Nocturnal NO3 radical chemistry in Houston,TX

Radical chemistry in the nocturnal urban boundary layer is dominated by the nitrate radical, NO₃, which oxidizes hydrocarbons and, through the aerosol uptake of N₂O₅, indirectly influences the nitrogen budget. The impact of NO₃ chemistry on polluted atmospheres and urban air quality is, however, not well understood, due to a lack of observations and the strong impact of vertical stability of the boundary layer, which makes nocturnal chemistry highly altitude dependent.Here we present long-path DOAS observations of the vertical distribution of the key nocturnal species O₃, NO₂, and NO₃ during the TRAMP experiment in Summer 2006 in Houston, TX. Our observations confirm the altitude dependence of nocturnal chemistry, which is reflected in the concentration profiles of all trace gases at night. In contrast to other study locations, NO₃ chemistry in Houston is dominated by industrial emissions of alkenes, in particular of isoprene, isobutene, and sporadically 1,3-butadiene, which are responsible for more than 70% of the nocturnal NO₃ loss. The nocturnally averaged loss of NO_x in the lowest 300 m of the Houston atmosphere is ～0.9 ppb h^?1, with little day-to-day variability. A comparison with the daytime NO_x loss shows that NO₃ chemistry is responsible for 16–50% of the NO_x loss in a 24-h period in the lowest 300 m of the atmosphere. The importance of the NO₃ + isoprene/1,3-butadiene reactions implies the efficient formation of organic nitrates and secondary organic aerosol at night in Houston.     

The predictive power of the elimination of dioxin-like pollutants from pigs: an in vivo study

Pigs accidentally given feed contaminated by dioxin-like pollutants are a serious public health issue. We have examined whether pigs with limited exposure during early periods of fattening would be categorized as non-compliant with the EU limit at slaughtering when growth-dilution, excretion and metabolism effects are considered. Sixteen female and sixteen castrated male weaned pigs were divided into four groups (e.g. DG0, DG1, DG2 and DG3) in week 2 after birth. From weeks 3 to 13, groups DG1, DG2, and DG3 pigs were fed with a polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) and polychlorinated biphenyl (PCB) mixture at dosages of 1, 10 and 100 ng-toxic equivalent (TEQ) per kg dry mass feed in capsules, respectively. From weeks 13 to 23, the animals were nourished with clear feed. Control group DG0 was always fed with clear feed. Subcutaneous fat samples were collected at weeks 13, 18 and 23 by biopsies. The pollutant residues were analyzed by high resolution gas chromatography-high resolution mass spectrometry and quantified by a ¹³C-isotope dilution method. The results showed the following: (1) when slaughtered at week 23, the TEQ for DG1 pigs (0.66 ± 0.21 pg/g fat) was under the EU limit of 1 pg PCDD/F-TEQ/g fat; (2) PCDD/F congener-specific first-order elimination rates were linearly correlated with their toxicity equivalency factors (TEFs), and the rates were significantly dose-dependent for the more toxic congeners (TEF ≥ 0.1). Therefore, the pigs' exposure above the EU limit during the early fattening stage did not necessarily lead to their categorization as non-compliant pork; and the residual TEQ for pork can be predicted from early exposure concentrations based on the models established here.     

Temporal variation and spatial distribution of PAH in water of Three Gorges Reservoir during the complete impoundment period

Bioavailable concentrations of polycyclic aromatic hydrocarbons (PAHs) were investigated in water of Three Gorges Reservoir (TGR) using semipermeable membrane devices during the period of completely impounding water. ∑PAH concentrations in water of TGR in the period of completely impounding water were 15–381 ng?L^?1. ∑PAH concentrations increased from town or counties to big industrialized cities in TGR, indicating urbanization effects on PAH pollution in the water. Tributaries in TGR have a certain contribution of PAH pollution to the mainstream of Yangtze River and their pollution could not be neglected. An obvious decrease of PAH concentration was observed after 175-m water impounding in 2011 in TGR. Several factors may account for this decrease, including execution of comprehensive treatment and management measures in TGR, less rainfall in 2011, and sedimentation effect caused by the dam. Passive sampling method has been successfully applied in the investigation of trace PAH in water of TGR and proved to be a useful and efficient tool for the management and sustainable development of the big reservoir. The results of the study provide valuable information about PAH pollution in the whole reservoir including some tributaries, and the pollution status is dynamically related with human activities. Therefore, PAH could be used as a marker compound or indicator in the network monitoring system to surveil and trace the pollution status in TGR.     

Shrines in Central Italy conserve plant diversity and large trees

Sacred natural sites (SNS) are instances of biocultural landscapes protected for spiritual motives. These sites frequently host important biological values in areas of Asia and Africa, where traditional resource management is still upheld by local communities. In contrast, the biodiversity value of SNS has hardly been quantitatively tested in Western contexts, where customs and traditions have relatively lost importance due to modernization and secularization. To assess whether SNS in Western contexts retain value for biodiversity, we studied plant species composition at 30 SNS in Central Italy and compared them with a paired set of similar but not sacred reference sites. We demonstrate that SNS are important for conserving stands of large trees and habitat heterogeneity across different land-cover types. Further, SNS harbor higher plant species richness and a more valuable plant species pool, and significantly contribute to diversity at the landscape scale. We suggest that these patterns are related not only to pre-existent features, but also to traditional management. Conservation of SNS should take into account these specificities, and their cultural as well as biological values, by supporting the continuation of traditional management practices.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0738-5) contains supplementary material, which is available to authorized users.     

Hydrochemistry of urban groundwater, Seoul, Korea: the impact of subway tunnels on groundwater quality

Hydrogeologic and hydrochemical data for subway tunnel seepage waters in Seoul (Republic of Korea) were examined to understand the effect of underground tunnels on the degradation of urban groundwater. A very large quantity of groundwater (up to 63 million m³ year^− 1) is discharged into subway tunnels with a total length of 287 km, resulting in a significant drop of the local groundwater table and the abandonment of groundwater wells. For the tunnel seepage water samples (n = 72) collected from 43 subway stations, at least one parameter among pathogenic microbes (total coliform, heterotrophic bacteria), dissolved Mn and Fe, NH₄⁺, NO₃⁻, turbidity, and color exceeded the Korean Drinking Water Standards. Locally, tunnel seepage water was enriched in dissolved Mn (avg. 0.70 mg L^− 1, max. 5.58 mg L^− 1), in addition to dissolved Fe, NH₄⁺, and pathogenic microbes, likely due to significant inflow of sewage water from broken or leaking sewer pipes.Geochemical modeling of redox reactions was conducted to simulate the characteristic hydrochemistry of subway tunnel seepage. The results show that variations in the reducing conditions occur in urban groundwater, dependent upon the amount of organic matter-rich municipal sewage contaminating the aquifer. The organic matter facilitates the reduction and dissolution of Mn- and Fe-bearing solids in aquifers and/or tunnel construction materials, resulting in the successive increase of dissolved Mn and Fe. The present study clearly demonstrates that locally significant deterioration of urban groundwater is caused by a series of interlinked hydrogeologic and hydrochemical changes induced by underground tunnels.     

Potential impact model to assess agricultural pressure to landscape ecological functions

Conservation and protection of soil and water resources and visual aspects of landscape, as well as the promotion of biodiversity, are some of the central tasks of environmental policy development and social politics in the future. One of the main questions is: ‘which agricultural systems are able to guarantee sustained resource-conserving land use?’ Based on the ecological risk concepts of the 1970s and 1980s, a potential impact model was developed using a universal assessment algorithm derived from fuzzy logic. The model estimated the potential impact of agricultural land use on ecosystem function using a few resource indicators. Intervention intensities of agricultural land-use are set in relation to site conditions and aggregated for each of several defined potential impact categories. The interpretation with respect to risk and the calculation of potential impact values are explained.     

The use of ion exchange membranes for isotope analyses on soil water sulfate: laboratory experiments

To investigate the potential use of anion exchange membranes (plant root simulator [PRS] probes) for isotope investigations of the soil sulfur cycle, laboratory experiments were performed to examine the sulfate exchange characteristics and to determine the extent of sulfur and oxygen isotope fractionation during sulfate sorption and desorption on the probes in aqueous solutions and simulated soil solutions. The sulfate-exchange tests in aqueous solutions under varying experimental conditions indicated that the amount of sulfate exchanged onto PRS probes increased with increasing reaction time, initial sulfate concentration, and the number of probes used (= surface area), whereas the percentage of removal of available sulfate was constant irrespective of the initial sulfate concentration. The competition of nitrate and chloride in the solution lowered the amount of exchanged sulfate. The exchange experiments in a simulated soil under water-saturated and water-unsaturated conditions showed that a considerable proportion of the soil sulfate was exchanged by the PRS probes after about 10 d. There was no evidence for significant sulfur and oxygen isotope fractionation between soil sulfate and sulfate recovered from the PRS probes. Therefore, we recommend the use of PRS probes as an efficient and easy way to collect soil water sulfate for determination of its isotope composition.     

Sorption of U(VI) onto an artificial humic substance-kaolinite-associate

An artificial humic substance-kaolinite-associate (HSKA) was synthesized as a model substance for natural clays containing organic matter in clay formations, soils, and sediments. The U(VI) sorption onto this model substance was studied in batch experiments as a function of pH and compared to the U(VI) sorption onto kaolinite in absence and presence of separately added humic acid (HA). The HSKA has a TOC content of 4.9 mg g(-1). It was found that the humic matter associated with kaolinite exhibits an immobilizing as well as an mobilizing effect on U(VI). Between pH 3 and 5, humic matter causes an increase of the U(VI) sorption onto kaolinite, whereas at pH above 5 the release of humic matter from the associate into the solution and the formation of dissolved uranyl humate complexes reduces the U(VI) sorption. The U(VI) sorption onto the synthetic HSKA differs from that of U(VI) in the system U(VI)/HA/kaolinite with comparable amounts of separately added HA. Separately added HA causes a stronger mobilizing effect on U(VI) than humic matter present in HSKA. This can be attributed to structural and functional dissimilarities of the humic substances.