Nitrogen isotope variations in camphor (Cinnamomum Camphora) leaves of different ages in upper and lower canopies as an indicator of atmospheric nitrogen sources

Nitrogen isotopic composition of new, middle-aged and old camphor leaves in upper and lower canopies has been determined in a living area, near a motorway and near an industrial area (Jiangan Chemical Fertilizer Plant). We found that at sites near roads, more positive δ¹⁵N values were observed in the camphor leaves, especially in old leaves of upper canopies, and ?δ¹⁵N = δ¹⁵N_upper − δ¹⁵N_lower > 0, while those near the industrial area had more negative δ¹⁵N values and ?δ¹⁵N < 0. These could be explained by two isotopically different atmospheric N sources: greater uptake from isotopically heavy pools of atmospheric NO_x by old leaves in upper canopies at sites adjacent to roads, and greater uptake of ¹⁵N-depleted NH_y in atmospheric deposition by leaves at sites near the industrial area. This study presents novel evidence that ¹⁵N natural abundance of camphor leaves can be used as a robust indicator of atmospheric N sources.     

Tissue S/N ratios and stable isotopes (δS and δN) of epilithic mosses (Haplocladium microphyllum) for showing air pollution in urban cities in Southern China

In urban cities in Southern China, the tissue S/N ratios of epilithic mosses (Haplocladium microphyllum), varied widely from 0.11 to 0.19, are strongly related to some atmospheric chemical parameters (e.g. rainwater SO₄²⁻/NH₄⁺ ratios, each people SO₂ emission). If tissue S/N ratios in the healthy moss species tend to maintain a constant ratio of 0.15 in unpolluted area, our study cities can be divided into two classes: class I (S/N > 0.15, S excess) and class II (S/N < 0.15, N excess), possibly indicative of stronger industrial activity and higher density of population, respectively. Mosses in all these cities obtained S and N from rainwater at a similar ratio. Sulphur and N isotope ratios in mosses are found significantly linearly correlated with local coal δ³⁴S and NH₄⁺-N wet deposition, respectively, indicating that local coal and animal NH₃ are the major atmospheric S and N sources.     

Photocatalytic removal of organic pollutants in aqueous solution by Bi(4)Nb(x)Ta((1-x))O(8)I

In this work, Bi₄Nb_xTa_(1−x)O₈I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi₄Nb_xTa_(1−x)O₈I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi₄Nb_0.1Ta_0.9O₈I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L⁻¹, catalyst dosage of 6 g L⁻¹ and natural pH (6-8), the MO molecules could be completely degradated by Bi₄Nb_0.1Ta_0.9O₈I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi₄Nb_0.1Ta_0.9O₈I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.     

Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs

A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L⁻¹) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ¹³C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ¹³C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ¹³C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ¹³C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ¹³C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.     

Stable sulphur and nitrogen isotopes of the moss Haplocladium microphyllum at urban,rural and forested sites

Elemental (S and N) and isotopic (δ³⁴S and δ¹⁵N) contents in the moss Haplocladium microphyllum at urban, rural and forested sites in acid rain area of South China have been analyzed for comparisons to show whether they are different and can be effectively used to identify S and N sources of atmospheric deposition. Average moss S content at rural sites (0.29 ± 0.06%) was found to be in between those at urban (0.35 ± 0.05%) and forested (0.25 ± 0.04%) sites, which are significantly different. Average N contents of urban (2.60 ± 0.56%) and rural mosses (2.84 ± 0.77%) are not significantly different, while both are significantly different to that of forested mosses at most areas, indicating that the atmosphere over rural sites has been polluted by N as seriously as that over urban sites. Nitrogen supply, relative to S supply, was in excess of the requirement for protein synthesis, especially at rural and forested sites. Moss stable isotope signatures have been proven to be effective tools for deciphering atmospheric S and N sources at these sites. Through moss δ³⁴S signatures, we found that atmospheric S at urban and forested sites was mainly from local coal combustion and domestic biomass burning, respectively, whereas northerly air masses contributed more S to forested sites. The relatively negative moss δ¹⁵N values (?7.5 ± 3.0, ?3.4 ± 2.1 and ?0.8 ± 2.1‰) demonstrated that the main form in the N deposition was NH_x in these sites. More negative δ¹⁵N signatures in urban mosses (?7.5 ± 3.0‰) indicated the contribution of NH₃ released from untreated city sewage and wastes, while relatively less negative δ¹⁵N for rural and forested mosses (3.4 ± 2.1 and ?0.8 ± 2.1‰) was largely derived from agricultural NH₃.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Comparison of forest edge effects on throughfall deposition in different forest types

This study examined the influence of distance to the forest edge, forest type, and time on Cl⁻, SO₄²⁻, NO₃⁻, and NH₄⁺ throughfall deposition in forest edges. The forests were dominated by pedunculate oak, silver birch, or Corsican/Austrian pine, and were situated in two regions of Flanders (Belgium). Along transects, throughfall deposition was monitored at distances of 0-128 m from the forest edge. A repeated-measures analysis demonstrated that time, forest type, and distance to the forest edge significantly influenced throughfall deposition of the ions studied. The effect of distance to the forest edge depended significantly on forest type in the deposition of Cl⁻, SO₄²⁻, and NO₃⁻: the edge effect was significantly greater in pine stands than in deciduous birch and oak stands. This finding supports the possibility of converting pine plantations into oak or birch forests in order to mitigate the input of nitrogen and potentially acidifying deposition.     

Assessing the recovery potential of alpine moss-sedge heath: reciprocal transplants along a nitrogen deposition gradient

The potential of alpine moss-sedge heath to recover from elevated nitrogen (N) deposition was assessed by transplanting Racomitrium lanuginosum shoots and vegetation turfs between 10 elevated N deposition sites (8.2-32.9 kg ha⁻¹ yr⁻¹) and a low N deposition site, Ben Wyvis (7.2 kg ha⁻¹ yr⁻¹). After two years, tissue N of Racomitrium shoots transplanted from higher N sites to Ben Wyvis only partially equilibrated to reduced N deposition whereas reciprocal transplants almost matched the tissue N of indigenous moss. Unexpectedly, moss shoot growth was stimulated at higher N deposition sites. However, moss depth and biomass increased in turfs transplanted to Ben Wyvis, apparently due to slower shoot turnover (suggested to result partly from decreased tissue C:N slowing decomposition), whilst abundance of vascular species declined. Racomitrium heath has the potential to recover from the impacts of N deposition; however, this is constrained by the persistence of enhanced moss tissue N contents.     

Historical nitrogen content of bryophyte tissue as an indicator of increased nitrogen deposition in the Cape Metropolitan Area, South Africa

Information on changes in precipitation chemistry in the rapidly expanding Cape Metropolitan Area (CMA) of South Africa is scarce. To obtain a long-term record of N deposition we investigated changes in moss foliar N, C:N ratios and nitrogen isotope values that might reflect precipitation chemistry. Tissue from 9 species was obtained from herbarium specimens collected between 1875 and 2000 while field samples were collected in 2001/2002. There is a strong trend of increasing foliar N content in all mosses collected over the past century (1.32-1.69 %N). Differences exist between ectohydric mosses which have higher foliar N than the mixohydric group. C:N ratios declined while foliar δ¹⁵N values showed no distinct pattern. From relationships between moss tissue N and N deposition rates we estimated an increase of 6-13 kg N ha⁻¹ a⁻¹ since 1950. Enhanced N deposition rates of this magnitude could lead to biodiversity losses in native ecosystems.     

Response of stable carbon isotope in epilithic mosses to atmospheric nitrogen deposition

Epilithic mosses are characterized by insulation from substratum N and hence meet their N demand only by deposited N. This study investigated tissue C, total Chl and δ¹³C of epilithic mosses along 2 transects across Guiyang urban (SW China), aiming at testing their responses to N deposition. Tissue C and total Chl decreased from the urban to rural, but δ¹³C_moss became less negative. With measurements of atmospheric CO₂ and δ¹³CO₂, elevated N deposition was inferred as a primary factor for changes in moss C and isotopic signatures. Correlations between total Chl, tissue C and N signals indicated a nutritional effect on C fixation of epilithic mosses, but the response of δ¹³C_moss to N deposition could not be clearly differentiated from effects of other factors. Collective evidences suggest that C signals of epilithic mosses are useful proxies for N deposition but further works on physiological mechanisms are still needed.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Nano-TiO2 enhances the toxicity of copper in natural water to Daphnia magna

The acute toxicity of engineered nanoparticles (NPs) in aquatic environments at high concentrations has been well-established. This study demonstrates that, at a concentration generally considered to be safe in the environment, nano-TiO₂ remarkably enhanced the toxicity of copper to Daphnia magna by increasing the copper bioaccumulation. Specifically, at 2 mg L⁻¹ nano-TiO₂, the (LC₅₀) of Cu²⁺ concentration observed to kill half the population, decreased from 111 μg L⁻¹ to 42 μg L⁻¹. Correspondingly, the level of metallothionein decreased from 135 μg g⁻¹ wet weight to 99 μg g⁻¹ wet weight at a Cu²⁺ level of 100 μg L⁻¹. The copper was found to be adsorbed onto the nano-TiO₂, and ingested and accumulated in the animals, thereby causing toxic injury. The nano-TiO₂ may compete for free copper ions with sulfhydryl groups, causing the inhibition of the detoxification by metallothioneins.     

Perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish blood collected near the outfall of wastewater treatment plant (WWTP) in Beijing

Perfluorinated compounds (PFCs) were measured in zooplankton and five fish species collected from Gaobeidian Lake, which receives discharge from wastewater treatment plant (WWTP) in Beijing, China. The mean total PFCs in five fish were in the order: crucian carp > common carp > leather catfish > white semiknife carp > tilapia. Perfluorooctane sulfonate (PFOS) occurred at the greatest concentrations, with mean concentrations ranging from 5.74 to 64.2 ng/ml serum. Perfluorodecanoic acid (PFDA) was the second dominant PFC in fish samples except for common carp in which perfluorooctane sulfonamide (PFOSA) was dominant. A positive linear relationship (r² = 0.85, p < 0.05) was observed between ln PFOS concentrations (ln ng/ml) and trophic level (based on δ¹⁵N) if tilapia was excluded. The risk assessment showed that PFOS might not pose an immediate risk to fish in Gaobeidian Lake.     

Bioaccumulation and depuration of anthracene in Penaeus monodon (Fibricius) through food ingestion

Understanding on the bioaccumulation and depuration of PAHs (polycyclic aromatic hydrocarbons) in Penaeus monodon is important in seafood safety because it is one of the most popular seafood consumed worldwide. In this study, we used anthracene as the precursor compound for PAHs accumulation and depuration in the shrimp. Commercial feed pellets spiked with anthracene were fed to P. monodon. At 20 mg kg⁻¹ anthracene, P. monodon accumulated 0.1% of the anthracene from the feed. P. monodon deputed the PAH two times faster than its accumulation. The shrimp reduced its feed consumption when anthracene content in the feed exceeded 20 mg kg⁻¹. At 100 mg kg⁻¹ anthracene, P. monodon started to have necrosis tissues on the posterior end of their thorax. The bioaccumulation factor (BAF), uptake rate constant (k₁) and depuration rate constant (k₂) of anthracene in P. monodon were 1.15 × 10⁻³, 6.80 × 10⁻⁴ d⁻¹ and 6.28 × 10⁻¹ d⁻¹, respectively. The depuration rate constant is about thousand times higher than the uptake rate constant and this indicated that this crustacean is efficient in depurating hydrocarbons from their tissue.     

Does nitrogen deposition increase forest production? The role of phosphorus

Effects of elevated N deposition on forest aboveground biomass were evaluated using long-term data from N addition experiments and from forest observation plots in Switzerland. N addition experiments with saplings were established both on calcareous and on acidic soils, in 3 plots with Fagus sylvatica and in 4 plots with Picea abies. The treatments were conducted during 15 years and consisted of additions of dry NH₄NO₃ at rates of 0, 10, 20, 40, 80, and 160 kg N ha⁻¹ yr⁻¹. The same tree species were observed in permanent forest observation plots covering the time span between 1984 and 2007, at modeled N deposition rates of 12-46 kg N ha⁻¹ yr⁻¹. Experimental N addition resulted in either no change or in a decreased shoot growth and in a reduced phosphorus concentration in the foliage in all experimental plots. In the forest, a decrease of foliar P concentration was observed between 1984 and 2007, resulting in insufficient concentrations in 71% and 67% of the Fagus and Picea plots, respectively, and in an increasing N:P ratio in Fagus. Stem increment decreased during the observation period even if corrected for age. Forest observations suggest an increasing P limitation in Swiss forests especially in Fagus which is accompanied by a growth decrease whereas the N addition experiments support the hypothesis that elevated N deposition is an important cause for this development.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

Even low to medium nitrogen deposition impacts vegetation of dry, coastal dunes around the Baltic Sea

Coastal dunes around the Baltic Sea have received small amounts of atmospheric nitrogen and are rather pristine ecosystems in this respect. In 19 investigated dune sites the atmospheric wet nitrogen deposition is 3-8 kg N ha⁻¹ yr⁻¹. The nitrogen content of Cladonia portentosa appeared to be a suitable biomonitor of these low to medium deposition levels. Comparison with EMEP-deposition data showed that Cladonia reflects the deposition history of the last 3-6 years. With increasing nitrogen load, we observed a shift from lichen-rich short grass vegetation towards species-poor vegetation dominated by the tall graminoid Carex arenaria. Plant species richness per field site, however, does not decrease directly with these low to medium N deposition loads, but with change in vegetation composition. Critical loads for acidic, dry coastal dunes might be lower than previously thought, in the range of 4-6 kg N ha⁻¹ yr⁻¹ wet deposition.     

Photocatalytic degradation with immobilised TiO(2) of three selected neonicotinoid insecticides: imidacloprid, thiamethoxam and clothianidin

This research focused on photocatalytic degradation of imidacloprid, thiamethoxam and clothianidin employing a tailor-made photoreactor with six polychromatic fluorescent UVA (broad maximum at 355 nm) lamps and immobilised titanium dioxide (TiO₂) on glass slides. The disappearance was followed by high pressure liquid chromatography (HPLC-DAD) analyses, wherein the efficiency of mineralization was monitored by measurements of total organic carbon (TOC). Within 2 h of photocatalysis, all three neonicotinoids were degraded following first order kinetics with rate constants k = 0.035 ± 0.001 min⁻¹ for imidacloprid, k = 0.019 ± 0.001 min⁻¹ for thiamethoxam and k = 0.021 ± 0.000 min⁻¹ for clothianidin. However, the rate of mineralization was low, i.e. 19.1 ± 0.2% for imidacloprid, 14.4 ± 2.9% for thiamethoxam and 14.1 ± 0.4% for clothianidin. This indicates that several transformation products were formed instead. Some of them were observed within HPLC-DAD analyses and structures were proposed according to the liquid chromatography-electro spray ionization tandem mass spectrometry analyses (LC-ESI-MS/MS). The formation of clothianidin, as thiamethoxam transformation product, was reported for the first time.     

Comparison of the cytotoxic responses of Escherichia coli (E. coli) AMC 198 to different fullerene suspensions (nC60)

Fullerenes are set to be produced on an industrial scale in anticipation of their wide applications. This calls for research on their environmental and health impacts. This study investigates and compares the cell toxicity of different aqueous fullerene aggregates. Popular C₆₀ dispersal methods were used to prepare four types of nC₆₀ aggregates. These aggregates were tested against the indicator species Escherichia coli (E. coli) AMC 198. With aggregates of around 150 nm in diameter, the THF/nC₆₀ suspension was very toxic and gave rise to a half maximal effective concentration (EC₅₀) of 0.54 mg L⁻¹ in E. coli. By contrast, the Tol/nC₆₀ suspension exhibited a cytoprotective role while the Aqu-N₂/nC₆₀ and Aqu-O₂/nC₆₀ suspensions enhanced the metabolism of E. coli. Although some toxicants, such as THF and THF-peroxide, were introduced into the THF/nC₆₀ suspension during the dispersion, the toxicity of nC₆₀ itself cannot be neglected.     

Phthalate esters (PAEs): emerging organic contaminants in agricultural soils in peri-urban areas around Guangzhou, China

This study reports the first data on the concentrations and distribution of phthalate esters (PAEs) in the agricultural soils from the peri-urban areas of Guangzhou city. Σ₁₆PAEs concentrations ranged from 0.195 to 33.6 μg g⁻¹-dry weight (dw). Elevated levels of PAEs were recorded in the vegetable fields located next to the urban districts, and a decreasing trend exists following the distance away from the urban center. Diisobutyl phthalate (DiBP), Di-n-butyl phthalate (DnBP), and Di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs in the agricultural soils. Significant relationship (correlation coefficient R² = 0.85, p < 0.01, n = 40) was present between the accumulation of PAEs and total organic carbons in agricultural soils. In addition, both pH and texture of soils are found to be important factors affecting the level of PAEs. This study shows that the agricultural soils in the peri-urban area of Guangzhou city were moderately polluted by PAEs.