Sulfur isotopic signatures in rainwater and moss Haplocladium microphyllum indicating atmospheric sulfur sources in Nanchang City (SE China)

Sulfur source identification previously reported has been based on sulfur isotopic ratios in either rainwater or mosses. The δ³⁴S values of rainwater sulfate and the epilithic moss Haplocladium microphyllum in Nanchang region (China) were determined for comparisons and used to delineate atmospheric sulfur sources. At the urban and rural sites, similar mean δ³⁴S values were observed between rainwater sulfate (+ 1.6‰ and − 0.2‰, respectively) and epilithic mosses (+ 1.7‰ and + 0.6‰, respectively), suggesting that mosses acquire δ³⁴S values similar to those found for rainwater sulfate. This has further demonstrated that moss δ³⁴S signatures hold valuable source-specific information as rainwater δ³⁴S values do. The δ³⁴S values of both rainwater sulfate and epilithic mosses indicated that atmospheric sulfur in Nanchang region was mainly associated with coal combustion. The lower δ³⁴S values at the rural site can be explained by higher contribution of local coals (lower δ³⁴S values relative to those of north Chinese coals) and biogenic sulfur.     

Erratum to “Sources of nitrate and ammonium contamination in groundwater under developing Asian megacities”

The status of nitrate (NO₃⁻), nitrite (NO₂⁻) and ammonium (NH₄⁺) contamination in the water systems, and the mechanisms controlling their sources, pathways, and distributions were investigated for the Southeast Asian cities of Metro Manila, Bangkok, and Jakarta. GIS-based monitoring and dual isotope approach (nitrate δ¹⁵N and δ¹⁸O) suggested that human waste via severe sewer leakage was the major source of nutrient contaminants in Metro Manila and Jakarta urban areas. Furthermore, the characteristics of the nutrient contamination differed depending on the agricultural land use pattern in the suburban areas: high nitrate contamination was observed in Jakarta (dry fields), and relatively lower nutrients consisting mainly of ammonium were detected in Bangkok (paddy fields).The exponential increase in NO₃⁻-δ¹⁵N along with the NO₃⁻ reduction and clear δ¹⁸O/δ¹⁵N slopes of NO₃⁻ (∼ 0.5) indicated the occurrence of denitrification. An anoxic subsurface system associated with the natural geological setting (e.g., the old tidal plain at Bangkok) and artificial pavement coverage served to buffer NO₃⁻ contamination via active denitrification and reduced nitrification.Our results showed that NO₃⁻ and NH₄⁺ contamination of the aquifers in Metro Manila, Bangkok, and Jakarta was not excessive, suggesting low risk of drinking groundwater to human health, at present. However, the increased nitrogen load and increased per capita gross domestic product (GDP) in these developing cities may increase this contamination in the very near future. Continuous monitoring and management of the groundwater system is needed to minimize groundwater pollution in these areas, and this information should be shared among adjacent countries with similar geographic and cultural settings.     

Pollution of montane soil with Cu, Zn, As, Sb, Pb, and nitrate in Kanto, Japan

Soil cores and rainwater were sampled under canopies of Cryptomeria japonica in four montane areas along an atmospheric depositional gradient in Kanto, Japan. Soil cores (30 cm in depth) were divided into 2-cm or 4-cm segments for analysis. Vertical distributions of elemental enrichment ratios in soils were calculated as follows: (X/Al)_i/(X/Al)_BG (where the numerator and denominator are concentration ratios of element-X and Al in the i- and bottom segments of soil cores, respectively). The upper 14-cm soil layer showed higher levels of Cu, Zn, As, Sb, and Pb than the lower (14-30 cm) soil layer. In the four areas, the average enrichment ratios in the upper 6-cm soil layer were as follows: Pb (4.93) ≥ Sb (4.06) ≥ As (3.04) > Zn (1.71) ≥ Cu (1.56). Exogenous elements (kg/ha) accumulated in the upper 14-cm soil layer were as follows: Zn (26.0) > Pb (12.4) > Cu (4.48) ≥ As (3.43) ≥ Sb (0.49). These rank orders were consistent with those of elements in anthropogenic aerosols and polluted (roadside) air, respectively, indicating that air pollutants probably caused enrichment of these elements in the soil surface layer. Approximately half of the total concentrations of As, Sb, and Pb in the upper 14-cm soil layer were derived from exogenous (anthropogenic) sources. Sb showed the highest enrichment factor in anthropogenic aerosols, and shows similar deposition behavior to NO₃⁻, which is a typical acidic air pollutant. There was a strong correlation between Sb and NO₃⁻ concentrations in rainfall (e.g., in the throughfall under C. japonica: [NO₃⁻] = 21.1 [dissolved Sb], r = 0.938, p < 0.0001, n = 182). Using this correlation, total (cumulative) inputs of NO₃⁻ were estimated from the accumulated amounts of exogenous Sb in soils, i.e., 16.7 t/ha at Mt. Kinsyo (most polluted), 8.6 t/ha at Mt. Tsukuba (moderately polluted), and 5.8 t/ha at the Taga mountain system (least polluted). There are no visible ecological effects of these accumulated elements in the Kanto region at present. However, the concentrations of some elements are within a harmful range, according to the Ecological Soil Screening Levels determined by the U.S. Environmental Protection Agency.     

Sediment reworking rates in deep sediments of the Mediterranean Sea

Different pelagic areas of the Mediterranean Sea have been investigated in order to quantify physical and biological mixing processes in deep sea sediments. Herein, results of eleven sediment cores sampled at different deep areas (> 2000 m) of the Western and Eastern Mediterranean Sea are presented.²¹⁰Pb_xs and ¹³⁷Cs vertical profiles, together with ¹⁴C dating, are used to identify the main processes characterising the different areas and, finally, controlling mixing depths (SML) and bioturbation coefficients (D_b). Radionuclide vertical profiles and inventories indicate that bioturbation processes are the dominant processes responsible for sediment reworking in deep sea environments.Results show significant differences in sediment mixing depths and bioturbation coefficients among areas of the Mediterranean Sea characterised by different trophic regimes. In particular, in the Oran Rise area, where the Almeria-Oran Front induces frequent phytoplankton blooms, we calculate the highest values of sediment mixing layers (13 cm) and bioturbation coefficients (0.187 cm² yr⁻¹), and the highest values of ²¹⁰Pb_xs and ¹³⁷Cs inventories. Intermediate values of SML and D_b (~ 6 cm and ~ 0.040 cm² yr⁻¹, respectively) characterise the mesothrophic Algero-Balearic basin, while in the Southern Tyrrhenian Sea mixing parameters (SML of 3 cm and D_b of 0.011 cm² yr⁻¹) are similar to those calculated for the oligotrophic Eastern Mediterranean (SML of 2 cm and D_b of ~ 0.005 cm² yr⁻¹).     

Effect of COD/SO4ratio and Fe(II) under the variable hydraulic retention time (HRT) on fermentative hydrogen production

The effect of chemical oxygen demand/sulfate (COD/SO₄²⁻) ratio on fermentative hydrogen production using enriched mixed microflora has been studied. The chemostat system maintained with a substrate (glucose) concentration of 15 g COD L⁻¹ exhibited stable H₂ production at inlet sulfate concentrations of 0-20 g L⁻¹ during 282 days. The tested COD/SO₄²⁻ ratios ranged from 150 to 0.75 (with control) at pH 5.5 with hydraulic retention time (HRT) of 24, 12 and 6 h. The hydrogen production at HRT 6 h and pH 5.5 was not influenced by decreasing the COD/SO₄²⁻ ratio from 150 to 15 (with control) followed by noticeable increase at COD/SO₄²⁻ ratios of 5 and 3, but it was slightly decreased when the COD/SO₄²⁻ ratio further decreased to 1.5 and 0.75. These results indicate that high sulfate concentrations (up to 20,000 mg L⁻¹) would not interfere with hydrogen production under the investigated experimental conditions. Maximum hydrogen production was 2.95, 4.60 and 9.40 L day⁻¹ with hydrogen yields of 2.0, 1.8 and 1.6 mol H₂ mol⁻¹ glucose at HRTs of 24, 12 and 6 h, respectively. The volatile fatty acid (VFA) fraction produced during the reaction was in the order of butyrate > acetate > ethanol > propionate in all experiments. Fluorescence In Situ Hybridization (FISH) analysis indicated the presence of Clostridium spp., Clostridium butyricum, Clostridium perfringens and Ruminococcus flavefaciens as hydrogen producing bacteria (HPB) and absence of sulfate reducing bacteria (SRB) in our study.     

Comparison of toxicity and release rates of Cu and Zn from anti-fouling paints leached in natural and artificial brackish seawater

Biocide-containing anti-fouling paints are regulated and approved according to the added active ingredients, such as Cu. Biocide-free paints are considered to be less environmentally damaging and do not need an approval. Zn, a common ingredient in paints with the potential of causing adverse effects has received only minor attention. Laboratory experiments were conducted in artificial brackish seawater (ASW) and natural brackish seawater (NSW) to quantify release rates of Cu and Zn from biocide-containing and biocide-free labeled eroding anti-fouling paints used on commercial vessels as well as leisure boats. In addition, organisms from three trophic levels, the crustacean Nitocra spinipes, the macroalga Ceramium tenuicorne and the bacteria Vibrio fischeri, were exposed to Cu and Zn to determine the toxicity of these metals. The release rate of Cu in NSW was higher from the paints for professional use (3.2-3.6 µg cm⁻² d^− 1) than from the biocide leaching leisure boat paint (1.1 µg cm⁻² d^− 1). Biocide-free paints did leach considerably more Zn (4.4-8.2 µg cm⁻² d^− 1) than biocide-containing leisure boat paint (3.0 µg cm⁻² d^− 1) and ship paints (0.7-2.0 µg cm⁻² d^− 1). In ASW the release rates of both metals were notably higher than in NSW for most tested paints. The macroalga was the most sensitive species to both Cu (EC₅₀ = 6.4 µg l^− 1) and Zn (EC₅₀ = 25 µg l^− 1) compared to the crustacean (Cu, LC₅₀ = 2000 µg l^− 1 Zn, LC₅₀ = 890 µg l^− 1), and the bacteria (Cu, EC₅₀ = 800 µg l^− 1 and Zn, EC₅₀ = 2000 µg l^− 1). The results suggest that the amounts of Zn and Cu leached from anti-fouling paints may attain toxic concentrations in areas with high boat density. To fully account for potential ecological risk associated with anti-fouling paints, Zn as well as active ingredients should be considered in the regulatory process.     

Application of the Nernst-Planck approach to lead ion exchange in Ca-loaded Pelvetia canaliculata

Ca-loaded Pelvetia canaliculata biomass was used to remove Pb²⁺ in aqueous solution from batch and continuous systems. The physicochemical characterization of algae Pelvetia particles by potentiometric titration and FTIR analysis has shown a gel structure with two major binding groups - carboxylic (2.8 mmol g⁻¹) and hydroxyl (0.8 mmol g⁻¹), with an affinity constant distribution for hydrogen ions well described by a Quasi-Gaussian distribution. Equilibrium adsorption (pH 3 and 5) and desorption (eluents: HNO₃ and CaCl₂) experiments were performed, showing that the biosorption mechanism was attributed to ion exchange among calcium, lead and hydrogen ions with stoichiometry 1:1 (Ca:Pb) and 1:2 (Ca:H and Pb:H). The uptake capacity of lead ions decreased with pH, suggesting that there is a competition between H⁺ and Pb²⁺ for the same binding sites. A mass action law for the ternary mixture was able to predict the equilibrium data, with the selectivity constants α_Ca^H = 9 ± 1 and α_Ca^Pb = 44 ± 5, revealing a higher affinity of the biomass towards lead ions. Adsorption (initial solution pH 4.5 and 2.5) and desorption (0.3 M HNO₃) kinetics were performed in batch and continuous systems. A mass transfer model using the Nernst-Planck approximation for the ionic flux of each counter-ion was used for the prediction of the ions profiles in batch systems and packed bed columns. The intraparticle effective diffusion constants were determined as 3.73 × 10⁻⁷ cm² s⁻¹ for H⁺, 7.56 × 10⁻⁸ cm² s⁻¹ for Pb²⁺ and 6.37 × 10⁻⁸ cm² s⁻¹ for Ca²⁺.     

Distribution of artificial radionuclides in deep sediments of the Mediterranean Sea

Artificial radionuclides enter the Mediterranean Sea mainly through atmospheric deposition following nuclear weapons tests and the Chernobyl accident, but also through the river discharge of nuclear facility effluents. Previous studies of artificial radionuclides impact of the Mediterranean Sea have focussed on shallow, coastal sediments. However, deep sea sediments have the potential to store and accumulate pollutants, including artificial radionuclides. Deep sea marine sediment cores were collected from Mediterranean Sea abyssal plains (depth > 2000 m) and analysed for ^239,240Pu and ¹³⁷Cs to elucidate the concentrations, inventories and sources of these radionuclides in the deepest areas of the Mediterranean. The activity — depth profiles of ²¹⁰Pb, together with ¹⁴C dating, indicate that sediment mixing redistributes the artificial radionuclides within the first 2.5 cm of the sedimentary column. The excess ²¹⁰Pb inventory was used to normalize ^239,240Pu and ¹³⁷Cs inventories for variable sediment fluxes. The ^239,240Pu/²¹⁰Pb_xs ratio was uniform across the entire sea, with a mean value of 1.24 × 10^− 3, indicating homogeneous fallout of ^239,240Pu. The ¹³⁷Cs/²¹⁰Pb_xs ratio showed differences between the eastern (0.049) and western basins (0.030), clearly significant impact of deep sea sediments from the Chernobyl accident. The inventory ratios of ^239,240Pu/¹³⁷Cs were 0.041 and 0.025 in the western and eastern basins respectively, greater than the fallout ratio, 0.021, showing more efficient scavenging of ^239,240Pu in the water column and major sedimentation of ¹³⁷Cs in the eastern basin. Although areas with water depths of > 2000 m constitute around 40% of the entire Mediterranean basin, the sediments in these regions only contained 2.7% of the ^239,240Pu and 0.95% of the ¹³⁷Cs deposited across the Sea in 2000. These data show that the accumulation of artificial radionuclides in deep Mediterranean environments is much lower than predicted by other studies from the analysis of continental shelf sediments.     

Dry deposition of gaseous radioiodine and particulate radiocaesium onto leafy vegetables

Radionuclides released to the atmosphere during dry weather (e.g. after a nuclear accident) may contaminate vegetable foods and cause exposure to humans via the food chain. To obtain experimental data for an appropriate assessment of this exposure path, dry deposition of radionuclides to leafy vegetables was studied under homogeneous and controlled greenhouse conditions. Gaseous ¹³¹I-tracer in predominant elemental form and particulate ¹³⁴Cs-tracer at about 1 μm diameter were used to identify susceptible vegetable species with regard to contamination by these radionuclides. The persistence was examined by washing the harvested product with water. The vegetables tested were spinach (Spinacia oleracea), butterhead lettuce (Lactuca sativa var. capitata), endive (Cichorium endivia), leaf lettuce (Lactuca sativa var. crispa), curly kale (Brassica oleracea convar. acephala) and white cabbage (Brassica oleracea convar. capitata). The variation of radionuclides deposited onto each vegetable was evaluated statistically using the non-parametric Kruskal-Wallis Test and the U-test of Mann-Whitney. Significant differences in deposited ¹³¹I and ¹³⁴Cs activity concentration were found among the vegetable species.For ¹³¹I, the deposition velocity to spinach normalized to the biomass of the vegetation was 0.5-0.9 cm³ g^− 1 s^− 1 which was the highest among all species. The particulate ¹³⁴Cs deposition velocity of 0.09 cm³ g^− 1 s^− 1 was the highest for curly kale, which has rough and structured leaves. The lowest deposition velocity was onto white cabbage: 0.02 cm³ g^− 1 s^− 1 (iodine) and 0.003 cm³ g^− 1 s^− 1 (caesium). For all species, the gaseous iodine deposition was significantly higher compared to the particulate caesium deposition. The deposition depends on the sensitive parameters leaf area, stomatal aperture, and plant morphology. Decontamination by washing with water was very limited for iodine but up to a factor of two for caesium.     

Retrospective determination of 137Cs specific activity distribution in spruce bark and bark aggregated transfer factor in forests on the scale of the Czech Republic ten years after the Chernobyl accident

The ¹³⁷Cs specific activities (mean 32 Bq kg⁻¹) were determined in spruce bark samples that had been collected at 192 sampling plots throughout the Czech Republic in 1995, and were related to the sampling year. The ¹³⁷Cs specific activities in spruce bark correlated significantly with the ¹³⁷Cs depositions in areas affected by different precipitation sums operating at the time of the Chernobyl fallout in 1986. The ratio of the ¹³⁷Cs specific activities in bark and of the ¹³⁷Cs deposition levels yielded bark aggregated transfer factor T_ag about 10.5 × 10⁻³ m⁻² kg⁻¹. Taking into account the residual specific activities of ¹³⁷Cs in bark 20 Bq kg⁻¹ and the available pre-Chernobyl data on the ¹³⁷Cs deposition loads on the soil surface in the Czech Republic, the real aggregated transfer factor after and before the Chernobyl fallout proved to be T*_ag = 3.3 × 10⁻³ m⁻² kg⁻¹ and T**_ag = 4.0 × 10⁻³ m⁻² kg⁻¹, respectively. The aggregated transfer factors T*_ag for ¹³⁷Cs and spruce bark did not differ significantly in areas unequally affected by the ¹³⁷Cs fallout in the Czech Republic in 1986, and the figures for these aggregated transfer factors were very similar to the mean bark T_ag values published from the extensively affected areas near Chernobyl. The magnitude of the ¹³⁷Cs aggregated transfer factors for spruce bark for the pre-Chernobyl and post-Chernobyl period in the Czech Republic was also very similar. The variability in spruce bark acidity caused by the operation of local anthropogenic air pollution sources did not significantly influence the accumulation and retention of ¹³⁷Cs in spruce bark. Increasing elevation of the bark sampling plots had a significant effect on raising the remaining ¹³⁷Cs specific activities in bark in areas affected by precipitation at the time when the plumes crossed, because the sums of this precipitation increased with elevation (covariable).     

Human impacts on groundwater flow and contamination deduced by multiple isotopes in Seoul City, South Korea

The influence of human activities on the flow system and contamination of groundwater were investigated in Seoul City, South Korea, one of the largest Asian cities, using a combination of isotopes (δD, T, δ¹⁵N, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr). Eighteen representative groundwater and river water samples, which were collected over a wide area of the city, were compared with previously reported data. The distribution of stable isotopes (δD and δ¹⁸O) with groundwater potential data shows that recharged groundwater from either the surrounding mountainous area as well as the Han River and other surface streams discharged towards the northern-central part of the city, where a subway tunnel pumping station is located. It is suggested from T values (3.3 to 5.8 T.U.) that groundwater was recharged in the last 30 to 40 years. The δ³⁴S and δ¹⁵N of SO₄²⁻ and NO₃⁻ data were efficiently used as indicators of contamination by human activities. These isotopes clarified that the contribution of anthropogenic contaminants i.e., industrial and household effluents, waste landfills, and fertilizers, are responsible for the enrichment by SO₄²⁻ (> 30 ppm as SO₄²⁻) and NO₃⁻ (> 20 ppm as NO₃⁻) of groundwater. The ⁸⁷Sr/⁸⁶Sr values of groundwater vary (0.71326 to 0.75058) in accordance with the host rocks of different origins. Mineral elements such as Ca are also suggested to be derived naturally from rocks. The groundwater under Seoul City is greatly affected by transportation of pollutants along the groundwater flow controlled by subway tunnel pumping, contributing to the degradation of water quality in urbanized areas.     

Pb and stable lead content in fungi: Its transfer from soil

The uptake and transfer of natural radionuclides, other than ⁴⁰K, from soil to mushrooms has been somewhat overlooked in the literature. Their contribution to the dose due to the consumption of mushrooms was considered negligible. But the contribution of ²¹⁰Pb in areas unaffected by any recent radioactive fallout has been found to be significant, up to 35% of the annual dose commitment in Spain. More than 30 species of mushrooms were analyzed, and the ²¹⁰Pb detected was in the range of 0.75-202 Bq/kg d.w. A slight difference was observed between species with different nutritional mechanisms (saprophytes ≥ mycorrhizae). The ²¹⁰Pb content was correlated with the stable lead content, but not with its predecessor in the uranium radioactive series, ²²⁶Ra. This suggested that ²¹⁰Pb was taken up from the soil by the same pathway as stable lead. The bioavailability of ²¹⁰Pb in soil was determined by means of a sequential extraction procedure (NH₄OAc, 1M HCl, 6M HCl, and residue). About 30% of the ²¹⁰Pb present in the soil was available for transfer to mushrooms, more than other natural radionuclides in the same ecosystem. Lycoperdon perlatum, Hebeloma cylindrosporum, and Amanita curtipes presented the highest values of the available transfer factor, ATF. As reflected in their ATF values, the transfer from soil to mushroom of some natural and anthropogenic radionuclides was in the following order:

^228,230,232Th ≈ ⁴⁰K ≥ ¹³⁷Cs ≥ ^234,238U ≈ ²²⁶Ra ≥ ⁹⁰Sr ≥ ²¹⁰Pb ≈ ^239 + 240Pu ≈ ²⁴¹Am.     

Characterisation of atmospheric deposition as a source of contaminants in urban rainwater tanks

To characterise atmospheric input of chemical contaminants to urban rainwater tanks, bulk deposition (wet + dry deposition) was collected at sixteen sites in Brisbane, Queensland, Australia on a monthly basis during April 2007-March 2008 (N = 175). Water from rainwater tanks (22 sites, 26 tanks) was also sampled concurrently. The deposition/tank water was analysed for metals, soluble anions and selected samples were additionally analysed for PAHs, pesticides, phenols, organic & inorganic carbon. Flux (mg/m²/d) of total solids mass was found to correlate with average daily rainfall (R² = 0.49) indicating the dominance of the wet deposition contribution to total solids mass. On average 97% of the total mass of analysed components was accounted for by Cl⁻ (25.0%), Na (22.6%), organic carbon (20.5%), NO₃⁻ (10.5%), SO₄²⁻ (9.8%), inorganic carbon (5.7%), PO₄³⁻ (1.6%) and NO₂⁻ (1.5%). For other minor elements the average flux from highest to lowest was in the order of Fe > Al > Zn > Mn > Sr > Pb > Ba > Cu > Se. There was a significant effect of location on flux of K, Sb, Sn, Li, Mn, Fe, Cu, Zn, Ba, Pb and SO₄²⁻ but not other metals or anions. Overall the water quality resulting from the deposition (wet + dry) was good but 10.3%, 1.7% and 17.7% of samples had concentrations of Pb, Cd and Fe respectively greater than the Australian Drinking Water Guidelines (ADWG). This generally occurred in the drier months. In comparison 14.2% and 6.1% of tank samples had total Pb and Zn concentrations exceeding the guidelines. The cumulative mean concentration of lead in deposition was on average only 1/4 of that in tank water over the year at a site with high concentrations of Pb in tank water. This is an indication that deposition from the atmosphere is not the major contributor to high lead concentrations in urban rainwater tanks in a city with reasonable air quality, though it is still a significant portion.     

Evolution model of δ³⁴S and δ¹⁸O in dissolved sulfate in volcanic fan aquifers from recharge to coastal zone and through the Jakarta urban area, Indonesia

The sources of sulfate in an aquifer system, and its formation/degradation via biogeochemical reactions, were investigated by determining sulfate isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) in dissolved sulfate in groundwater from the Jakarta Basin. The groundwater flow paths, water ages, and geochemical features are well known from previous studies, providing a framework for the groundwater chemical and isotopic data, which is supplemented with data for spring water, river water, hot spring water, seawater, detergents, and fertilizers within the basin. The sulfate isotope composition of groundwater samples varied widely from − 2.9‰ to + 33.4‰ for δ³⁴S_SO4 and + 4.9‰ to + 17.8‰ for δ¹⁸O_SO4 and changed systematically along its flow direction from the mountains north to the coastal area. The groundwater samples were classified into three groups showing (1) relatively low and narrow δ³⁴S_SO4 (+ 2.3‰ to + 7.6‰) with low and varied δ¹⁸O_SO4 (+ 4.9‰ to + 12.9‰) compositions, (2) high and varied δ³⁴S_SO4 (+ 10.2‰ to + 33.4‰) with high δ¹⁸O_SO4 (+ 12.4‰ to + 17.3‰) compositions, and (3) low δ³⁴S_SO4 (<+6.1‰) with high δ¹⁸O_SO4 (up to + 17.8‰) compositions. These three types of groundwater were observed in the terrestrial unconfined aquifer, the coastal unconfined and confined aquifers, and the terrestrial confined aquifer, respectively. A combination of field measurements, concentrations, and previously determined δ¹⁵N_NO3 data, showed that the observed isotopic heterogeneity was mainly the result of contributions of pollutants from domestic sewage in the rural area, mixing of seawater sulfate that had experienced previous bacterial sulfate reduction in the coastal area, and isotopic fractionation during the formation of sulfate through bacterial disproportionation of elemental sulfur. Our results clearly support the hypothesis that human impacts are important factors in understanding the sulfur cycle in present-day subsurface environments. A general model of sulfate isotopic evolution along with groundwater flow has rarely been proposed, due to the complicated hydrogeological research setting that causes varied isotope ratios, although its understanding has recently received great attention. This pioneer study on a simple volcanic fan aquifer system with a well-understood groundwater flow mechanism provides a useful model for future studies.     

Bacterial responses to Cu-doped TiO2 nanoparticles

The toxicity of Cu-doped TiO₂ nanoparticles (NPs, 20 nm), synthesized by a flame aerosol reactor, to Mycobacterium smegmatis and Shewanella oneidensis MR-1, is the primary focus of this study. Both doped and non-doped TiO₂ NPs (20 nm) tended to agglomerate in the medium solution, and therefore did not penetrate into the cell and damage cellular structures. TiO₂ particles (< 100 mg/L) did not apparently interfere with the growth of the two species in aqueous cultures. Cu-doped TiO₂ NPs (20 mg/L) significantly reduced the M. smegmatis growth rate by three fold, but did not affect S. oneidensis MR-1 growth. The toxicity of Cu-doped TiO₂ NPs was driven by the release of Cu²⁺ from the parent NPs. Compared to equivalent amounts of Cu²⁺, Cu-doped TiO₂ NPs exhibited higher levels of toxicity to M. smegmatis (P-value < 0.1). Addition of EDTA in the culture appeared to significantly decrease the anti-mycobacterium activity of Cu-doped TiO₂ NPs. S. oneidensis MR-1 produced a large amount of extracellular polymeric substances (EPS) under NP stress, especially extracellular protein. Therefore, S. oneidensis MR-1 was able to tolerate a much higher concentration of Cu²⁺ or Cu-doped TiO₂ NPs. S. oneidensis MR-1 also adsorbed NPs on cell surface and enzymatically reduced ionic copper in culture medium with a remediating rate of 61 µg/(liter?OD₆₀₀? hour) during its early exponential growth phase. Since the metal reducing Shewanella species can efficiently “clean” metal-oxide NPs, the activities of such environmentally relevant bacteria may be an important consideration for evaluating the ecological risk of metal-oxide NPs.     

Atmospheric NH3 and NO2 concentration and nitrogen deposition in an agricultural catchment of Eastern China

To assess the atmospheric environmental impacts of anthropogenic reactive nitrogen in the fast-developing Eastern China region, we measured atmospheric concentrations of nitrogen dioxide (NO₂) and ammonia (NH₃) as well as the wet deposition of inorganic nitrogen (NO₃⁻ and NH₄⁺) and dissolved organic nitrogen (DON) levels in a typical agricultural catchment in Jiangsu Province, China, from October 2007 to September 2008_. The annual average gaseous concentrations of NO₂ and NH₃ were 42.2 μg m⁻³ and 4.5 μg m⁻³ (0 °C, 760 mm Hg), respectively, whereas those of NO₃⁻, NH₄⁺, and DON in the rainwater within the study catchment were 1.3, 1.3, and 0.5 mg N L⁻¹, respectively. No clear difference in gaseous NO₂ concentrations and nitrogen concentrations in collected rainwater was found between the crop field and residential sites, but the average NH₃ concentration of 5.4 μg m⁻³ in residential sites was significantly higher than that in field sites (4.1 μg m⁻³). Total depositions were 40 kg N ha⁻¹ yr⁻¹ for crop field sites and 30 kg N ha⁻¹ yr⁻¹ for residential sites, in which dry depositions (NO₂ and NH₃) were 7.6 kg N ha⁻¹ yr⁻¹ for crop field sites and 1.9 kg N ha⁻¹ yr⁻¹ for residential sites. The DON in the rainwater accounted for 16% of the total wet nitrogen deposition. Oxidized N (NO₃⁻ in the precipitation and gaseous NO₂) was the dominant form of nitrogen deposition in the studied region, indicating that reactive forms of nitrogen created from urban areas contribute greatly to N deposition in the rural area evaluated in this study.     

(210)Po and (210)Pb in the tissues of the deep-sea hydrothermal vent mussel Bathymodiolus azoricus from the Menez Gwen field (Mid-Atlantic Ridge)

The hydrothermal deep-sea vent fauna is naturally exposed to a highly specific environment enriched in potentially toxic species such as sulfides, metals and natural radionuclides due to the convective seawater circulation inside the oceanic crust and its interaction with basaltic or ultramafic host rocks. However, data on radionuclides in biota from such environment are very limited. An investigation was carried out on tissue partitioning of ²¹⁰Po and ²¹⁰Pb, two natural radionuclides within the ²³⁸U decay chain, in Bathymodiolus azoricus specimens from the Mid-Atlantic Ridge (Menez Gwen field). These two elements showed different distributions with high ²¹⁰Pb levels in gills and high ²¹⁰Po levels in both gills and especially in the remaining parts of the body tissue (including the digestive gland). Various factors that may explain such partitioning are discussed. However, ²¹⁰Po levels encountered in B. azoricus were not exceptionally high, leading to weighted internal dose rate in the range 3 to 4 μGy h^− 1. These levels are slightly higher than levels characterizing coastal mussels (~ 1 μGy h^− 1).     

The adsorption of saxitoxin to clays and sediments in fresh and saline waters

The adsorption of saxitoxin to Na- and Ca-montmorillonite, kaolin (crystalline and amorphous), kaolinite, Bread and Butter Creek sediment (an estuarine tidal creek), Gulf of Mexico sediment, and Santa Barbara Basin sediment in deionized water and 32‰ salinity simulated seawater (Instant Ocean™) is reported. Adsorption was partially reversible for all cases and best described using a Freundlich isotherm. The corresponding Freundlich constants (K_F) ranged from 8.83 × 10³ μmol/kg to 6.76 × 10⁴ μmol/kg for freshwater and 4.73 × 10³ μmol/kg-1.11 × 10⁴ μmol/kg for seawater. There is a positive linear correlation seen between the K_F values and the cation-exchange capacity of the adsorbents. The release of saxitoxin from previously equilibrated adsorbents was determined in freshwater (0-18%) and seawater (4-53%).     

Aerobic degradation of acid orange 7 in a vertical-flow constructed wetland

Biological, aerobic degradation of an azo dye and of the resultant, recalcitrant, aromatic amines in a constructed wetland (CW) was demonstrated for the first time. A vertical-flow CW, planted with Phragmites sp. was fed with 127 mg l⁻¹ of acid orange 7 (AO7) at hydraulic loads of 28, 40, 53 and 108 l m⁻²day⁻¹. Color removal efficiencies of up to 99% clearly demonstrate cleavage of the azo bond, also confirmed by the similar AO7 removal and SO₄²⁻ release rates revealing that adsorption onto the matrix was constant. The positive redox potential at the outlet demonstrates that aerobic conditions were present. Chemical oxygen demand and total organic carbon removal efficiencies of up to 93% were also indicative of AO7 mineralization. The degradation of sulfanilic acid was confirmed by the presence of NO₃⁻, SO₄²⁻ and secondary metabolites, which suggest at least two degradation pathways leading to a common compound, 3-oxoadipate.     

Investigating the potential role of ammonia in ion chemistry of fine particulate matter formation for an urban environment

To investigate the potential role of ammonia in ion chemistry of PM_2.5 aerosol, measurements of PM_2.5 (particulate matter having aerodynamic diameter < 2.5 µm) along with its ionic speciation and gaseous pollutants (sulfur dioxide (SO₂), nitrogen oxides (NO_x), ammonia (NH₃) and nitric acid (HNO₃)) were undertaken in two seasons (summer and winter) of 2007-2008 at four sampling sites in Kanpur, an urban-industrial city in the Ganga basin, India. Mean concentrations of water-soluble ions were observed in the following order (i) summer: SO₄²⁻ (26.3 µg m^− 3) > NO₃⁻ (16.8) > NH₄⁺ (15.1) > Ca²⁺ (4.1) > Na⁺ (2.4) > K⁺ (2.1 µg m^− 3) and (ii) winter: SO₄²⁻ (28.9 µg m^− 3) > NO₃⁻ (23.0) > NH₄⁺ (16.4) > Ca²⁺(3.4) > K⁺(3.3) > Na⁺ (3.2 µg m^− 3). The mean molar ratio of NH₄⁺ to SO₄²⁻ was 2.8 ± 0.6 (mostly >2), indicated abundance of NH₃ to neutralize H₂SO₄. The excess of NH₄⁺ was inferred to be associated with NO₃⁻ and Cl⁻. Higher sulfur conversion ratio (F_s: 58%) than nitrogen conversion ratio (F_n: 39%) indicated that SO₄²⁻ was the preferred secondary species to NO₃⁻. The charge balance for the ion chemistry of PM_2.5 revealed that compounds formed from ammonia as precursor are (NH₄)₂SO₄, NH₄NO₃ and NH₄Cl. This study conclusively established that while there are higher contributions of NH₄⁺, SO₄²⁻ to PM_2.5 in summer but for nitrates (in particulate phase), it is the winter season, which is critical because of low temperatures that drives the reaction between ammonia and HNO₃ in forward direction for enhanced nitrate formation. In summary, inorganic secondary aerosol formation accounted for 30% mass of PM_2.5 and any particulate control strategy should include optimal control of primary precursor gases including ammonia.