Effects of selected pharmaceutically active compounds on the ammonia oxidizing bacterium Nitrosomonas europaea

Pharmaceutically active compounds (PhACs) are commonly found in wastewater influent. However, little research has focused on determining their impact on fundamental processes in wastewater treatment such as nitrogen removal. In this study, focus was placed on 4 commonly occurring PhACs (ketoprofen, naproxen, carbamazepine and gemfibrozil). Their effect was ascertained in the ammonia oxidizing bacterium (AOB), Nitrosomonaseuropaea in terms of membrane integrity and nitrite production. These PhACs were shown to inhibit nitrite production at concentrations of 1 and 10 μM while no effect was observed at 0.1 μM. The maximum observed nitrification inhibition was 25%, 29%, 22% and 26% for ketoprofen, naproxen, carbamazepine and gemfibrozil, respectively. A decrease in the live/dead ratio ranging from 10% to 16% suggests that these PhACs affect membrane integrity in N.europaea. The difference in nitrite production between PhACs treated cells and non PhAC treated controls was still significant following washing suggesting that inhibition is irreversible. Finally, nitrite production when adjusted to the live fraction of cells was also found to decrease suggesting that PhACs inhibited the activity of surviving cells. These results suggest that the presence of PhACs may affect AOB activity and may impact nitrogen removal, a key function in wastewater treatment. Follow up studies with additional AOB and in mixed culture are needed to further confirm these results.     

PCDD/Fs and dioxin-like PCBs in sediment and biota from the Mondego estuary (Portugal)

The concentrations of 17 polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in sediment and key species as an initial investigation on PCDD/Fs and dl-PCBs contamination in the Mondego estuary (Portugal). The results demonstrated that the values of the total PCDD/Fs (∑PCDD/Fs) concentrations were considerably lower than those of the sum of dl-PCBs (∑dl-PCBs) in all the studied samples. Regarding the contribution of individual congeners, OCDD was the predominant PCDD/F and the mono-ortho PCB 118 and PCB 105 were the dominant PCBs in the majority of the samples. Our results suggest that PCDD/Fs and PCBs behave quite differently along the aquatic food web: ∑PCDD/Fs concentrations were lower in higher trophic-level organisms with fish presenting a distinct PCDD/Fs congeners profile; on the contrary, the higher ∑dl-PCBs values were found in upper-level biota, although not exclusively, and quite similar dl-PCBs congener profiles were observed in nearly all the studied species.     

Representative measurement of two-dimensional reactive phosphate distributions and co-distributed iron(II) and sulfide in seagrass sediment porewaters

The high degree of heterogeneity within sediments can make interpreting one-dimensional measurements difficult. The recent development and use of in situ techniques that measure two-dimensional distributions of porewater solutes have facilitated investigation of the role of spatial heterogeneity in sediment biogeochemistry. A colourimetric diffusive equilibration in thin films method has been developed that allows two-dimensional, high-resolution measurement of reactive phosphate in sediment porewaters. A method detection limit of 0.22 μM, an effective upper limit of ∼1000 μM and relative standard deviations typically below 5% were achieved. This method was evaluated by deployment in seagrass (Zostera capricorni) colonised sediments, as part of combined probes with similar colourimetric methods for sulfide and iron(II). The two-dimensional, high resolution distributions obtained provide a highly representative measurement of the co-distributions of porewater solutes, allowing heterogeneous features and biogeochemical processes to be observed and interpreted. Microniches of high phosphate concentration >100 μM were observed throughout the distributions and were interpreted to be due to localised zones of rapid organic matter mineralisation, possibly using electron acceptors other than iron(III) oxyhydroxides (e.g. aerobic respiration) as often they did not correspond with microniches of higher Fe(II) concentration.     

Heavy metal accumulation in Halimione portulacoides: intra- and extra-cellular metal binding sites

Salt marsh plants can sequestrate and inherently tolerate high metal concentrations found in salt marsh sediments. This work intended to understand the Halimione portulacoides (L.) Aellen strategies to prevent metal toxicity, by investigating the metal location in different plant organs and in the cell. A sequential extraction was performed on leaves, stems and roots of H. portulacoides in order to determine and compare the metal (Zn, Pb, Co, Cd, Ni and Cu) concentration in several fractions of the plant material (ethanolic, aqueous, proteic, pectic, polissacaridic, lenhinic and cellulosic). This study shows that all plant organs of H. portulacoides mostly retain metals in the cell wall (65% is the average for all studied metals stored in the root cell wall, 55% in the stems and 53% in the leaves), and the metal content in the intracellular compartment is much lower (21% in roots, 25% in stems and 32% in leaves). High levels of heavy metal in the sedimentary environment do not cause toxicity to H. portulacoides, because H. portulacoides immobilizes them in different cell compartments (cell wall+proteic fraction+intracellular) outside key metabolic sites.     

Bioavailable metals and cellular effects in the digestive gland of marine limpets living close to shallow water hydrothermal vents

The pressure exerted by shallow water hydrothermal vents on edible gastropods and their cellular responses triggered by these stresses are almost unknown. The aims of this study were to evaluate the bioavailability of metals in the Macaronesian endemic limpet Patella candei gomesii living close to shallow water hydrothermal vents, and the structural differences in their digestive gland as well as the levels of apoptosis in that organ. Limpets were sampled in four sites, two with the presence of hydrothermalism and the other two without it. Whole body concentrations of several metals (Ca, Cd, Cs, Co, Cu, Fe, Hg, Mg, Mn, Pb, Rb, Se, Sr, and Zn) were obtained, morphometry analysis of the digestive gland and TUNEL test for apoptosis were also performed. Results revealed that the presence of shallow water hydrothermal vents is a source of chronic metal stress to limpets, imposing modifications in the morphometry and cell composition of the digestive gland of those limpets that may constitute cell and tissue adaptations to the environment they live in. This study sets up new baseline data for further research on the influence of shallow water hydrothermal vents over communities living in these habitats.     

Uptake and depuration of anatoxin-a by the mussel Mytilus galloprovincialis (Lamarck, 1819) under laboratory conditions

Cyanobacterial blooms tend to be more common in warm and nutrient-enriched waters and are increasing in many aquatic water bodies due to eutrophication. The aim of this work is to study the accumulation and depuration of anatoxin-a by Mytilus galloprovincialis a widespread distributed mussel living in estuarine and coastal waters and recognized worldwide as a bioindicator (e.g. Mussel Watch programs). Research on the distribution and biological effects of anatoxin-a in M. galloprovincialis is important. Nevertheless, the risk of human intoxication due to the consumption of contaminated bivalves should also be considered. A toxic bloom was simulated in an aquarium with 5 x 10(5) cell ml(-1) of Anabaena sp. (ANA 37), an anatoxin-a producing strain. Mussels were exposed to Anabaena for 15 days and then 15 days of depuration followed. Three or more animals were sampled every 24h for total toxin quantification and distribution in soft tissues (edible parts). Water samples were also taken every 24h in order to calculate total dissolved and particulate anatoxin-a concentrations. Anatoxin-a was quantified by HPLC with fluorescence detection. No deaths occurred during accumulation and depuration periods. One day after the beginning of depuration, the toxin could not be detected in the animals. Anatoxin-a is distributed in the digestive tract, muscles and foot and is probably actively detoxified.     

Identification and quantification of new polybrominated dimethoxybiphenyls (PBDMBs) in marine mammals from Australia

Marine mammals from Queensland, Australia, are bioaccumulating elevated concentrations of a range of polybrominated natural products. In this study, we detected three new polybrominated dimethoxybiphenyls (PBDMBs) in the blubber of selected marine mammal samples which were identified as 2,6'-dimethoxy-3,3',5-tribromobiphenyl (2,6'-diMeO-BB 36), 2,2'-dimethoxy-3,3'-dibromobiphenyl (2,2'-diMeO-BB 36), and 6,6'-dimethoxy-3,3'-dibromobiphenyl (6,6'-diMeO-BB 11). These three PBDMBs are structurally related to the known natural product 2,2'-dimethoxy-3,3',5,5'-tetrabromobiphenyl (2,2'-diMeO-BB 80). In the first part of this study, 2,2'-diMeO-BB 80 was photochemically debrominated under UV irradiation. This resulted in seven of eight possible mono- to triBDMBs as debromination products. In the second part of this study, the structure of all PBDMBs debromination products was investigated. This was supported by synthesis of two diBDMB and one triBDMB via bromination and subsequent methylation of 2,2'-biphenyldiol. Structures of the remaining PBDMBs were tentatively assigned by considering the retention times, mass spectra and amounts formed during UV irradiation of 2,2'-diMeO-BB 80 . In the third part of this study, blubber of marine mammals from Australia was analysed for PBDMBs using gas chromatography in combination with electron ionization mass spectrometry (GC/EI-MS) in the selected ion monitoring mode. In these samples, 2,2'-diMeO-BB 80 was found at concentrations of 200-1800ngg(-1) lipid weight (lw). The latter represents the highest concentration reported for this compound in environmental samples. 6,6'-diMeO BB 11, 2,2'-diMeO BB 36, and 2,6'-diMeO BB 36 were present at approximately 7ngg(-1) lipids, or 0.43-1.5% of diMeO-BB 80. No further PBDMBs were detected in the samples. The di- and triBDMBs identified in marine mammal blubber have not been reported as natural products. They may represent either new natural products or transformation products of 2,2'-diMeO-BB 80.     

Relationship between blood concentrations of heavy metals and cytogenetic and endocrine parameters among subjects involved in cleaning coastal areas affected by the 'Prestige' tanker oil spill

The sinking of the 'Prestige' oil tanker in front of the Galician coast (NW of Spain) in November 2002 offered a unique opportunity to analyze intermediate cytogenetic and endocrine effects among people exposed to the complex mixture of substances that oil constitutes, including several toxic heavy metals. In this work we evaluated the relationship between exposure to heavy metals (blood concentrations of aluminium, cadmium, nickel, lead and zinc) and genotoxic parameters (sister chromatid exchanges, micronucleus test and comet assay) or endocrine parameters (plasmatic concentrations of prolactin and cortisol) in subjects exposed to 'Prestige' oil during cleaning tasks developed after the spillage. Concentrations of lead were significantly related to the comet assay even after adjusting by age, sex and smoking. Cortisol concentrations were significantly influenced by aluminium, nickel (both, inversely) and cadmium (positively). Women had clearly higher concentrations of prolactin and cortisol, even when adjusting by age, smoking, cadmium, aluminium or nickel. Plasmatic cortisol was jointly influenced by gender, smoking and aluminium or nickel (all p<0.05). In women there was a strong relationship between concentrations of cadmium and prolactin (beta=0.37, p=0.031). When the effects of cadmium, aluminium and nickel on cortisol were simultaneously assessed, only the latter two metals remained statistically significant. Among parameters analysed, cortisol appeared to be the most sensitive to the effects of metal exposure. Plasma levels of cortisol deserve further evaluation as a potentially relevant biomarker to assess the effects of exposure to heavy metals.     

Environmental risks of farmed and barren alkaline coal ash landfills in Tuzla, Bosnia and Herzegovina

The disposal of coal combustion residues (CCR) has led to a significant consumption of land in the West Balkan region. In Tuzla (Bosnia and Herzegovina) we studied previously soil-covered (farmed) and barren CCR landfills including management practises, field ageing of CCR and the transfer of trace elements into crops, wild plants and wastewaters. Soil tillage resulted in mixing of cover soil with CCR. Medicago sativa showed very low Cu:Mo ratios (1.25) which may cause hypocuprosis in ruminants. Total loads of inorganic pollutants in the CCR transport water, but not pH ( approximately 12), were below regulatory limits of most EU countries. Arsenic concentrations in CCR transport water were <2microgl(-1) whereas reductive conditions in an abandoned landfill significantly enhanced concentrations in leachates (44microgl(-1)). The opposite pattern was found for Cr likely due to large initial leaching of CrVI. Public use of landfills, including farming, should be based on a prior risk assessment due to the heterogeneity of CCR.     

Heterogeneity of soil surface ammonium concentration and other characteristics, related to plant specific variability in a Mediterranean-type ecosystem

Heterogeneity and dynamics of eight soil surface characteristics essential for plants—ammonium and nitrate concentrations, water content, temperature, pH, organic matter, nitrification and ammonification rates—were studied in a Mediterranean-type ecosystem on four occasions over a year. Soil properties varied seasonally and were influenced by plant species. Nitrate and ammonium were present in the soil at similar concentrations throughout the year. The positive correlation between them at the time of greatest plant development indicates that ammonium is a readily available nitrogen source in Mediterranean-type ecosystems. The results presented here suggest that plant cover significantly affects soil surface characteristics.