Zero-valent iron/persulfate(Fe0/PS) oxidation acetaminophen in water

Zero-valent iron (Fe⁰), as an alternative iron source, was evaluated to activate persulfate (PS) to degrade acetaminophen (APAP), a representative pharmaceutically active compound in water. Effects of key factors in the so-called Fe⁰/PS process, including Fe⁰ dosage, initial pH, temperatures and chelating agents, were studied. Under all the conditions tested, the APAP degradation followed a pseudo-first-order kinetics pattern. The degradation efficiency of APAP was highest when the Fe⁰ to PS molar ratio increased to 1:1, and the degradation rate constant and removal were 23.19 × 10^?3 min^?1 and 93.19 %, respectively. Comparing with Fe²⁺, Fe⁰ served as an alternative iron source that can gradually release Fe²⁺ into water, thereby consistently activating PS to produce sulfate radicals. The Fe⁰/PS system was effective in a broader pH range from 3 to 8.5. Heat could facilitate production of sulfate radicals and enhance the APAP degradation in the Fe⁰/PS system. High reaction temperature also improved the Fe²⁺/PS oxidation of APAP. Finally, sodium citrate (a chelating agent) at an appropriate concentration could improve the APAP degradation rate in the Fe²⁺/PS and Fe⁰/PS system. The optimal molar ratio of Fe⁰ to citrate depended on solution pH. Our results demonstrated that Fe⁰ was an alternative iron source to activate PS to degrade APAP in water.     

Characterizing land condition variability in Northern China from 1982 to 2011

For the last three decades, Northern China has been considered as one of the most sensitive areas regarding global environmental change. The integration of AVHRR GIMMS and MODIS NDVI data (1982–2011), of which for the overlapping period of 2000–2006 show good consistency, were used for characterizing land condition variability. The trends of standardized annually ΣNDVI, temperature, precipitation and PDSI were obtained using a linear regression model. The results showed that Northern China has a general increase in greenness for the period 1982–2011 (a = 0.05). Also, annually ΣNDVI is significantly correlated with temperature and precipitation data at the regional scale (p < 0.05), implying that temperature and precipitation are the dominant limiting factors for vegetation growth. Since the greening is not uniform, factors other than temperature and precipitation may contribute to greening in some areas, while the grassland and cropland ecosystem are becoming increasingly vulnerable to drought. The results of trend analysis indicate that greenness seems to be evident in most of the study areas.     

Spatial evaluation of phosphorus retention in riparian zones using remote sensing data

Riparian zones act as important buffer zones for non-point source pollution, thus improving the health of aquatic ecosystems. Previous research has shown that riparian zones play an important role, and that land use has an important effect, on phosphorus (P) retention. A spatial basin-scale approach for analyzing P retention and land use effects could be important in preventing pollution in riparian zones. In this study, a riparian phosphorus cycle model based on EcoHAT was generated with algorithms from soil moisture and heat models, simplified soil and plant phosphorus models, plant growth models, and universal soil loss equations. Based on remote sensing data, model performance was enhanced for spatial and temporal prediction of P retention in the riparian zone. A modified soil and plant P model was used to simulate the soil P cycle of a riparian zone in a temperate continental monsoon climate in northern China. A laboratory experiment and a field experiment were conducted to validate the P cycle model. High coefficients of determination (R ²) between simulated and observed values indicate that the model provides reliable results. P uptake variations were the same as the net primary productivity (NPP) trends, which were affected by soil temperature and moisture in the temperate continental monsoon climate. Beginning in June, the monthly content increased, with the maximum appearing in August, when the most precipitation and the highest temperatures occur. The spatial distribution of P uptake rates from March to September showed that areas near water frequently had relatively high values from May to August, which is contrary to results obtained in March, April, and September. The P uptake amounts for different land uses changed according to expectation. The average monthly P uptake rates for farmlands and grasslands were more than those for orchards and lowlands, which had moderate P uptake rates, followed by shrubs and forests. The spatial distribution of soil erosion demonstrated that the soil erosion came primarily from high-intensity agricultural land in the western and central areas, while the northern and eastern study regions, which were less affected by human activity, experienced relatively slight soil erosion. From the point of view of P pollution prevention, the spatial structure of riparian zones and the spatial distribution of land use around the Guanting reservoir are thus not favorable.     

Responses of microorganisms and enzymes to soil contamination with metazachlor

A greenhouse pot experiment was conducted at the University of Warmia and Mazury in Olsztyn, with the aim of describing the influence of metazachlor on counts and biodiversity of soil microorganisms, soil enzymatic activity, physicochemical properties of soil and yield of spring oilseed rape. The first experimental factor was soil contamination with increasing rates of metazachlor: 0 (soil without the herbicide), 0.333 (recommended by the manufacturer), 6.666, 13.332, 26.665, 53.328, 106.656 and 213.312 mg kg^?1 dm of soil, while the second factor comprised two dates of determination: 30 and 60 days after starting the experiment. The tested herbicide had an adverse effect on reproduction of all analyzed microorganisms: oligotrophic bacteria and their endospore forms, Azotobacter spp. bacteria, organotrophic bacteria, actinomycetes and fungi. The values of the colony development and eco-physiological diversity indices decreased under the influence of excessive doses of the herbicide. Also, significant fluctuation in the enzymatic activity of soil was observed in response to the higher doses of metazachlor and depending on the date of determinations. The herbicide had an invariably negative influence on the activity of soil enzymes, causing the inhibition of dehydrogenases, catalase, urease, acid phosphatase, alkaline phosphatase, arylsulfatase and β-glucosidase. The physicochemical status of soil depended significantly on the degree of soil contamination with the herbicide, same as the yield of spring oilseed rape.     

Streamflow response to regional climate model output in the mountainous watershed: a case study from the Swiss Alps

Regional climate model (RCM) outputs are often used in hydrological modeling, in particular for streamflow forecasting. The heterogeneity of the meteorological variables such as precipitation, temperature, wind speed and solar radiation often limits the ability of the hydrological model performance. This paper assessed the sensitivity of RCM outputs from the PRUDENCE project and their performance in reproducing the streamflow. The soil and water assessment tool was used to simulate the streamflow of the Rhone River watershed located in the southwestern part of Switzerland, with the climate variables obtained from four RCMs. We analyzed the difference in magnitude of precipitation, maximum and minimum air temperature, and wind speed with respect to the observed values from the meteorological stations. In addition, we also focused on the impact of the grid resolution on model performance, by analyzing grids with resolutions of 50 × 50 and 25 × 25 km². The variability of the meteorological inputs from various RCMs is quite severe in the studied watershed. Among the four different RCMs, the Danish Meteorological Institute provided the best performance when simulating runoff. We found that temperature lapse rate is significantly important in the mountainous snow and glacier dominated watershed as compared to other variables like precipitation, and wind speed for hydrological performance. Therefore, emphasis should be given to minimum and maximum temperature in the bias correction studies for downscaling climatic data for impact modeling in the mountainous snow and glacier dominated complex watersheds.     

Behaviour of radiogenic Pb in zircon during ultrahigh-temperature metamorphism: an ion imaging and ion tomography case study from the Kerala Khondalite Belt,southern India

Zircon crystals from a locally charnockitized Paleoproterozoic high-K metagranite from the Kerala Khondalite Belt (KKB) of southern India have been investigated by high-spatial resolution secondary ion mass spectrometry analysis of U–Th–Pb and rare earth elements (REE), together with scanning ion imaging and scanning ion tomography (depth-profiled ion imaging). The spot analyses constrain the magmatic crystallization age of the metagranite to ca. 1,850 Ma, with ultrahigh-temperature (UHT) metamorphism occurring at ca. 570 Ma and superimposed charnockite formation at ca. 520–510 Ma, while the ion imaging reveals a patchy distribution of radiogenic Pb throughout the zircon cores. Middle- to heavy-REE depletion in ca. 570 Ma zircon rims suggests that these grew in equilibrium with garnet and therefore date the UHT metamorphism in the KKB. The maximum apparent ²⁰⁷Pb/²⁰⁶Pb age obtained from the unsupported radiogenic Pb concentrations is also consistent with formation of the Pb patches during this event. The superimposed charnockitization event appears to have caused additional Pb-loss in the cores and recrystallization of the rims. The results of depth-profiling of the scanning ion tomography image stack show that the Pb-rich domains range in size from <5 nm to several 10 nm (diameter if assumed to be spherical). The occurrence of such patchy Pb has previously been documented only from UHT metamorphic zircon, where it likely results from annealing of radiation-damaged zircon. The formation of a discrete, heterogeneously distributed and subsequently immobile Pb phase effectively arrests the normal Pb-loss process seen at lower grades of metamorphism.     

Petrogenesis of a voluminous Quaternary adakitic volcano: the case of Baru volcano

The origin of adakite magmas remains controversial because initially the term adakite had petrogenetic significance implying an origin by direct melting of the eclogitized subducting oceanic crust. Many models have been produced for their origin, and until now there has not been a straightforward method to discriminate between these models in a given adakite suite. Here, we use detailed chronological and geochemical studies of selected adakitic edifices that allows for the determination of the magmatic output rate parameter (Qe), which has been correlated with the rates of magma generation deep within subduction zones. By providing temporal and eruption rate estimates, we provide constraints on the possible petrogenetic processes involved in the generation of adakite-like signatures. Adakite magmas derived from the melting of the subducting slab should be volumetrically insignificant when compared to the adakite-like magmas produced by typical arc magma generation processes. In this study, we use this observation and the extraordinary stratigraphic exposure from Miocene to present in an adakitic volcano in Panama and to study the temporal and chemical variation in erupted magmas to estimate rates of magma generation. Detailed chemical and geochronological analyses of Baru volcano indicate that the volcanic edifice was constructed in its entirety during the Quaternary and magmas display adakite-like features such as steep rare earth elements patterns, pronounced depletions in the heavy rare earth elements, low Y, high Sr, and high Sr/Y. The magmatic output rates (Qe) that we have calculated show that compared to other typical adakitic volcanoes, most of the volcanic edifice of Baru volcano was constructed extremely rapidly (<~213 k.a.) and in time frames that are similar to typical arc volcanoes. The observed chemical and mineralogical variation, coupled with the high magma production rates, indicate that Baru volcano is more representative of a typical arc volcano than a small-volume melt of the subducting oceanic crust. The technique we outline may have broader application in determining the petrogenetic conditions of other adakite suites.     

Origin and significance of poikilitic and mosaic peridotite xenoliths in the western Pannonian Basin: geochemical and petrological evidences

Peridotite xenoliths erupted by alkali basaltic volcanoes in the western Pannonian Basin can be divided into two fundamentally contrasting groups. Geochemical characteristics of the abundant protogranular, porphyroclastic and equigranular nodules suggest that these samples originate from an old consolidated and moderately depleted lithospheric mantle domain. In contrast, the geochemical features of the worldwide rare, but in the Pannonian Basin relatively abundant, poikilitic xenoliths attest to a more complex evolution. It has been argued that the origin of the peculiar texture and chemistry may be intimately linked to melt/rock reactions at successively decreasing liquid volumes in a porous melt flow system. The most likely site where such reactions can take place is the asthenosphere–lithosphere boundary. In this context, poikilitic xenoliths may provide petrological and geochemical evidence for reactions between magmatic liquids issued from the uprising asthenosphere and the solid mantle rocks of the lithosphere. These reactions are important agents of the thermal erosion of the lithosphere; thus, they could have considerably contributed to the thinning of the lithosphere in the Pannonian region. We suggest that in the Pannonian Basin, there could be a strong relation between the unusual abundance of poikilitic mantle xenoliths and the strongly eroded lithosphere.     

Overstepping the garnet isograd: a comparison of QuiG barometry and thermodynamic modeling

The consequences of overstepping the garnet isograd reaction have been investigated by comparing the composition of garnet formed at overstepped P–T conditions (the overstep or “OS” model) with the P–T conditions that would be inferred by assuming garnet nucleated in equilibrium with the matrix assemblage at the isograd (the equilibrium or “EQ” model). The garnet nucleus composition formed at overstepped conditions is calculated as the composition that produces the maximum decrease in Gibbs free energy from the equilibrated, garnet-absent, matrix assemblage for the bulk composition under study. Isopleths were then calculated for this garnet nucleus composition assuming equilibrium with the matrix assemblage (the EQ model). Comparison of the actual P–T conditions of nucleation (the OS model) with those inferred from the EQ model reveals considerable discrepancy between the two. In general, the inferred garnet nucleation P–T conditions (the EQ model) are at a lower temperature and higher or lower pressure (depending on the coexisting calcic phase(s)) than the actual (OS model) nucleation conditions. Moreover, the degree of discrepancy increases with the degree of overstepping. Independent estimates of the pressure of nucleation of garnet were made using the Raman shift of quartz inclusions in garnet (quartz-in-garnet or QuiG barometry). To test the validity of this method, an experimental synthesis of garnet containing quartz inclusions was made at 800 °C, 20 kbar, and the measured Raman shift reproduced the synthesis conditions to within 120 bars. Raman band shifts from three natural samples were then used to calculate an isochore along which garnet was presumed to have nucleated. Model calculations were made at several temperatures along this isochore (the OS model), and these P–T conditions were compared to those computed assuming equilibrium nucleation (the EQ model) to estimate the degree of overstepping displayed by these samples. A sample from the garnet isograd in eastern Vermont is consistent with overstepping of around 10 degrees and 0.6 kbar (affinities of around 2 kJ/mole garnet). A sample from the staurolite–kyanite zone in the same terrane requires overstepping of around 50 °C and 2–5 kbar (affinities of around 10–18 kJ/mole garnet). A similar amount of overstepping was inferred for a blueschist sample from Sifnos, Greece. These results indicate that overstepping of garnet nucleation reactions may be common and pronounced in regionally metamorphosed terranes, and that the P–T conditions and paths inferred from garnet zoning studies may be egregiously in error.     

Fluoride and arsenic hydrogeochemistry of groundwater at Yuncheng basin,Northern China

High fluoride and arsenic concentrations in groundwater have led to serious health problems to local inhabitants at Yuncheng basin, Northern China. In this study, groundwater with high fluoride and arsenic concentration at Yuncheng basin was investigated. A majority of the samples (over 60%) belong to HCO₃ type water. The predominant water type for the shallow groundwater collected from southern and eastern mountain areas was Ca/Mg-Ca-HCO₃ types. For the shallow groundwater from flow through and discharge area it is Na-HCO₃/SO₄-Cl/SO₄/Cl type. The predominant water type for the intermediate and deep groundwater is of Na/Ca/Mg-Ca-HCO₃ type. According to our field investigation, fluoride concentration in groundwater ranges between 0.31 and 14.2 mg/L, and arsenic concentration ranges between 0.243 and 153.7 μg/L. Out of seventy collected groundwater samples, there are 31 samples that exceed the World Health Organization (WHO) standard of 1.5 mg/L for fluoride, and 15 samples exceeds the WHO standard of 10 μg/L for arsenic. Over 40% of high fluoride and arsenic groundwater are related to the Na-HCO₃ type water, and the other fifty percent associated with Na-SO₄-Cl/HCO₃-SO₄-Cl type water; little relation was found in calcium bicarbonate type water. A moderate positive correlation between fluoride and arsenic with pH were found in this study. It is due to the pH-dependent adsorption characteristics of F and As onto the oxide surfaces in the sediments. The observed negative correlation between fluoride and calcium could stem from the dissolution equilibrium of fluorite. The high concentration of bicarbonate in groundwater can serve as a powerful competitor and lead to the enrichment of fluoride and arsenic in groundwater. Most of the groundwater with high fluoride or arsenic content has nitrate content about or over 10 mg/L which, together with the observed positive correlations between nitrate and fluoride/arsenic, are indicative of common source of manmade pollution and of prevailing condition of leaching in the study area.