(Persistent) Organic pollutants in Germany: results from a pilot study within the 2015 moss survey

Background

Since 1990, every 5 years, moss sampling is conducted within the European moss monitoring programme to assess the atmospheric deposition of airborne pollutants. Besides many other countries, Germany takes regularly part at these evaluations. Within the European moss monitoring 2015, more than 400 moss samples across Germany were taken according to a harmonized methodology for the assessment heavy metal and nitrogen input. In a pilot programme, eight of these sites were chosen for additional investigations on a broad range of organic contaminants to evaluate their accumulation in moss and thereby their presence in atmospheric deposition in Germany. Target compound classes comprised polycyclic aromatic hydrocarbons (PAH), polychlorinated dibenzodioxins and –furans (PCDD/F), dioxin-like and non-dioxin-like polychlorinated biphenyls (dl-PCB, ndl-PCB), polyfluorinated alkyl substances, classical flame retardants as well as emerging chlorinated and brominated flame retardants. In total, 120 target compounds were analysed. For some analytes, comparisons of accumulation in moss and tree leave samples were possible.

Results

Except for certain flame retardants, PFAS, and ndl-PCB, substances of all other compound classes could be quantified in moss samples of all sites. Concentrations were highest for PAH (40–268 ng g^?1) followed by emerging flame retardants (0.5–7.7 ng g^?1), polybrominated diphenyl ethers (PBDE; 0.3–3.7 ng g^?1), hexabromocyclododecane (HBCD; 0.3–1.2 ng g^?1), dl-PCB (0.04–0.4 ng g^?1) and PCDD/F (0.008–0.06 ng g^?1).

Conclusions

Results show the widespread atmospheric distribution and deposition of organic contaminants across Germany as well as the suitability of moss as bioaccumulation monitor for most of these compound classes. Compared to nearby tree leaf samples, accumulation potential of moss appeared to be higher for pollutants of high octanol–air partition coefficient (K_OA) and octanol–water partition coefficient (K_OW).

     

Zur Beständigkeit von Aluminiumchloridlösungen mit tridekameren Kationen (Al<Subscript><Emphasis Type="Bold">13</Emphasis></Subscript>)

Background, aim, and scopeThe focus of popular interest on the subject of acid rain has been on the effects, which it has on aquatic ecosystems. Aluminium toxicity and the bioavailability depend on the species of aluminium present. The cationic aluminium species are important for the phytotoxocity and for the precipitation of aluminium containing precipitate.Materials and methodsSpeciation diagrams of aqueous aluminium chloride solutions with tridecameric cations (Al₁₃) at room temperature as function of concentration (1·10^–1–1·10^–5 mol·l^–1 Al) and aging time (9 month) have been obtained from a kinetic method; these Ferron method offers a simple and inexpensive alternative for identification and quantification of aluminium cations.ResultsThe Al₁₃-cation stability decrease with decreasing concentration and increasing aging time.DiscussionPolynuclear aluminium species can be formed in nature by the dissolution of Al-containing minerals, as a consequence of surface water acidification, followed by neutralization process. The question of the occurrence of the tridecameric polycation (Al₁₃) in natural soil solutions and stream waters is of considerable interest.ConclusionsThe results are important on the occurrence of the Al₁₃ in natural waters, for the precipitation of aluminium species by acidification and for the aluminium phytotoxicity.Recommendations and perspectivesThis research suggests strongly that Al₁₃ should be negligible in natural soil and surface waters. The toxicity of Al₁₃ to plants and aquatic organism in natural conditions may be considered to be very low.     

Influence of physico-chemical properties of soil clay fractions on the retention of dissolved organic carbon

This study investigated the effects of surface functional groups, cation exchange capacity (CEC), surface charge, sesquioxides and specific surface area (SSA) of three soil clay fractions (SCFs) (kaolinite–illite, smectite and allophane) on the retention of dissolved organic carbon (DOC) in soils. Physico-chemical properties of the SCFs before and after removing native carbon and/or sesquioxides were characterised, and the DOC adsorption–desorption tests were conducted by a batch method. Native organic carbon (OC)/sesquioxide removal treatments led to a small change in the CEC values of kaolinite–illite, but significant changes in those of smectite and allophane. The net negative surface charge increased in all samples with an increase in pH indicating their variable charge characteristics. The removal of native OC resulted in a slight increase in the net positive charge on soil clay surfaces, while sesquioxide removal increased the negative charge. Changes in the functional groups on the SCF surfaces contributed to the changes in CEC and zeta potential values. There was a strong relationship (R ² = 0.93, p < 0.05) between the Langmuir maximum DOC adsorption capacity (Q _max) and SSA. The Q _max value also showed a moderately strong relationship (R ² = 0.55, p < 0.05) with zeta potential (at pH 7). Q _max was only poorly correlated with CEC and native OC content. Therefore, along with SSA, the surface charge and functional groups of SCFs played the key role in determining the adsorption affinity and hence retention of DOC in soils.     

Environmental modeling of uranium interstitial compositions of non-stoichiometric oxides: experimental and theoretical analysis

Study of uranium interstitial compositions of non-stoichiometric oxides UO_2+x (x ∈ 0.1–0.02) in gas and condense phases has been presented, using various soft-ionization mass spectrometric methods such as ESI-, APCI-, and MALDI-MS at a wide dynamic temperature gradient (∈ 25–300 °C). Linearly polarized vibrational spectroscopy has been utilized in order to assign unambiguously, the vibrational frequencies of uranium non-stoichiometric oxides. Experimental design has involved xUO_2.66·yUO_2.33, xUO_2.66·yUO_2.33/SiO₂, xUO_2.66·yUO_2.33/SiO₂ (NaOH) and SiO₂/x′NaOH·y′UO₂(NO₃)₂·6H₂O, multicomponent systems (x = 1, y ∈ 0.1–1.0 and x′ = 1, y′ ∈ 0.1–0.6) as well as phase transitions UO₂(NO₃)₂·6H₂O → {U₄O₉(UO_2.25)} → U₃O₇(UO_2.33) → U₃O₈(UO_2.66) → {UO₃}, thus ensuring a maximal representativeness to real environmental conditions, where diverse chemical, geochemical and biochemical reactions, including complexation and sorption onto minerals have occurred. Experimental factors such as UV-irradiation, pH, temperature, concentration levels, solvent types and ion strength have been taken into consideration, too. As far as uranium speciation represents a challenging analytical task in terms of chemical identification diverse coordination species, mechanistic aspects relating incorporation of oxygen into UO _2+x form the shown full methods validation significantly impacts the field of environmental radioanalytical chemistry. UO₂ is the most commonly used fuel in nuclear reactors around the globe; however, a large non-stoichiometric range ∈ UO_1.65–UO_2.25 has occurred due to radiolysis of water on UO₂ surface yielding to H₂O₂, OH^·, and more. Each of those compositions has different oxygen diffusion. And in this respect enormous effort has been concentrated to study the potential impact of hazardous radionuclide on the environment, encompassing from the reprocessing to the disposal stages of the fuel waste, including the waste itself, the processes in the waste containers, the clay around the containers, and geological processes. In a broader sense, thereby, this study contributes to field of environmental analysis highlighting the great ability of various soft-ionization MS methods, particularly, MALDI-MS one, for direct assay of complex multicomponent heterogeneous mixtures at fmol–attomol concentration ranges, along with it the great instrumental features allowing, not only meaningful quantitative, but also structural information of the analytes, thus making the method indispensable for environmental speciation of radionuclides, generally.     

Blood concentrations of lead,cadmium, mercury and their association with biomarkers of DNA oxidative damage in preschool children living in an e-waste recycling area

Reactive oxygen species (ROS)-induced DNA damage occurs in heavy metal exposure, but the simultaneous effect on DNA repair is unknown. We investigated the influence of co-exposure of lead (Pb), cadmium (Cd), and mercury (Hg) on 8-hydroxydeoxyguanosine (8-OHdG) and human repair enzyme 8-oxoguanine DNA glycosylase (hOGG1) mRNA levels in exposed children to evaluate the imbalance of DNA damage and repair. Children within the age range of 3–6 years from a primitive electronic waste (e-waste) recycling town were chosen as participants to represent a heavy metal-exposed population. 8-OHdG in the children’s urine was assessed for heavy metal-induced oxidative effects, and the hOGG1 mRNA level in their blood represented the DNA repair ability of the children. Among the children surveyed, 88.14% (104/118) had a blood Pb level >5 μg/dL, 22.03% (26/118) had a blood Cd level >1 μg/dL, and 62.11% (59/95) had a blood Hg level >10 μg/dL. Having an e-waste workshop near the house was a risk factor contributing to high blood Pb (r _s  = 0.273, p < 0.01), while Cd and Hg exposure could have come from other contaminant sources. Preschool children of fathers who had a college or university education had significantly lower 8-OHdG levels (median 242.76 ng/g creatinine, range 154.62–407.79 ng/g creatinine) than did children of fathers who had less education (p = 0.035). However, we did not observe a significant difference in the mRNA expression levels of hOGG1 between the different variables. Compared with children having low lead exposure (quartile 1), the children with high Pb exposure (quartiles 2, 3, and 4) had significantly higher 8-OHdG levels (β _Q2 = 0.362, 95% CI 0.111–0.542; β _Q3 = 0.347, 95% CI 0.103–0.531; β _Q4 = 0.314, 95% CI 0.087–0.557). Associations between blood Hg levels and 8-OHdG were less apparent. Compared with low levels of blood Hg (quartile 1), elevated blood Hg levels (quartile 2) were associated with higher 8-OHdG levels (β _Q2 = 0.236, 95% CI 0.039–0.406). Compared with children having low lead exposure (quartile 1), the children with high Pb exposure (quartiles 2, 3, and 4) had significantly higher 8-OHdG levels.     

Respiration and lipid content of the Arctic copepod<Emphasis Type="Italic"> Calanus hyperboreus</Emphasis> overwintering 1 m above the seafloor at 2,300 m water depth in the Fram Strait

In August 2000 high concentrations of the dominant herbivorous copepod Calanus hyperboreus were detected in the Arctic Fram Strait, west of Spitsbergen, 1 m above the seafloor at 2,290 m water depth. Individuals from that layer were sampled by a hyper-benthic net attached to the frame of an epi-benthic sledge. For comparison, the vertical distribution of C. hyperboreus in the water column was studied simultaneously by a multiple opening/closing net haul from 2,250 m depth to the surface. Maximum abundance was found close to the surface with 6.6 and 10.0 ind. m^?3 at 0–50 m and 50–100 m depth, respectively. However, the major fraction of the population (>40%) occurred between 1,000 and 1,500 m depth. In the deepest layer (2,000–2,250 m) abundance measured 2.2 ind. m^?3 and was twice as high as between 100 and 1,000 m depth. In comparison to individuals from surface waters, copepods from the hyper-benthic layer were torpid and did not react to mechanical stimuli. Stage CV copepodids and females from the deep sample contained 4–10% less lipid and showed significantly reduced respiration rates of 0.24 and 0.26 ml O₂ h^?1 g^?1 dry mass (DM) as compared to surface samples (0.49 and 0.43 ml O₂ h^?1 g^?1 DM). All these observations indicate that the hyper-benthic part of the population had already started a dormant overwintering phase at great depth. Based on the lipid deposits and energy demands, the potential maximum duration of the non-feeding dormant phase was estimated at 76–110 days for females and at 98–137 days for CV copepodids, depending on what indispensable minimum lipid content was assumed. In any case, the estimated times could not meet the necessary requirements for a starvation period of >6 months until the next phytoplankton bloom in the following spring. The ecological implications of these results are discussed with respect to the life cycle and eco-physiological adaptations of C. hyperboreus to its high-Arctic habitat.     

In vitro mass multiplication of screw pines (<Emphasis Type="Italic">Pandanus</Emphasis> spp.) - an important costal bio- resource

An efficient in vitro mass multiplication protocol was developed for selected species of screw pine (Pandanus fascicularis Lam., P. furcatus Roxb.). The protocol could be successfully used for large scale production of planting materials leading to cultivation and making bio-fences or green belts in coastal areas, wetlands for protection and preventing soil erosion. This will facilitate the replenishment of the bio resource and also provide good breeding space for various fauna associated with it. For developing the tissue culture protocol, shoot tips and tillers from the mature plants were used as the explants. Surface sterilization with 0.1 % mercuric chloride for 1 min. Yielded good fraction (65 %) of contamination free explants. Explants inoculated in MS solid medium supplemented with 6-benzylaminopurine (BAP, 2.5 mg/l) and indole-3-acetic acid (IAA, 0.5 mg/l), induced 2–3 shoot buds in 5 weeks. These buds either individually or along with the explant portion, sub-cultured to fresh media containing the same hormonal combinations, resulted induction of 5–6 shoot buds in 4 weeks. Repeated subcultures of shoot buds in the same medium produced 8–10 shoot buds in every 4 weeks. Shoot elongation was achieved (~ 3 cm) by transferring the shoot clusters or individual shoots to basal medium, and the elongated shoots were rooted in vitro or ex vitro. Root induction in shoots (87.4 %) was achieved in MS medium supplemented with 0.1 mg/l indole-3-butyric acid (IBA). Rooted shoots were established in paper/polythene cups filled with fine sand, which subsequently recorded 85 % establishment under the shade-net house with proper irrigation. Plants grown in poly-bags were later successfully established in different field conditions and recorded 100 % survival.     

Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces

This study examines the adsorption isotherms, kinetics and mechanisms of Pb²⁺ sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²⁺ in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²⁺ with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²⁺ and PO₄ ^3? concentrations during the metal sorption processes. The Pb²⁺ sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb⁺. The sorption isotherm results indicated that Pb²⁺ sorption onto the Langmuir and Freundlich constant q _max and K _F is 9.52 and 8.18 mg g^?1, respectively. Sorption kinetics results indicated that Pb²⁺ sorption onto WCBP was pseudo-second-order rate constants K ₂ was 1.12 g mg^?1 h^?1. The main mechanism is adsorption or surface complexation (≡POPb⁺: 61.6%), co-precipitation or ion exchange [Ca_3.93 Pb_1.07 (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L^?1 and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²⁺ removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²⁺ indicates its potential as another promising way to remediate Pb²⁺-contaminated media.     

Characterization and speciation of mercury in mosses and lichens from the high-altitude Tibetan Plateau

The accumulation and species of mercury (Hg) in mosses and lichens collected from high-altitude Tibetan Plateau were studied. The altitudes of the sampling sites spanned from 1983 to 5147 m, and a total of 130 mosses and 52 lichens were analyzed. The total mercury (THg) contents in mosses and lichens were in the ranges of 13.1–273.0 and 20.2–345.9 ng/g, respectively. The average ratios of methylmercury (MeHg) in THg in mosses and lichens were 2.4 % (0.3–11.1 %) and 2.7 % (0.4–9.6 %), respectively, which were higher than those values reported in other regions. The contents of THg in both mosses and lichens were not correlated with the THg in soils (p > 0.05). The lipid contents displayed a significantly positive correlation with concentrations of MeHg in mosses (r = 0.461, p < 0.01, n = 90), but not in lichens. The correlations between Hg contents in mosses and the altitudes, latitudes and longitudes of sampling sites indicated the mountain trapping and spatial deposition of Hg in the Tibetan Plateau.     

HCHs and DDTs in Yellow River of Henan section—a typical agricultural area in China: levels,distributions and risks

The levels, potential sources and ecological risks of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) in Yellow River of Henan section, a typical agricultural area in China, were investigated. Surface water samples and suspended particulate matters (SPMs) were collected from 23 sites during two seasons. In wet season, the residues of ∑HCHs (α-HCH, β-HCH, γ-HCH and δ-HCH) and ∑DDTs (p,p′-DDT, o,p′-DDT, p,p′-DDE, p,p′-DDD) ranged from 41.7 to 290 and 4.42 to 269 ng/L in surface water, while those varied from 0.86 to 157 and 1.79 to 96.1 ng/g dw in SPM, respectively. Moreover, in surface water, the levels of HCHs and DDTs in wet season were much higher than those in dry season. The reverse was true for residues of HCHs and DDTs in SPM. Compared with the large rivers in other regions, the levels of HCHs and DDTs in the studied area ranked at high levels and the residual concentrations might cause adverse biological risk, especially for ∑HCHs during wet season. Distributions of HCHs and DDTs delineated that the input of tributaries made a significant effect on the residue of HCHs and DDTs in the mainstream. ∑HCHs in surface water were consist of 26.7 % α-HCH, 30.0 % β-HCH, 37.9 % γ-HCH and 5.45 % δ-HCH and those in SPM contained 5.16 % α-HCH, 22.1 % β-HCH, 60.5 % γ-HCH and 12.2 % δ-HCH on average. Combined with ratios of α-HCH/γ-HCH in surface water (0.70) and in SPM (0.09), the results strongly indicated that lindane was recently used or discharged in the studied area. The mean percentage of DDTs′ isomers were 28.7 % p,p′-DDT, 29.8 % o,p′-DDT, 28.1 % p,p′-DDE and 13.4 % p,p′-DDD in surface water, while those were 12.5 % p,p′-DDT, 31.8 % o,p′-DDT, 30.5 % p,p′-DDE and 25.1 % p,p′-DDD in SPM. The ratios of (DDE + DDD)/∑DDTs and o,p′-DDT/p,p′-DDT revealed that the DDTs in the studied area mainly derived from long-term weathering of technical DDTs residue and the input of dicofol.     

Clean electrochemical deposition of calcium carbonate to prevent scale formation in cooling water systems

Calcium carbonate (CaCO₃) deposited in water systems leads to scale formation, decreases flow rate, reduces heat transfer and favors microbial proliferation of toxic bacteria such as Legionella. This issue may be solved by electrochemical deposition, without adding toxic chemicals. Therefore, we studied here the deposition of CaCO₃ by electrochemical reduction of oxygen into hydroxide ions with stainless steel and titanium (Ti) working electrodes. Analysis was done using cyclic voltammetry, chronoamperometry, dynamic impedance spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (EDX) coupled with X-ray diffraction (XRD). Results show that optimal formation of CaCO₃ is done at ?1.2 V with the stainless steel electrode and at ?1.4 V for the Ti electrode. More negative potentials induce the formation of calcite. Using the Ti electrode, we found that aragonite is the major form (82 %), with only one capacitive loop. Using the stainless steel electrode at 1.2 V, we found 47 % of aragonite and 38 % of calcite. Overall, our findings demonstrate the feasibility of the electrochemical deposition of CaCO₃ in cooling water systems, without the addition of any chemical.     

Phototransformation of oxamyl in aqueous solution

The photolysis of the N methyl carbamate pesticide oxamyl (Z isomer) has been studied in aqueous solution. Continuous irradiation at mainly λ = 254 and λ > 290 nm has been performed to characterise the pesticide photochemical behaviour in water at pH = 6.0. Upon monochromatic irradiation, the phototransformation quantum yield was evaluated to be roughly constant, with a value of 0.54 ± 0.08. Upon polychromatic irradiation, a photochemical efficiency has been estimated to be 0.5 ± 0.1 by using phenol as a reference compound. Two main degradation products were identified: the isomer (E) of oxamyl and the nitrile derivative (N,N-dimethyl-2-nitrilo-acetamide). The photolysis of the oximino derivative, an hydrolysis product of oxamyl, was also studied. Upon irradiation at 254 nm, the quantum yield of phototransformation was found to be 0.28. A unique photoproduct was detected: it corresponds to the (E) isomer of the oximino derivative. For prolonged irradiations, a photostationary state was reached between the oximino and its (E) isomer. From kinetics data, the removal of oxamyl and of the oximino derivative during a UV disinfection step used in drinking water production was calculated to be 45 and 13%, respectively.     

Ecotoxicological risks of the abandoned F–Ba–Pb–Zn mining area of Osor (Spain)

Due to its potential toxic properties, metal mobilization is of major concern in areas surrounding Pb–Zn mines. In the present study, metal contents and toxicity of soils, aqueous extracts from soils and mine drainage waters from an abandoned F–Ba–Pb–Zn mining area in Osor (Girona, NE Spain) were evaluated through chemical extractions and ecotoxicity bioassays. Toxicity assessment in the terrestrial compartment included lethal and sublethal endpoints on earthworms Eisenia fetida, arthropods Folsomia candida and several plant species, whereas aquatic tests involved bacteria Vibrio fischeri, microalgae Raphidocelis subcapitata and crustaceans Daphnia magna. Total concentrations of Ba (250–5110 mg kg^?1), Pb (940 to >5000 mg kg^?1) and Zn (2370–11,300 mg kg^?1) in soils exceeded intervention values to protect human health. Risks for the aquatic compartment were identified in the release of drainage waters and in the potential leaching and runoff of metals from contaminated soils, with Cd (1.98–9.15 µg L^?1), Pb (2.11–326 µg L^?1) and Zn (280–2900 µg L^?1) concentrations in filtered water samples surpassing US EPA Water Quality Criteria (2016a, b). Terrestrial ecotoxicity tests were in accordance with metal quantifications and identified the most polluted soil as the most toxic. Avoidance and reproduction tests with earthworms showed the highest sensitivity to metal contamination. Aquatic bioassays performed in aqueous extracts from soils confirmed the results from terrestrial tests and also detected toxic effects caused by the mine drainage waters. Algal growth inhibition was the most sensitive aquatic endpoint. In view of the results, the application of a containment or remediative procedure in the area is encouraged.     

Buffer sensitivity of photosynthetic carbon utilisation in eight tropical seagrasses

Some of the mechanisms involved in inorganic carbon (Ci) acquisition by tropical seagrasses from the western Indian Ocean were described by Björk et al. (Mar Biol 129:363–366, 1997). However, since then, it has been found that an additional, buffer-sensitive, system of Ci utilisation may operate in some temperate seagrasses (Hellblom et al. in Aquat Bot 69:55–62, 2001, Hellblom and Axelsson in Photos Res 77:173–191, 2003); this buffer sensitivity indicates a mechanism in which electrogenic H⁺ extrusion may form acidic diffusion boundary layers, in which either HCO ₃ ^? –H⁺ is co-transported into the cells, or where HCO ₃ ^? is converted to CO₂ (as catalysed by carbonic anhydrase) prior to uptake of the latter Ci form. Because a buffer was used in the 1997 study, we found it important to reinvestigate those same eight species, taking into account the direct effect of buffers on this potential mode of Ci acquisition in these plants. In doing so, it was found that all seagrass species investigated except Cymodocea serrulata were sensitive to 50 mM TRIS buffer of the same pH as the natural seawater in which they grew (pH 8.0). Especially sensitive were Halophila ovalis, Halodule wrightii and Cymodocea rotundata, which grow high up in the intertidal zone (only ca. 50–65% of the net photosynthetic activity remained after the buffer additions), followed by the submerged Enhalus acoroides and Syringodium isoetifolium (ca. 75% activity remaining), while Thalassia hemprichii and Thalassodendron ciliatum, which grow in-between the two zones, were less sensitive to buffer additions (ca. 80–85% activity remaining). In addition to buffer sensitivity, all species were also sensitive to acetazolamide (AZ, an inhibitor of extracellular carbonic anhydrase activity) such that ca. 45–80% (but 90% for H. ovalis) of the net photosynthetic activity remained after adding this inhibitor. Raising the pH to 8.8 (in the presence of AZ) drastically reduced net photosynthetic rates (0–14% remaining in all species); it is assumed that this reduction in rates was due to the decreased CO₂ concentration at the higher pH. These results indicate that part of the 1997 results for the same species were due to a buffer effect on net photosynthesis. Based on the present results, it is concluded that (1) photosynthetic Ci acquisition in six of the eight investigated species is based on carbonic anhydrase catalysed HCO ₃ ^? to CO₂ conversions within an acidified diffusion boundary layer, (2) C. serrulata appears to support its photosynthesis by extracellular carbonic anhydrase catalysed CO₂ formation from HCO ₃ ^? without the need for acidic zones, (3) H. ovalis features a system in which H⁺ extrusion may be followed by HCO ₃ ^? –H⁺ co-transport into the cells, and (4) direct, non-H⁺-mediated, uptake of HCO ₃ ^? is improbable for any of the species.     

Comparative degradation rates of chitinous exoskeletons from deep-sea environments

Hydrothermal vent environments, particularly those associated with the vestimentiferan Riftia pachyptila, are believed to be among the highest chitin-producing systems. In order to elucidate the chitin cycle in these environments, we estimate the in situ chitin degradation rates of tube-worm exoskeletons. Our in situ experiments show that the tubes of Riftia are highly stable structures. Comparative measurements of the degradation rates of Riftia tubes and crab shells immersed at deep-sea vents show that the tubes would be degraded within 2.5 years, whereas the time for the total degradation of the vent crab (Bythograea thermydron) carapaces would not exceed 36 days. The importance of the microbial participation in this degradation was estimated for Riftia tubes. Based on previous work, we calculated chitin production by a population of Riftia tubes of about 750 g m^-2 year^-1 (763). From our in situ experiments, we estimated a microbial chitinolysis rate of about 500 g m^-2 year^-1 (496) (65% of the chitin produced).Exoskeletons containing β-chitin appear more stable in natural environments than those containing α-chitin and would thus be less available as carbon and nitrogen sources. In contrast, isolated β-chitin was hydrolysed faster than α-chitin during in vitro degradation experiments; for instance, Riftia β-chitin was degraded about 3- to 4-fold faster than Bythograea α-chitin. A stabilization process by disulfide bonds of the proteins-chitin link, rather than the crystalline form of the chitin (α/β), accounts for the resistance of Riftia tubes to enzymatic attacks.     

Differences in the species- and size-composition of fish assemblages in three distinct seagrass habitats with differing plant and meadow structure

Fish faunas were sampled seasonally using a large and a small beam trawl in three seagrass habitats comprising predominantly Amphibolis griffithii or Posidonia sinuosa or Posidonia coriacea, which differ in seagrass and meadow structure. Amphibolis griffithii and P. sinuosa both produce a relatively dense leaf canopy, but the former exhibits a distinct architecture, with the leaf canopy overlying relatively open spaces surrounding woody stems, compared to the uniformly dense blade-like leaves of P. sinuosa which emerge directly from the sediment. In comparison, P. coriacea provides a landscape of patchy seagrass amongst areas of bare sand. Since the latter seagrass habitat contains large areas of sand, fish were also sampled in adjacent unvegetated areas. The number of species and density of fish were greater (P<0.05) in P. sinuosa than in either A. griffithii or P. coriacea. The mean number of species caught using the large trawl ranged from 16 to 24 in the first of these habitats compared to 14–21 and 9–15 in the last two habitats, respectively, and the mean densities ranged between 78 and 291 fish 1000 m^?2 in P. sinuosa compared to 31–59 fish 1000 m^?2 in A. griffithii and 31–59 fish 1000 m^?2 in P. coriacea. The biomass of fish was greater (P<0.05) in both P. sinuosa and A. griffithii than in P. coriacea (4.2–5.3 kg and 3.3–6.2 kg versus 0.7–1.9 kg 1000 m^?2, respectively). Furthermore, the size-structure of fish differed among these habitats, where the median weight of fish was 72.1 g in A. griffithii, compared to 7.5 g and 19.8 g in P. sinuosa and P. coriacea, respectively. Ordination and ANOSIM demonstrated that the species-composition differed markedly among the three seagrass habitats (P<0.001), suggesting that fish species display a distinct preference for particular seagrasses characterised by different architecture. Differences in species-composition among the seagrass habitats partly reflected the size-composition of fish in each habitat. The open space below the canopy of A. griffthii is likely to allow larger fish to occupy this habitat, whereas only small fish would be able to penetrate the dense foliage of P. sinuosa. Differences in species- and size-composition of fish among these habitats may be the result of settlement-sized larvae discriminating between particular seagrass and meadow structures, or fish being subject to different levels of predation and/or accessibility to food or space. The species-composition in P. coriacea was highly dispersed and did not differ from that of unvegetated areas. While several species were associated with both P. coriacea and bare-sand habitats, some species did display a high affinity with the seagrass P. coriacea. This may reflect an association with the sparse and narrower leaves of this seagrass or with the patchy occurrence of the seagrass Heterozostera tasmanica, which commonly occurs as an understorey in this habitat.     

Front velocity and structure of bottom gravity currents with a low volume of release propagating in a porous medium

The paper reports results of large eddy simulations of lock exchange compositional gravity currents with a low volume of release advancing in a horizontal, long channel. The channel contains an array of spanwise-oriented square cylinders. The cylinders are uniformly distributed within the whole channel. The flow past the individual cylinders is resolved by the numerical simulation. The paper discusses how the structure and evolution of the current change with the main geometrical parameters of the flow (e.g., solid volume fraction, ratio between the initial height of the region containing lock fluid and the channel depth, ratio between the initial length and height of the region containing lock fluid) and the Reynolds number. Though in all cases with a sufficiently large solid volume fraction the current transitions to a drag-dominated regime, the value of the power law coefficient, α, describing the front position’s variation with time (x _f  ~ t ^α , where t is the time measured from the removal of the lock gate) is different between full depth cases and partial depth cases. The paper also discusses how large eddy simulation (LES) results compare with findings based on shallow-water equations. In particular, LES results show that the values of α are not always equal to values predicted by shallow water theory for the limiting cases where the current height is comparable, or much smaller, than the channel depth.     

Photodegradation of Ibuprofen,Cetirizine, and Naproxen by PAN-MWCNT/TiO<Subscript>2</Subscript>–NH<Subscript>2</Subscript> nanofiber membrane under UV light irradiation

Background

In this study, the photodegradation of three pharmaceuticals, namely Ibuprofen (IBP), Naproxen (NPX), and Cetirizine (CIZ) in aqueous media was investigated under UV irradiation. The photocatalyst used in this work consists of surface functionalized titanium dioxide (TiO₂–NH₂) nanoparticles grafted into Polyacrylonitrile (PAN)/multi-walled carbon nanotube composite nanofibers. Surface modification of the fabricated composite nanofibers was illustrated using XRD, FTIR, and SEM analyses.

Results

Sets of experiments were performed to study the effect of pharmaceuticals initial concentration (5–50 mg/L), solution pH (2–9), and irradiation time on the degradation efficiency. The results demonstrated that more than 99% degradation efficiency was obtained for IBP, CIZ, and NPX within 120, 40, and 25 min, respectively.

Conclusions

Comparatively, the photocatalytic degradation of pharmaceuticals using PAN-CNT/TiO₂–NH₂ composite nanofibers was much more efficient than with PAN/TiO₂–NH₂ composite nanofibers.

     

Stabilization of the As-contaminated soil from the metal mining areas in Korea

Phytoextraction is a remediation technology with a promising application for removing arsenic (As) from soils and waters. Several plant species were evaluated for their As accumulation capacity in hydroponic culture amended with As. Cucumis sativus (cucumber) displayed the highest tolerance against As among 4 plants tested in this study (corn, wheat, sorghum and cucumber). The germination ratio of Cucumis sativus was more than 50% at the high concentration of 5,000 mg-As/l. In Cucumis sativus grown in a solution contaminated with 25 mg-As/l, the accumulated As concentrations in the shoot and root were 675.5 ± 11.5 and 312.0 ± 163.4 mg/kg, respectively, and the corresponding values of the translocation and bioaccumulation factors for As were 1.9 ± 0.9 and 21.1 ± 8.4, respectively. These results indicate Cucumis sativus is to be a candidate plant for phytoextraction of As from soils and water.