Study of the uncertainty in NO<Subscript>2</Subscript> chemiluminescence measurements due to the NO–O<Subscript>3</Subscript> reaction in sampling lines

Introduction  

The change in light intensity that takes place when an ambient air sample is drawn into the detection chamber of a chemiluminescence monitor generates changes in the concentrations of several species, such as NO₂, NO and O₃. Although this phenomenon has been known for several decades, there is still no commonly accepted approach on when or how to correct for it in NO₂ and O₃ readings.     

Assessing the steady-state [·NO<Subscript>2</Subscript>] in environmental samples

Based on available literature data of [NO₂ ⁻], steady-state [·OH], and ·OH generation rate upon nitrate photolysis in environmental aqueous samples under sunlight, the steady-state [·NO₂], could be calculated. Interestingly, one to two orders of magnitude more ·NO₂ would be formed in photochemical processes in atmospheric water droplets compared to transfer from the gas phase. The relative importance of nitrite oxidation compared to nitrate photolysis as an ·NO₂ source would be higher in atmospheric than in surface waters. The calculated levels of ·NO₂ could lead to substantial transformation of phenol into nitrophenols in both atmospheric and surface waters.     

Catalase and ascorbate peroxidase—representative H<Subscript>2</Subscript>O<Subscript>2</Subscript>-detoxifying heme enzymes in plants

Plants have to counteract unavoidable stress-caused anomalies such as oxidative stress to sustain their lives and serve heterotrophic organisms including humans. Among major enzymatic antioxidants, catalase (CAT; EC 1.11.1.6) and ascorbate peroxidase (APX; EC 1.11.1.11) are representative heme enzymes meant for metabolizing stress-provoked reactive oxygen species (ROS; such as H₂O₂) and controlling their potential impacts on cellular metabolism and functions. CAT mainly occurs in peroxisomes and catalyzes the dismutation reaction without requiring any reductant; whereas, APX has a higher affinity for H₂O₂ and utilizes ascorbate (AsA) as specific electron donor for the reduction of H₂O₂ into H₂O in organelles including chloroplasts, cytosol, mitochondria, and peroxisomes. Literature is extensive on the glutathione-associated H₂O₂-metabolizing systems in plants. However, discussion is meager or scattered in the literature available on the biochemical and genomic characterization as well as techniques for the assays of CAT and APX and their modulation in plants under abiotic stresses. This paper aims (a) to introduce oxidative stress-causative factors and highlights their relationship with abiotic stresses in plants; (b) to overview structure, occurrence, and significance of CAT and APX in plants; (c) to summarize the principles of current technologies used to assay CAT and APX in plants; (d) to appraise available literature on the modulation of CAT and APX in plants under major abiotic stresses; and finally, (e) to consider a brief cross-talk on the CAT and APX, and this also highlights the aspects unexplored so far.     

Measurements of β and α hexachlorocyclohexane in <Emphasis Type="Italic">Juglans regia</Emphasis> and <Emphasis Type="Italic">Prunus spinosa</Emphasis> trees in a contaminated area,central Italy

Vegetables play an important role in the human diet, and the transfer of toxic contaminants from the soil to plants has been little studied for most tree species and their edible portions. In an area affected by hexachlorocyclohexane (HCH) contamination, in the Sacco River Valley (central Italy), measurements of β- and α-HCH isomers were made on different parts of two tree species: Juglans regia and Prunus spinosa. Concentrations were analysed in roots, branches, leaves, fruits, and seeds. A spatial evaluation of the results highlighted an inverse association of contamination with distance from the river, which is the main route of transport in the environment. Results in J. regia showed decreasing values in this order: branches > leaves > husks > nutmeat. Results in P. spinosa showed decreasing values in the following order: branches > leaves > fruits. In J. regia, nutmeat values were all below limit of detection (LOD, 0.0005 mg/kg), except in one case in which a very low concentration of β-HCH was found (0.006 mg/Kg), compliant with maximum residue limits (MRLs). The ability of J. regia to store large quantities of β-HCH in wooden and leafy parts but not in edible kernels makes this plant a potential and precious tool in remediation and economical reconversion of polluted areas. It is also valuable for food and wood manufacturing.     

Behaviour and dynamics of di-ammonium phosphate in bauxite processing residue sand in Western Australia—I. NH<Subscript>3</Subscript> volatilisation and residual nitrogen availability

Background, aim and scope

Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa’s residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha^?1 of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications.

Methods

The sponge-trapping and KCl-extraction method was used for determining NH₃ volatilisation from surface-applied DAP in samples of BRS collected from each of Alcoa’s three Western Australia Refineries (Kwinana, Pinjarra, Wagerup) under various pH conditions (pH 4, 7, 9 and 11). Following cessation of volatilisation, the residual N was extracted from BRS using 2 M KCl and concentrations of NH ₄ ⁺ –N and NO ₃ ^? –N were determined by flow injection analysis.

Results

The quantities of NH₃ volatilised increased dramatically as the pH increased from 4 to 11. Much of the N lost as NH₃ (up to 95.2%) occurred within a short period (24 h to 7 days), particularly for the pH 9 and 11 treatments. Concentrations of residual NH ₄ ⁺ –N recovered in DAP-treated BRS at the end of the experiment decreased with increasing pH. This finding was consistent with increasing loss of N via volatilisation as pH increased. The concentration of NO ₃ ^? –N was very low due to no nitrification in BRS.

Discussion

The pH was a key driver for NH₃ volatilisation from DAP-treated BRS and primarily controlled N dynamics in BRS. Results indicate that NH₄ not adsorbed by BRS was highly susceptible to volatilisation. The likely lack of nitrifying bacteria did not allow conversion of ammonium to nitrate, thereby further exacerbating the potential for loss via volatilisation

Conclusions

It was demonstrated that the pH is the key factor controlling the loss of inorganic N from BRS. Although volatilisation was considerably lower at pH 4, achieving this pH reduction in the field is not possible at present. Findings from this study highlight the need to better understand which forms of N fertiliser are most suitable for use in highly alkaline BRS.

Recommendation and perspectives

Although pH reduction is the most likely means of stopping NH₃ volatilisation in BRS, it is economically and operationally unfeasible to add sufficient acidity for adequately lowering pH in the BRS for revegetation. More attention on forms of fertilisers more suitable to highly alkaline, microbially inert soil conditions appears to be warranted.

     

Sediment contact test with <Emphasis Type="Italic">Potamopyrgus antipodarum</Emphasis> in effect-directed analyses—challenges and opportunities

Background and scope  

Effect-directed analysis is increasingly used for the identification of key toxicants in environmental samples and there is a growing need for in vivo biotests as diagnostic tools. Within this study, we performed an in vivo sediment contact test, applicable on both native field samples and their extracts or fractions, in order to be able to compare the results from both field and laboratory studies.     

Importance of exposure route for behavioural responses in <Emphasis Type="Italic">Lumbriculus variegatus</Emphasis> Müller (Oligochaeta: Lumbriculida) in short-term exposures to Pb

Goal, Scope and Background

Lumbriculus variegatus Müller (Oligochaeta), a common freshwater sediment-dweller, has frequently been used in toxicokinetic studies, although has been less used in ecotoxicity tests.

Methods

For the first time the Multispecies Freshwater Biomonitor® (MFB) was applied in a short-term whole-sediment toxicity test. The MFB automatically and quantitatively recorded the spontaneous locomotory behaviour of Lumbriculus variegatus in exposures with two compartments, water and sediment. The study questioned, whether the animals altered their locomotion depending on the compartment which was spiked with lead (Pb).

Results and Discussion

As in the exposures to Pb-contaminated water/clean sediment, the animals exposed to Pb-contaminated sediment/clean water showed higher activities in intermediate Pb-concentrations. This indicates, that spontaneous locomotory activity is affected by Pb-concentrations at sublethal levels regardless of whether the Pb-concentration is found in the water or in the sediment, because these animals use both environmental compartments simultaneously. However, within the same Pb-levels, the animals showed higher locomotory activity in contaminated water compared with contaminated sediment. This indicates a possible tendency to withdraw from (‘avoidance’) contaminated water into the clean sediment compartment, whereas there was no withdrawal from contaminated sediment into clean water. The latter might be explained by the fact that withdrawal from sediment to water might increase the risk of predation and drift in nature, whereas retracting to sediment might provide shelter.

Conclusions

The study showed that spontaneous locomotory responses of L. variegatus to Pb depend on whether the water or sediment is contaminated. The study also concluded that the Multispecies Freshwater Biomonitor® can be applied effectively in sediment toxicity testing.

Recommendations and Perspectives

More emphasis should be given to the interactions of water/sediment in sediment ecotoxicity tests to better simulate field conditions and increase ecological realism in risk assessment, especially as quantitative recording methods exisit.

     

PCA and multidimensional visualization techniques united to aid in the bioindication of elements from transplanted <Emphasis Type="Italic">Sphagnum palustre</Emphasis> moss exposed in the Gdańsk City Area

GOAL, SCOPE AND BACKGROUND: During the last decades, a technique for assessing atmospheric deposition of heavy elements was developed based on the principle that samples of moss are able to accumulate elements and airborne particles from rain, melting snow and dry deposition. Despite a broad interest in bioindication there are still ongoing works aimed at the preparation of a standard procedure allowing for a comparison of research carried out in various areas. This is why the comparison of living and dry moss of the same species and growth site seems to be interesting, logical and promising. A most reliable approach seems to be the application of bioindication connected with multivariate statistics and efficient visualization techniques in the interpretation of monitoring data. The aim of this study was: (i) to present cumulative properties of transplanted Sphagnum palustre moss with differentiation into dry and living biomaterial; (ii) to determine and geographically locate types of pollution sources responsible for a structure of the monitoring data set; (iii) to visualize geographical distribution of analytes in the Gdańsk metropolitan area and to identify the high-risk areas which can be targeted for environmental hazards and public health. MATERIALS AND METHODS: A six month air pollution study based on Sphagnum palustre bioindication is presented and a simplified procedure of the experiment is given. The study area was located at the mouth of the Vistula River on the Baltic Sea, in Gdańsk City (Poland). Sphagnum palustre was selected for research because of its extraordinary morphological properties and its ease in being raised. The capability of dry and living moss to accumulate elements characteristic for anthropogenic and natural sources was shown by application of Principal Component Analysis. The high-risk areas and pollution profiles are detected and visualized using surface maps based on Kriging algorithm. RESULTS: The original selection of elements included all those that could be reliably determined by Neutron Activation Analysis in moss samples. Elimination of variables covered the elements whose concentrations in moss were lower than the reported detection limits for INAA for most observations or in cases where particular elements did not show any variation. Eighteen elements: a, Ca, Sc, Fe, Co, Zn, As, Br, Mo, Sb, Ba, La, Ce, Sm, Yb, Lu, Hf, Th, were selected for the research presented. DISCUSSION: Two runs of PCA were performed since, in the first-run a heavy polluted location (Stogi - 'Sto') understood as outlier in the term of PCA approach was detected and results in the form of block diagrams and surface maps were presented. As ensues from the first-run PCA analysis, the factor layout for both indicators is similar but not identical due to the differences in the elements accumulation mechanism. Three latent factors ('phosphatic fertilizer plant impact', 'urban impact' and 'marine impact') explain over 89% and 82% of the total variance for dry and living moss respectively. In the second-run PCA three latent factors are responsible for the data structure in both moss materials. However, in the case of dry moss analysis these factors explain 85% of the total variance but they are rather hard to interpret. On the other hand living moss shows the same pattern as in first-run PCA. Three latent factors explain over 84% of the total variance in this case. The pollution profiles extracted in PCA of dry moss data differ tremendously between both runs, while no deterioration was found after removal of Stogi from data set in case of living moss. Performance of the second-run PCA with exception of Stogi as a heavy polluted location has led to the conclusion that living moss shows better indication properties than dry one. CONCLUSIONS: While using moss as wet and dry deposition sampier it is not possible to calculate deposition values since the real volume of collected water and dust is hard to estimate due to a splash effect and irregular surface. Therefore, accumulation values seam to be reasonable for moss-based air pollution surveys. Both biomaterials: dry and living Sphagnum palustre show cumulative properties relative to elements under interest. Dry moss has a very loose collection of the atmospheric particles, which can also easily get lost upon rinsing with rainwater running through exposed dry moss material. The living moss may, on the contrary, incorporate the elements in its tissue, thus being less susceptible to rinsing and thus better reflecting the atmospheric conditions. Despite the differences in element uptake and uphold capabilities dry and living moss reflect characteristic anthropogenic and natural profiles. Visible differences in impacts' map coverage exist mostly due to the accumulation mechanisms differentiating dry from living moss. However, in case of each indicator 'phosphatic fertilizer plant impact' is recognized as the strongest pollution source present in examined region. RECOMMENDATIONS AND PERSPECTIVES: General types of pollution sources responsible for a structure of monitoring data set were determined as high-risk/low-risk areas and visualized in form of geographic distribution maps. These locations can be targeted for environmental hazards and public health. Chemometric results in the form of easy defined surface maps can became a powerful instrument in hands of decision-makers working in the field of sustainable development implementation.     

<Emphasis Type="Italic">Cylindrospermopsis raciborskii</Emphasis> exudate–Cu complexes: impact on copper dynamics and bioavailability in an aquatic food chain

INTRODUCTION: The increasing contamination of aquatic environments motivates studies on the interactions among natural dissolved organic matter, metals, and the biota. This investigation focused on the organic exudates of the toxic cyanobacteria Cylindrospermopsis raciborskii as a Cu carrier through a three-level aquatic trophic chain (bacteria, protozoa, and copepod). DISCUSSION: The effects of bacteria activity and growth on the metal-organic complexes were evaluated through changes in free Cu(2+) ions, total dissolved, and total particulate Cu. To be sure that the added copper would be complexed to the exudates, its complexing properties were previously determined. The cyanobacteria exudate-Cu complexes were furnished to bacteria that were further used as a food source to the protozoan Paramercium caudatum. This was then furnished as food to the copepod Mesocyclops sp. The results showed that, in general, the cyanobacterial exudates decreased Cu bioavailability and toxicity to the first trophic level (bacteria), but because the heterotrophic bacteria accumulated Cu, they were responsible for the transference for the otherwise low availability metal form. Both the bacteria and protozoan organisms accumulated Cu, but no metal accumulation was detected in the copepods.     

Synergetic effects of Sr-doped CuBi<Subscript>2</Subscript>O<Subscript>4</Subscript> catalyst with enhanced photoactivity under UVA– light irradiation

Sr-doped CuBi₂O₄ micro-particles were successively synthesized via a solid-state technique and were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and UV–vis diffuse reflectance spectroscopy (UV–vis-DRS) techniques. Results show that Sr-doped CuBi₂O₄ was crystallized with a spinel-type structure and tetragonal crystal system, and the band gap energy was about 1.35 eV. The as-prepared Sr-doped CuBi₂O₄ treated at 573 °C for 12 h exhibited the highest efficiency, as a result of 97.22 % of CR degradation within 220 min, which is approximately 31 times greater than CR photodegradation when catalyzed by CuBi₂O₄ (3.13 %) and about 2.3 times superior than that catalyzed by the untreated Sr–doped CuBi₂O₄ sample (42.08 %). Pseudo-first-order kinetic model gave the best fit, with highest correlation coefficients (R ²?=?0.94–0.97). The Sr–doping and extending reaction time up to 12 h could be effective in producing Sr-doped CuBi₂O₄ materials that delay electron–hole recombination, thereby increasing the lifetime of the electron electron–hole separation and support the charge carrier transfer to the catalyst surface. On the basis of the calculated energy band positions, superoxide radical anions (O₂ ^?–) were the main oxidative species responsible for the photocatalytic degradation of CR dye solution.     

Endpoint ‘floating leaves’ of <Emphasis Type="Italic">Potamogeton natans</Emphasis>: A new method to evaluate the development of macrophytes in pond mesocosms

Goal, Scope and Background One of the advantages of long-term mesocosm experiments as compared to short-term standard toxicity tests in the laboratory is the potential for detecting secondary effects due to the interaction of species and recovery with biomass of macrophytes being an important endpoint. However, generating biomass data by harvesting is often laborious, time-consuming, costly and restricted to the end of the experiment. Moreover, valuable information may get lost, in particular in single application studies, since maximal primary effects and secondary effects or recovery occur per se at different times. Potamogeton natans was used as an example in order to test whether number and area of floating leaves can be reliably measured and be used as intermediate and final endpoints in mesocosm effect studies. Methods Digital photos, which were taken of the water surface in the course of an indoor pond mesocosm study on herbicide effects, were subjected to image analysis. The results were compared to wet weight and ash-free dry weight of Potamogeton at the end of the herbicide study. Results and Discussion Both number and area of floating leaves indicated the same herbicide effects as wet weight and ash-free dry weight of Potamogeton. Error introduced by the different work steps is small and can be further minimised by a number of method improvements. Recommendations and Perspectives In indoor mesocosm studies, errors due to the perspective adjustment may be circumvented by taking the photos perpendicular to the water surface. Correction for lens aberration, identical light conditions and the use of fluorescence images are considered promising. Field applications are proposed.     

Biological effect monitoring in dab (<Emphasis Type="Italic">Limanda limanda</Emphasis>) using gene transcript of CYP1A1 or EROD—a comparison

BACKGROUND, AIM, AND SCOPE: Gene expression analyses with real-time (RT)-polymerase chain reaction (PCR) gains importance in marine monitoring. This new technique has to be compared to the classical approaches like the well known biomarker ethoxyresorufin-O-deethylase (EROD) to test their suitability for monitoring programmes. The goal of the present study is to compare EROD activity and CYP1A1 mRNA expression in the important monitoring fish species dab (Limanda limanda) and to answer the question of whether these parameters reflect the polycyclic aromatic hydrocarbon (PAH) contamination of the fish. Further on, glyceraldehyd-3-phosphate dehydrogenase (GAPDH) was investigated as a potential housekeeping gene. MATERIALS AND METHODS: Female dab were caught in the summer of 2004 in the North Sea and in the Baltic. EROD activity was determined in liver samples by a kinetic fluorimetric assay according to a standard protocol. The gene expression of CYP1A (cytochrome P450 1A) and GAPDH were determined by means of RT-PCR. Results were compared to gonado somatic index and to the concentration of PAH metabolite 1OHPyr (1-hydroxypyrene) analysed in the bile fluids of the fish, respectively. RESULTS: Dab from all stations showed a considerable individual variation in the levels of both CYP1A mRNA and EROD. Highest mean values for CYP1A mRNA and EROD were detected in the northern part of the sampling area. In contrast, the PAH metabolite 1OHPyr was found at the highest concentration in fish caught near the German coast. CYP1A mRNA and EROD showed only a minor but significant correlation (r = 0.32, p < 0.05, n = 123). 1OHPyr in bile correlated significantly (p < 0.05) with the amount of GAPDH mRNA content in the liver. DISCUSSION: The significant but low correlation of CYP1A mRNA and EROD activity on an individual basis illustrates that these two parameters are apparently not closely linked. However, maximum EROD values correspond with maximum CYP1A mRNA concentrations when station means are regarded. Because EROD and CYP1A mRNA in dab follow different physiological principles, their application will lead to related but not identical monitoring results. This should be taken into account when future marine monitoring programmes are designed. The results also indicate that PAH are not the crucial factor for CYP1A and EROD levels in dab from the off-shore areas in the North Sea. This is remarkable because the PAH metabolism is known to be CYP1A-dependent and the widely used biomarker EROD has been recommended for monitoring PAH-related effects in fish from the North Sea. Due to a correlation between GAPDH and 1OHPyr, GAPDH was not suitable as housekeeping gene for dab. CONCLUSIONS: Neither the results from EROD nor from CYP1A1 mRNA measurements in dab reflected their exposure to PAH as measured by the PAH metabolite 1OHPyr. Thus, the question arises of whether EROD or CYP1A mRNA is a suitable biomarker at all to indicate PAH exposure in dab from the open North Sea. RECOMMENDATIONS AND PERSPECTIVES: For future biological effect monitoring, it is advisable to measure more and predominately independent parameters by RT-PCR and to incorporate more components of the detoxification system.     

Is small hydropower beautiful? Social impacts of river fragmentation in China’s Red River Basin

Small hydropower (SHP) is promoted as a pro-poor renewable energy source that does not have the negative social impacts of large dams. This article challenges these claims, using data from a household survey in China’s upper Red River Basin. We find that SHP can fragment river systems in ways that reduce irrigation water availability, provoke changes to agricultural practices, and negatively impact river health. These social impacts of river fragmentation mainly occur in villages situated between a plant’s intake and outflow. The frequency of plant water diversions due to continued generation in the dry season significantly predicts all social impacts; installed capacity of the plant and the quality of the village’s irrigation infrastructure predict some impacts. Villages with strong local governance can negotiate with the plant to temporarily halt generation when irrigation water is needed, lessening social impacts. Our findings reveal that SHP plants are not as benign as they are made out to be; they must be built and managed according to community needs.     

Collection efficiency of a midget impinger for nanoparticles in the range of 3–100 nm

Impingers have been employed for collection of biological particles for a long time and the collection efficiency for submicron particles has been well studied for a few impinger models, like the SKC Biosampler and the AGI 30. These efficiency studies have been limited to particles larger than about 15 nm. The aim of this research is to determine the collection efficiency of ultrafine particles (from 3 to 100 nm) of a 25 ml midget impinger. The effect of different collection parameters (particle type, collection fluid volume and type and flow rate) was studied and results are presented here. All results showed minimum collection efficiencies from 3 to 10% at approximately 40–57 nm. Increasing the volume of the collection liquid and flow rate improved the collection efficiency of the impinger.     

Wetting mechanism and morphological adaptation; leaf rolling enhancing atmospheric water acquisition in wheat crop—a review

Environmental Science and Pollution Research - Several plant species such as grasses are dominant in many habitats including arid and semi-arid areas. These species survive in these regions by...