels similar to control plots. Incorporating swine manure when the probability of immediate rainfall is high reduces the risk of P loss in surface runoff; however, this benefit sharply decreases with time.     

An environmental perspective of the post-tsunami scenario along the coast of Tamil Nadu, India: role of sand dunes and forests

An endeavor to feel the pulse of a coast devastated by a powerful oceanographic event is made. Results of field investigations along Tamil Nadu seaside revealed that the tsunami of December 2004 demolished dwellings within strips ranging from 6 to 132m (average width, 41m) from the dune, and flooded up to 862m (average, 247m) from the shore. The event damaged sand dunes, ripped dune vegetation, created new water bodies and shattered high value assets. Comparatively, casuarina forests performed remarkably. Uprooting of trees was exclusively restricted to a frontal strip ranging from 5 to 25m (average width, 14m) nearest to the shore where the maximum wave run-up was 6.5m above sea level. Sand dunes in general, and casuarina forests in particular, posses an innate capacity to dissipate powerful waves. This inference is supported by (a) negligible over wash along belts characterized by high dune complexes, (b) intact villages shielded by dense forests as well as sand dunes, and (c) maximum destruction of open beach front influenced by intense human activity. In this context, the coastal regulation zone (CRZ) Notification of 1991 offers sufficient scientific validity to be endorsed. However, post-tsunami ecosystem management initiatives lack a scientific basis. Therefore, a coastal hazards policy, that considers adaptation, dune restoration and forested buffer zones, is a sustainable long-term option for Indian coasts.     

Multiscale analysis of heavy metal contents in Spanish agricultural topsoils

This study characterized and mapped the spatial variability patterns of seven topsoil heavy metals (Cr, Ni, Pb, Cu, Zn, Hg and Cd) within the Ebro river basin (9.3 million ha) by Multivariate Factorial Kriging. The variograms and cross-variograms of heavy metal concentrations showed the presence of multiscale variation that was modeled using three variogram models with ranges of 20km (short-range), 100km (medium-range) and 225km (long-range). Our results indicate that the heavy metal concentration is influenced by bedrock composition and dynamics at all the spatial scales, while human activities have a notorious effect only at the short- and medium-range scale of variation. Sources of Cu, Pb and Zn (and secondary Cd) are associated with agricultural practices (at the short-range scale of variation), whereas Hg variation at the short- and medium-range scale of variation is related to atmospheric deposition.