Effects of lanthanum and lanthanum-modified clay on growth, survival and reproduction of Daphnia magna

The novel lanthanum-modified clay water treatment technology (Phoslock^®) seems very promising in remediation of eutrophied waters. Phoslock^® is highly efficient in stripping dissolved phosphorous from the water column and in intercepting phosphorous released from the sediments. The active phosphorous-sorbent in Phoslock^® is the Rare Earth Element lanthanum. A leachate experiment revealed that lanthanum could be released from the clay, but only in minute quantities of 0.13-2.13 μg l⁻¹ for a worst-case Phoslock^® dosage of 250 mg l⁻¹. A life-history experiment with the zooplankton grazer Daphnia magna revealed that lanthanum, up to the 1000 μg l⁻¹ tested, had no toxic effect on the animals, but only in medium without phosphorous. In the presence of phosphorous, rhabdophane (LaPO₄ · nH₂O) formation resulted in significant precipitation of the food algae and consequently affected life-history traits. With increasing amounts of lanthanum, in the presence of phosphate, animals remained smaller, matured later, and reproduced less, resulting in lower population growth rates. Growth rates were not affected at 33 μg La l⁻¹, but were 6% and 7% lower at 100 and 330 μg l⁻¹, respectively, and 20% lower at 1000 μg l⁻¹. A juvenile growth assay with Phoslock^® tested in the range 0-5000 mg l⁻¹, yielded EC₅₀ (NOEC) values of 871 (100) and 1557 (500) mg Phoslock^® l⁻¹ for weight and length based growth rates, respectively. The results of this study show that no major detrimental effects on Daphnia are to be expected from Phoslock^® or its active ingredient lanthanum when applied in eutrophication control.     

Multiple site study of recent atmospheric metal (Pb, Zn and Cu) deposition in the NW Iberian Peninsula using peat cores

In order to estimate atmospheric metal deposition in Southern Europe since the beginning of the Industrial Period (~ 1850 AD), concentration profiles of Pb, Zn and Cu were determined in four ²¹⁰Pb-dated peat cores from ombrotrophic bogs in Serra do Xistral (Galicia, NW Iberian Peninsula). Maximum metal concentrations varied by a factor of 1.8 for Pb and Zn (70 to 128 μg g⁻¹ and 128 to 231 μg g⁻¹, respectively) and 3.5 for Cu (11 to 37 μg g⁻¹). The cumulative metal inventories of each core varied by a factor of 3 for all analysed metals (132 to 329 μg cm⁻² for Pb, 198 to 625 μg cm⁻² for Zn and 22 to 69 μg cm⁻² for Cu), suggesting differences in net accumulation rates among peatlands. Although results suggest that mean deposition rates vary within the studied area, the enhanced ²¹⁰Pb accumulation and the interpretation of the inventory ratios (²¹⁰Pb/Pb, Zn/Pb and Cu/Pb) in two bogs indicated that either a record perturbation or post-depositional redistribution effects must be considered. After correction, Pb, Zn and Cu profiles showed increasing concentrations and atmospheric fluxes since the mid-XX^th century to maximum values in the second half of the XX^th century. For Pb, maximum fluxes were observed in 1955-1962 and ranged from 16 to 22 mg m⁻² yr⁻¹ (mean of 18 ± 1 mg m⁻² yr⁻¹), two orders of magnitude higher than in the pre-industrial period. Peaks in Pb fluxes in Serra do Xistral before the period of maximum consumption of leaded petrol in Europe (1970s-1980s) suggest the dominance of local pollutant sources in the area (i.e. coal mining and burning). More recent peaks were observed for Zn and Cu, with fluxes ranging from 32 to 52 mg m⁻² yr⁻¹ in 1989-1996, and from 4 to 9 mg m⁻² yr⁻¹ in 1994-2001, respectively. Our results underline the importance of multi-core studies to assess both the integrity and reliability of peat records, and the degree of homogeneity in bog accumulation. We show the usefulness of using the excess ²¹⁰Pb inventory to distinguish between differential metal deposition, accumulation or anomalous peat records.     

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⁺.     

Organochlorine pesticides, polychlorinated biphenyls and trace elements in wild European sea bass (Dicentrarchus labrax) off European estuaries

Polychlorinated biphenyls (PCBs) and organochlorine pesticides like dichloro-diphenyl-trichloroethane (DDTs), hexachlorocyclohexanes (HCHs), aldrin, dieldrin and trace elements (Cd, Cu, Se, Pb, Zn and Hg) were analysed in the muscle of European sea bass (Dicentrarchus labrax) sampled in Atlantic coastal regions near several important European river mouths (Gironde, Charente, Loire, Seine and Scheldt). High contamination levels were measured in the muscles of European sea bass sampled in the coastal regions near those river mouths (e.g. Σ ICES PCB = 133-10,478 μg kg^− 1 lw and Hg = 250-2000 μg kg^− 1 dw).The Scheldt and the Seine are still among the most contaminated estuaries in Europe. Each region presented their specific contamination patterns reflecting different sources due to the input of the respective rivers. As fish and fishery products are the main contributors of the total dietary intake of organochlorinated pollutants, regular consumption of European sea bass with the reported contamination levels may represent a significant exposure route for the general human population.     

Temporal variations in arsenic uptake by rice plants in Bangladesh: The role of iron plaque in paddy fields irrigated with groundwater

The transfer of arsenic to rice grains is a human health issue of growing relevance in regions of southern Asia where shallow groundwater used for irrigation of paddy fields is elevated in As. In the present study, As and Fe concentrations in soil water and in the roots of rice plants, primarily the Fe plaque surrounding the roots, were monitored during the 4-month growing season at two sites irrigated with groundwater containing ∼ 130 μg l^− 1 As and two control sites irrigated with water containing < 15 μg l^− 1 As. At both sites irrigated with contaminated water, As concentrations in soil water increased from < 10 μg l^− 1 to > 1000 μg l^− 1 during the first five weeks of the growth season and then gradually declined to < 10 μg l^− 1 during the last five weeks. At the two control sites, concentrations of As in soil water never exceeded 40 µg l^− 1. At both contaminated sites, the As content of roots and Fe plaque rose to 1000-1500 mg kg^− 1 towards the middle of the growth season. It then declined to ∼ 300 mg kg^− 1 towards the end, a level still well above As concentration of ∼ 100 mg kg^− 1 in roots and plaque measured throughout the growing season at the two control sites. These time series, combined with simple mass balance considerations, demonstrate that the formation of Fe plaque on the roots of rice plants by micro-aeration significantly limits the uptake of As by rice plants grown in paddy fields. Large variations in the As and Fe content of plant stems at two of the sites irrigated with contaminated water and one of the control sites were also recorded. The origin of these variations, particularly during the last month of the growth season, needs to be better understood because they are likely to influence the uptake of As in rice grains.     

Adsorption, sedimentation, and inactivation of E. coli within wastewater treatment wetlands

Bacteria fate and transport within constructed wetlands must be understood if engineered wetlands are to become a reliable form of wastewater treatment. This study investigated the relative importance of microbial treatment mechanisms in constructed wetlands treating both domestic and agricultural wastewater. Escherichia coli (E. coli) inactivation, adsorption, and settling rates were measured in the lab within two types of wastewater (dairy wastewater lagoon effluent and domestic septic tank effluent). In situ E. coli inactivation was also measured within a domestic wastewater treatment wetland and the adsorption of E. coli was also measured within the wetland effluent.Inactivation of E. coli appears to be the most significant contributor to E. coli removal within the wastewaters and wetland environments examined in this study. E. coli survived longer within the dairy wastewater (DW) compared to the domestic wastewater treatment wetland water (WW). First order rate constants for E. coli inactivation within the WW in the lab ranged from 0.09 day⁻¹ (d⁻¹) at 7.6 °C to 0.18 d⁻¹ at 22.8 °C. The average in situ rate constant observed within the domestic wetland ranged from 0.02 d⁻¹ to 0.03 d⁻¹ at an average water temperature of 17 °C. First order rate constants for E. coli inactivation within the DW ranged from 0.01 d⁻¹ at 7.7 °C to 0.04 d⁻¹ at 24.6 °C. Calculated distribution coefficients (K_d) were 19,000 mL g⁻¹, 324,000 mL g⁻¹, and 293 mL g⁻¹ for E. coli with domestic septic tank effluent (STE), treated wetland effluent (WLE), and DW, respectively. Approximately 50%, 20%, and 90% of E. coli were “free floating” or associated with particles <5 μm in size within the STE, WLE, and DW respectively. Although 10-50% of E. coli were found to associate with particles >5 μm within both the STE and DW, settling did not appear to contribute to E. coli removal within sedimentation experiments, indicating that the particles the bacteria were associated with had very small settling velocities.The results of this study highlight the importance of wastewater characterization when designing a treatment wetland system for bacterial removal. This study illustrated the level of variability in E. coli removal processes that can be observed within different wastewater, and wetland environments.     

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.     

Enhanced removal of polychlorinated biphenyls from alfalfa rhizosphere soil in a field study: The impact of a rhizobial inoculum

Polychlorinated biphenyls (PCB) are persistent pollutants in soil environments where they continue to present considerable human health risks. Successful strategies to remediate contaminated soils are needed that are effective and of low cost. Bioremediation approaches that include the use of plants and microbial communities to promote degradation of PCB have significant potential but need further assessment under field conditions. The effects of growth of alfalfa (Medicago sativa L.) and inoculation with a symbiotic nitrogen fixing bacterium (Rhizobium meliloti) on the removal of polychlorinated biphenyls (PCB) from rhizosphere soil were evaluated in a field experiment. The initial PCB content of the soil ranged from 414 to 498 µg kg⁻¹. PCB removal for the rhizosphere soil was enhanced in the planted treatments, an average of 36% decrease in PCB levels compared to a 5.4% decrease in the unplanted soil, and further enhanced when plants were inoculated with the symbiotic Rhizobium (an average of 43% decrease) when evaluated at 90 days after planting. Plant biomass production was higher in the inoculated treatment. The total PCB content was increased from 3.30 µg kg⁻¹ to 26.72 µg kg⁻¹ in plant shoots, and from 115.07 µg kg⁻¹ to 142.23 µg kg⁻¹ in roots in the inoculated treatment compared to the planted treatment. Increased colony forming units (cfu) of total heterotrophic bacteria, biphenyl-degrading bacteria and fungi were observed in the rhizosphere of inoculated plants. PCB removal from the rhizosphere soil was not significantly correlated with the direct PCB uptake by the plants in any of the treatments but was significantly correlated with the stimulation of rhizosphere microflora. Changes in the soil microbial community structure in the planted and inoculated treatment were observed by profiling of bacterial ribosomal sequences. Some bacteria, such as Flavobacterium sp., may have contributed to the effective degradation of PCB and deserve further investigation.     

Analysis of dissolved microcystins in surface water samples from Kovada Lake, Turkey

Dissolved (extracellular) microcystin (MC) concentrations were determined at 3 sampling stations on Lake Kovada, Turkey. The dominant species of cyanobacteria found in August and September of 2006 were Microcystis aeruginosa, Synechococcus sp., Phormidium limosum, Phormidium formosa and Planktothrix limnetica. MC concentrations in water were measured by ELISA and MC variants were examined by HPLC-PDA. Quantitative analysis by HPLC indicated that five MC variants (MC-LR, -RR, -LA, -LW, -LF) were identified in water samples from Kovada Lake. The maximum concentration of dissolved MC-LW was 98.9 µg l^− 1 in October. MC-LR was only detected in May at a concentration of 0.5 µg l^− 1. The cross reactivity of the antibody (MC10E7) to variants such as MC-LA MC-LW & MC-LF was low. Hence the results determined by ELISA were lower than those determined by HPLC in September and October samples due to differences in the specificity of the antibody to MC variants. Total extraceullar MCs was quantified by ELISA and ranged from 0.73 to 48.5 µg MC-LR equivalents l^− 1, which in some cases exceeded the WHO provisional Guideline Value for MC-LR in drinking water. This study confirms that the lakes of Turkey should be monitored for toxic cyanobacteria and for MCs to avoid or reduce the potential exposure of people to these health hazards.     

Impact of toxic cyanobacteria on gastropods and microcystin accumulation in a eutrophic lake (Grand-Lieu, France) with special reference to Physa (= Physella) acuta

Hepatotoxic microcystins (MCs) produced by cyanobacteria are known to accumulate in gastropods following grazing of toxic cyanobacteria and/or absorption of MCs dissolved in water, with adverse effects on life history traits demonstrated in the laboratory. In the field, such effects may vary depending on species, according to their relative sensitivity and ecology. The aims of this study were to i) establish how various intensities of MC-producing cyanobacteria proliferations alter the structure of gastropod community and ii) compare MC tissue concentration in gastropods in the field with those obtained in our previous laboratory experiments on the prosobranch Potamopyrgus antipodarum and the pulmonate Lymnaea stagnalis. We explored these questions through a one-year field study at three stations at Grand-Lieu Lake (France) affected by different intensities of cyanobacteria proliferations. A survey of the community structure and MC content of both cyanobacteria and gastropods was associated with a caging experiment involving P. antipodarum and L. stagnalis. In total, 2592 gastropods belonging to 7 prosobranch and 16 pulmonate species were collected. However, distribution among the stations was unequal with 62% vs 2% of gastropods sampled respectively at the stations with the lowest vs highest concentrations of MC. Irrespective of the station, pulmonates were always more diverse, more abundant and occurred at higher frequencies than prosobranchs. Only the pulmonate Physa acuta occurred at all stations, with abundance and MC tissue concentration (≤ 4.32 µg g DW^− 1) depending on the degrees of MC-producing cyanobacteria proliferations in the stations; therefore, P. acuta is proposed as a potential sentinel species. The caging experiment demonstrated a higher MC accumulation in L. stagnalis (≤ 0.36 µg g DW^− 1 for 71% of individuals) than in P. antipodarum (≤ 0.02 µg g DW^− 1 for 12%), corroborating previous laboratory observations. Results are discussed in terms of differential gastropod sensitivity and MC transfer through the food web.     

Removal of organics in constructed wetlands with horizontal sub-surface flow: a review of the field experience

Constructed wetlands with horizontal sub-surface flow (HF CWs) have successfully been used for treatment various types of wastewater for more than four decades. Most systems have been designed to treat municipal sewage but the use for wastewaters from agriculture, industry and landfill leachate in HF CWs is getting more attention nowadays. The paper summarizes the results from more than 400 HF CWs from 36 countries around the world. The survey revealed that the highest removal efficiencies for BOD₅ and COD were achieved in systems treating municipal wastewater while the lowest efficiency was recorded for landfill leachate. The survey also revealed that HF CWs are successfully used for both secondary and tertiary treatment. The highest average inflow concentrations of BOD₅ (652 mg l^− 1) and COD (1865 mg l^− 1) were recorded for industrial wastewaters followed by wastewaters from agriculture for BOD₅ (464 mg l^− 1) and landfill leachate for COD (933 mg l^− 1). Hydraulic loading data reveal that the highest loaded systems are those treating wastewaters from agriculture and tertiary municipal wastewaters (average hydraulic loading rate 24.3 cm d^− 1). On the other hand, landfill leachate systems in the survey were loaded with average only 2.7 cm d^− 1. For both BOD₅ and COD, the highest average loadings were recorded for agricultural wastewaters (541 and 1239 kg ha^− 1 d^− 1, respectively) followed by industrial wastewaters (365 and 1212 kg ha^− 1 d^− 1, respectively). The regression equations for BOD₅ and COD inflow/outflow concentrations yielded very loose relationships. Much stronger relationships were found for inflow/outflow loadings and especially for COD. The influence of vegetation on removal of organics in HF CWs is not unanimously agreed but most studies indicated the positive effect of macrophytes.     

The intake of lead and associated metals by sheep grazing mining-contaminated floodplain pastures in mid-Wales, UK: II. Metal concentrations in blood and wool

Sheep grazing metal-contaminated floodplain pastures across mid-Wales ingest high concentrations of lead (Pb) in vegetation and directly in the form of soil. Sheep whole blood analysis indicated that Pb concentrations can be significantly elevated for animals grazing contaminated sites: in winter/spring, a median blood concentration of 147 µg Pb l^− 1 was found at the location with the highest soil enrichment of this metal compared to only 26 µg Pb l^− 1 for the control flock. There was within-flock variability in blood-Pb concentration, and overlap between blood-Pb ranges in animals grazing control and contaminated sites, although use of the Kruskal-Wallis H test established a number of significant (P < 0.05) differences between the blood-Pb content of flocks grazing the various study locations. Despite total daily intakes of up to 723 mg Pb d^− 1, only one individual sheep showed a blood-Pb content above the ‘normal safe’ concentration of 250 µg l^− 1. Blood and wool analyses were found to have limited value for the diagnosis of environmental exposure to Pb, and further consideration of metal accumulation in offal, bone and muscle tissue is recommended.     

Degradation of diclofenac by TiO2 photocatalysis: UV absorbance kinetics and process evaluation through a set of toxicity bioassays

In the present study the degradation kinetics and mineralization of diclofenac (DCF) by the TiO₂ photocatalysis were investigated in terms of UV absorbance and COD measurements for a wide range of initial DCF concentrations (5-80 mg L⁻¹) and photocatalyst loadings (0.2-1.6 g TiO₂ L⁻¹) in a batch reactor system. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Artemia salina) was performed to evaluate the potential detoxification of DCF. A pseudo-first-order kinetic model was found to fit well most of the experimental data, while at high initial DCF concentrations (40 and 80 mg L⁻¹) and at 1.6 g TiO₂ L⁻¹ photocatalyst loading a second-order kinetic model was found to fit the data better. The toxicity of the treated DCF samples on D. magna and P. subcapitata varied during the oxidation, probably due to the formation of some intermediate products more toxic than DCF. Unicellular freshwater algae was found to be very sensitive to the treated samples as well as the results from D. magna test were consistent to those of algae tests. A. salina was not found to be sensitive under the investigated conditions. Finally, UV absorbance analysis were found to be an useful tool for a fast and easy to perform measurement to get preliminary information on the organic intermediates that are formed during oxidation and also on their disappearance rate.     

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.     

The Posidonia oceanica marine sedimentary record: A Holocene archive of heavy metal pollution

The study of a Posidonia oceanica mat (a peat-like marine sediment) core has provided a record of changes in heavy metal abundances (Fe, Mn, Ni, Cr, Cu, Pb, Cd, Zn, As and Al) since the Mid-Holocene (last 4470 yr) in Portlligat Bay (NW Mediterranean). Metal contents were determined in P. oceanica. Both, the concentration records and the results of principal components analysis showed that metal pollution in the studied bay started ca. 2800 yr BP and steadily increased until present. The increase in Fe, Cu, Pb, Cd, Zn and As concentrations since ca. 2800 yr BP and in particular during Greek (ca. 2680-2465 cal BP) and Roman (ca. 2150-1740 cal BP) times shows an early anthropogenic pollution rise in the bay, which might be associated with large- and short-scale cultural and technological development. In the last ca. 1000 yr the concentrations of heavy metals, mainly derived from anthropogenic activities, have significantly increased (e.g. from ~ 15 to 47 μg g^− 1 for Pb, ~ 23 to 95 μg g^− 1 for Zn and ~ 8 to 228 μg g^− 1 for As). Our study demonstrates for the first time the uniqueness of P. oceanica meadows as long-term archives of abundances, patterns, and trends of heavy metals during the Late Holocene in Mediterranean coastal ecosystems.     

Design parameters for sludge reduction in an aquatic worm reactor

Reduction and compaction of biological waste sludge from waste water treatment plants (WWTPs) can be achieved with the aquatic worm Lumbriculus variegatus. In our reactor concept for a worm reactor, the worms are immobilised in a carrier material. The size of a worm reactor will therefore mainly be determined by the sludge consumption rate per unit of surface area. This design parameter was determined in sequencing batch experiments using sludge from a municipal WWTP. Long-term experiments using carrier materials with 300 and 350 μm mesh sizes showed surface specific consumption rates of 45 and 58 g TSS/(m² d), respectively. Using a 350 μm mesh will therefore result in a 29% smaller reactor compared to using a 300 μm mesh. Large differences in consumption rates were found between different sludge types, although it was not clear what caused these differences. Worm biomass growth and decay rate were determined in sequencing batch experiments. The decay rate of 0.023 d⁻¹ for worms in a carrier material was considerably higher than the decay rate of 0.018 d⁻¹ for free worms. As a result, the net worm biomass growth rate for free worms of 0.026 d⁻¹ was much higher than the 0.009-0.011 d⁻¹ for immobilised worms. Finally, the specific oxygen uptake rate of the worms was determined at 4.9 mg O₂/(g ww d), which needs to be supplied to the worms by aeration of the water compartment in the worm reactor.     

Parameters predictive of Legionella contamination in hot water systems: association with trace elements and heterotrophic plate counts

The contamination of hot water samples with Legionella spp. was studied in relation to temperature, total hardness, trace element concentrations (iron, zinc, manganese, and copper) and heterotrophic plate counts (HPC) at both 22 and 37 °C. Factor analysis and receiver operating characteristic (ROC) curves were used to establish the cut-off of water parameters as predictors for Legionella contamination. Legionella spp. was isolated in 194 out of 408 samples (47.5%), with Legionella pneumophila being the most common (92.8%). After multiple logistic regression analysis, the risk for legionellae colonisation was positively associated with Mn levels >6 μg l⁻¹, HPC at 22 °C >27 CFU l⁻¹, and negatively with temperature >55 °C and Cu levels >50 μg l⁻¹. Multiple regression analysis revealed that Legionella spp. counts were positively associated with Mn, HPC at 37 °C and Zn and negatively associated with temperature. Only 1 out of the 97 samples (1%) having a Mn concentration, an HPC at 22 °C and an HPC at 37 °C below the respective median values exhibited a Legionella spp. concentration exceeding 10⁴ CFU l⁻¹vs. 41 out of the 89 samples (46.1%) with the three parameters above the medians. Our results show a qualitative and quantitative relationship between Legionella spp., the Mn concentration and heterotrophic plate counts in hot water samples from different buildings, suggesting that these parameters should be included in a water safety plan. The role of manganese in biofilm formation and its possible involvement in the mechanisms favouring Legionella survival and growth in water niches should be investigated further.     

Water, vegetation and sediment gradients in submerged aquatic vegetation mesocosms used for low-level phosphorus removal

Gradients in phosphorus (P) removal and storage were investigated over 6 years using mesocosms (each consisting of three tanks in series) containing submerged aquatic vegetation (SAV) grown on muck and limerock (LR) substrates. Mean inflow total P concentrations (TP) of 32 μg L⁻¹ were reduced to 15 and 17 μg L⁻¹ in the muck and LR mesocosms, respectively. Mesocosm P loading rates (mean = 1.75 g m⁻² year⁻¹) varied widely during the study and were not correlated with outflow TP, which instead varied seasonally with lowest monthly mean values in December and January.The mesocosms initially were stocked with Najas guadalupensis, Ceratophyllum demersum, and Chara zeylanica, but became dominated by C. zeylanica. At the end of the study, highest vegetative biomass (1.1 and 1.4 kg m⁻² for muck and LR substrates) and tissue P content (1775 and 1160 mg kg⁻¹) occurred in the first tank in series, and lowest biomass (1.0 and 0.2 kg m⁻²) and tissue P (147 and 120 mg kg⁻¹) in the third tank. Sediment accretion rates (2.5, 1.9 and 0.9 cm yr⁻¹ on muck substrates), accrued sediment TP (378, 309 and 272 mg kg⁻¹), and porewater soluble reactive P (SRP) concentrations (40, 6 and 4 μg L⁻¹) in the first, second and third tanks, respectively, exhibited a similar decreasing spatial trend. Plant tissue calcium (Ca) near mesocosm inflow (19-30% dry weight) and outflow (23-26%) were not significantly different, and sediment Ca was also similar (range of 24 to 28%) among sequential tanks.Well-defined vegetation and sediment enrichment gradients developed in SAV wetlands operated under low TP conditions. While the mesocosm data did not reflect deterioration in treatment performance over 6 years, accumulation of P-enriched sediments near the inflow could eventually compromise hydraulic storage and P removal effectiveness of these shallow systems.     

Oxidative removal of aqueous steroid estrogens by manganese oxides

This study investigated the oxidative removal of steroid estrogens from water by synthetic manganese oxide (MnO₂) and the factors influencing the reactions. Using 1 × 10⁻⁵ M MnO₂ at pH 4, estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2), all at 4 × 10⁻⁶ M, were rapidly removed within 220 min, indicating the effectiveness of MnO₂ as an oxidizing agent towards estrogens. E2 removal increased with decreasing pH over the tested range of 4-8, due most likely to increased oxidizing power of MnO₂ and a cleaner reactive surface in acidic solutions. Coexisting metal ions of 0.01 M (Cu(II), Zn(II), Fe(III) and Mn(II)) and Mn(II) released from MnO₂ reduction competed with E2 for reactive sites leading to reduced E2 removal. Observed differential suppression on E2 removal may be related to different speciations of metals, as suggested by the MINTEQ calculations, and hence their different adsorptivities on MnO₂. By suppressing the metal effect, humic acid substantially enhanced E2 removal. This was attributed to complexation of humic acid with metal ions. With 0.01 M ZnCl₂ in solutions containing 1 mg l⁻¹ humic acid, the binding of humic acid for Zn(II) was determined at 251 mmol g⁻¹. An in vitro assay using human breast carcinoma MCF-7 cells indicated a near elimination of estrogenic activities without secondary risk of estrogen solutions treated with MnO₂. Synthetic MnO₂ is therefore a promising chemical agent under optimized conditions for estrogen removal from water. Metal chelators recalcitrant to MnO₂ oxidation may be properly used to further enhance the MnO₂ performance.     

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.