Occurrence of dissolved and particle-bound taste and odor compounds in Swiss lake waters

The occurrence of algal taste and odor (T&O) compounds was investigated in three Swiss lakes which exhibit different nutrient levels from eutrophic to oligotrophic (Lake Greifensee, Lake Zurich and Lake Lucerne). Apart from dissolved T&O compounds, the study also encompassed particle-bound compounds, i.e., compounds that can be released from damaged algal cells during drinking water treatment. A combined instrumental (SPME-GC-MS) and sensory method was applied that allowed to detect and quantify T&O compounds in natural waters in the sub ppt to low ppt-range.In addition to the prominent T&O compounds geosmin and 2-methyl-isoborneol (MIB), four other T&O compounds could be detected in the lake waters, though all at relatively low concentrations (maximum concentrations of geosmin 19 ng L⁻¹, MIB 3 ng L⁻¹, β-ionone 27 ng L⁻¹, β-cyclocitral 7 ng L⁻¹, 2-isobutyl-3-methoxypyrazine 2 ng L⁻¹, 2-isopropyl-3-methoxypyrazine 16 ng L⁻¹). The concentration peaks typically occurred in the epilimnion during summer concurrent with a high phytoplankton biomass. Consistently, the concentration levels for most of the compounds varied substantially between the three lakes and generally decreased in the order eutrophic Lake Greifensee > mesotrophic Lake Zurich > oligotrophic Lake Lucerne. Furthermore, our data revealed that the occurrence of β-ionone was largely influenced by Planktothrix rubescens. This is the first time that a correlation between β-ionone and this cyanobacterium has been reported for natural waters.     

The management of undesirable cyanobacteria blooms in channel catfish ponds using a constructed wetland: Contribution to the control of off-flavor occurrences

An exploratory study on the management of undesirable cyanobacteria blooms with respect to off-flavor problems using an integrated vertical-flow constructed wetland (CW) was performed at a small commercial-scale channel catfish farm from 2004 to 2007. The results of the three-year experiment indicated that water treatment by the CW could reduce the possibility of dominance by undesirable cyanobacteria species that often cause off-flavor problems. A detailed investigation in 2007, showed that the concentrations of geosmin, MIB (2-methylisoborneol), and β-cyclocitral in the water of the recirculating pond (4.3 ng L⁻¹, U.D. (undetected) and 0.2 ng L⁻¹, respectively) treated by the CW were significantly lower than those in the control pond (152.6 ng L⁻¹, 63.3 ng L⁻¹ and 254.8 ng L⁻¹, respectively). In addition, the relationships among the cyanobacteria species, the off-flavor compounds and ten environmental variables were explored by canonical correspondence analysis (CCA). The results showed that Oscillatoria sp., Oscillatoria kawamurae and Microcystis aeruginosa were the main sources of off-flavor compounds in the catfish ponds. The successful manipulation of undesirable cyanobacteria species potentially resulted in lower concentrations of odorous compounds in the water of the recirculating pond. An investigation of the concentrations of geosmin and MIB in catfish fillets showed that the levels of odorous compounds were below the OTC (odor threshold concentration) values in the recirculating pond but were above the OTC values from July to October in the control pond. Water recycling by the CW could potentially be one of the best management practices to control off-flavor occurrences in aquaculture.     

Occurrence and fate of organophosphorus flame retardants and plasticizers in urban and remote surface waters in Germany

Within this study, concentration levels and distribution of the organophosphates tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris(2-butoxyethyl) phosphate (TBEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) were investigated at nine lentic surface waters under different anthropogenic impact between June 2007 and October 2009. Furthermore, the possibility of in-lake photochemical degradation of the analytes was studied in laboratory experiments using spiked ultrapure water and lake water samples incubated in Teflon bottles (which transmit sunlight). TBEP, TiBP, and TnBP were photochemically degraded in spiked lake water samples upon exposure to sunlight. Organophosphate concentrations in the more remote lakes were often below or close to the limits of quantification (LOQ). TCPP was the substance with the highest median concentration in rural volcanic lakes (7-18 ng L⁻¹) indicating an atmospheric transport of the compound. At urban lakes their median concentrations were in the range of 23-61 ng L⁻¹ (TCEP), 85-126 ng L⁻¹ (TCPP), <LOQ-53 ng L⁻¹ (TBEP), 8-10 ng L⁻¹ (TiBP), and 17-32 ng L⁻¹ (TnBP). High variability but no significant seasonal trends were observed for all five organophosphates in urban lake water samples.     

Gas-particle partitioning and seasonal variation of polycyclic aromatic hydrocarbons in the atmosphere of Zonguldak, Turkey

Atmospheric concentrations and gas-particle partition coefficients were determined for polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of Zonguldak, Turkey between May 2007 and April 2008. Total concentrations of PAHs ranged from 0.52 ng m^− 3 to 636 ng m^− 3 in the particle phase and from 5.60 ng m^− 3 to 725 ng m^− 3 in the gas phase. The annual mean concentrations of PAHs in the particle and gas phase were found to be 114 ng m^− 3 and 184 ng m^− 3, respectively. Significant seasonal variations of particle and gas phase PAH concentrations were observed with higher levels during cold period. The distribution of PAHs between the particle and gas phase was investigated and it was found that three ring PAHs were associated primarily with the gas phase, four ring PAHs were distributed almost equally between the two phases and five and six ring PAHs were mainly associated with the particle phase. Gas-particle partition coefficients (K_p) of PAHs have been calculated and correlated with their subcooled liquid vapor pressures (P_Lº). The slopes (m_r) varied from − 0.63 to − 0.23 were far from the theoretical value (−1) due to the short distance between the sampling point and the emission sources. The relationships between temperature and gas phase partial pressures of PAHs were examined using the Clausius-Clapeyron equation and the obtained positive slopes indicated that PAH concentrations increased with decreasing air temperature as a result of high dominance of local emissions.     

Occurrence and fate of organophosphorus flame retardants and plasticizers in coastal and marine surface waters

This comprehensive study focused on the spatial and seasonal variations of organophosphorus flame retardants and plasticizers (OPs) in surface water from the estuary of the River Elbe and the German Bight (North Sea). 100 surface water samples were extracted by solid phase extraction (SPE) and analyzed by gas chromatography-mass spectrometry (GC-MS) with regard to 16 different OPs. The dominating substance was found to be tris(1-chloro-2-propyl) phosphate (TCPP) (Elbe: 40-250 ng L⁻¹, German Bight: 3-28 ng L⁻¹). Furthermore, triethyl phosphate (TEP), tri-iso-butyl phosphate (TiBP), tris(2-butoxyethyl) phosphate (TBEP), and triphenylphosphine oxide (TPPO) were detected in concentrations up to 180 ng L⁻¹. Seasonal trends were detected for the longitudinal profile of the Elbe estuary. Besides the dilution of river water with North Sea water toward the mouth, leading to decreasing concentrations at the four sampling cruises (March, May, August, and October, 2010), an additional depletion of non-halogenated OPs was observed in summer which is supposed to be due to biodegradation or photodegradation.In addition, a comparison of all important tributaries of the German Bight (Elbe, Ems, and Weser) as well as the indirect tributaries Meuse, Rhine, and Scheldt was done by multivariate statistical methods. It could be shown that the contribution of non-halogenated alkylated OPs in the Rhine was higher than in all other tributaries. The riverine input of OPs into the North Sea via the investigated tributaries was estimated to be about 50 t yr⁻¹.     

Polybrominated diphenyl ethers, perfluorinated alkylated substances, and metals in tile drainage and groundwater following applications of municipal biosolids to agricultural fields

Polybrominated diphenyl ethers (PBDEs), perfluorinated alkylated substances (PFAS), and metals were monitored in tile drainage and groundwater following liquid (LMB) and dewatered municipal biosolid (DMB) applications to silty-clay loam agricultural field plots. LMB was applied (93,500 L ha^− 1) in late fall 2005 via surface spreading on un-tilled soil (SS_LMB), and a one-pass aerator-based pre-tillage prior to surface spreading (AerWay SSD) (A). The DMB was applied (8 Mg dw ha^− 1) in early summer 2006 on the same plots by injecting DMB beneath the soil surface (DI), and surface spreading on un-tilled soil (SS_DMB). Key PBDE congeners (BDE-47, -99, -100, -153, -154, -183, -209) comprising 97% of total PBDE in LMB, had maximum tile effluent concentrations ranging from 6 to 320 ng L^− 1 during application-induced tile flow. SS_LMB application-induced tile mass loads for these PBDE congeners were significantly higher than those for control (C) plots (no LMB) (p < 0.05), but not A plots (p > 0.05). PBDE mass loss via tile (0-2 h post-application) as a percent of mass applied was ~ 0.04-0.1% and ~ 0.8-1.7% for A and SS_LMB, respectively. Total PBDE loading to soil via LMB and DMB application was 0.0018 and 0.02 kg total PBDE ha^− 1 yr^− 1, respectively. Total PBDE concentration in soil (0-0.2 m) after both applications was 115 ng g^− 1 dw, (sampled 599 days and 340 days post LMB and DMB applications respectively). Of all the PFAS compounds, only PFOS (max concentration = 17 ng L^− 1) and PFOA (12 ng L^− 1) were found above detectable limits in tile drainage from the application plots. Mass loads of metals in tile for the LMB application-induced tile hydrograph event, and post-application concentrations of metals in groundwater, showed significant (p < 0.05) land application treatment effects (SS_LMB > A > C for tile and SS_LMB and A > C for groundwater for most results). Following DMB application, no significant differences in metal mass loads in tile were found between SS_DMB and DI treatments (PBDE/PFAS were not measured). But for many metals (Cu, Se, Cd, Mo, Hg and Pb) both SS_DMB and DI loads were significantly higher than those from C, but only during < 100 days post DMB application. Clearly, pre-tilling the soil (e.g., A) prior to surface application of LMB will reduce application-based PBDE and metal contamination to tile drainage and shallow groundwater. Directly injecting DMB in soil does not significantly increase metal loading to tile drains relative to SS_DMB, thus, DI should be considered a DMB land application option.     

Organochlorines and mercury in livers of great cormorants (Phalacrocorax carbo sinensis) wintering in northeastern Mediterranean wetlands in relation to area, bird age, and gender

Wild birds are exposed to pollutants in their habitats. Top consumers of aquatic environments such as the fish-eating great cormorant (Phalacrocorax carbo sinensis) are especially affected due to the bioaccumulation of toxic substances in their tissues. This study analysed the livers of 80 great cormorants from Greece to estimate the concentration of organochlorines and mercury and to examine their possible toxic effects and origin. The results showed that mercury (geometric mean 8089 ng g⁻¹ dw), p,p′-DDE (2628 ng g⁻¹ dw), ∑ HCHs (47 ng g⁻¹ dw) and HCB (116 ng g⁻¹ dw) concentrations can be considered high compared with those found in great cormorant livers elsewhere except in highly polluted areas, whereas ∑ PCBs occurred in relatively low concentrations (1091 ng g⁻¹ dw). β-HCH was the dominant HCH isomer. Pollutant levels were generally unrelated to area, age and gender. However, p,p′-DDE and p,p′-DDD showed intersite differences, whilst the proportion of PCBs with 8 chlorine atoms were significantly higher in adult than 1st year great cormorants. Pollution did not reflect local patterns but rather these along the Baltic and Black Seas, whilst differences in p,p′-DDE concentration and ∑ DDTs/∑PCBs ratios between Evros, Axios or Amvrakikos, found on common migration route, suggested different bird origins. Most birds had toxic mercury concentrations; 83.7% above 4000 ng g⁻¹ dw and 16% above 17,000 ng g⁻¹ dw. Other pollutant levels were too low to have adverse effects.     

Manganese and lead in children's blood and airborne particulate matter in Durban, South Africa

Despite the toxicity and widespread use of manganese (Mn) and lead (Pb) as additives to motor fuels and for other purposes, information regarding human exposure in Africa is very limited. This study investigates the environmental exposures of Mn and Pb in Durban, South Africa, a region that has utilized both metals in gasoline. Airborne metals were sampled as PM_2.5 and PM₁₀ at three sites, and blood samples were obtained from a population-based sample of 408 school children attending seven schools. In PM_2.5, Mn and Pb concentrations averaged 17 ± 27 ng m^− 3 and 77 ± 91 ng m^− 3, respectively; Mn concentrations in PM₁₀ were higher (49 ± 44 ng m^− 3). In blood, Mn concentrations averaged 10.1 ± 3.4 μg L^− 1 and 8% of children exceeded 15 μg L^− 1, the normal range. Mn concentrations fit a lognormal distribution. Heavier and Indian children had elevated levels. Pb in blood averaged 5.3 ± 2.1 μg dL^− 1, and 3.4% of children exceeded 10 μg dL^− 1, the guideline level. Pb levels were best fit by a mixed (extreme value) distribution, and boys and children living in industrialized areas of Durban had elevated levels. Although airborne Mn and Pb concentrations were correlated, blood levels were not. A trend analysis shows dramatic decreases of Pb levels in air and children's blood in South Africa, although a sizable fraction of children still exceeds guideline levels. The study's findings suggest that while vehicle exhaust may contribute to exposures of both metals, other sources currently dominate Pb exposures.     

Treatment of estrogens and androgens in dairy wastewater by a constructed wetland system

Constructed wetland systems (CWS) have been used as a low cost bio-filtration system to treat farm wastewater. While studies have shown that CWS are efficient in removing organic compounds and pathogens, there is limited data on the presence of hormones in this type of treatment system.The objective of this study was to evaluate the ability of the CWS to reduce estrogenic and androgenic hormone concentration in dairy wastewater. This was achieved through a year long study on dairy wastewater samples obtained from a surface flow CWS. Analysis of hormonal levels was performed using a solid phase extraction (SPE) sample clean-up method, combined with reporter gene assays (RGAs) which incorporate relevant receptors capable of measuring total estrogenic or androgenic concentrations as low as 0.24 ng L⁻¹ and 6.9 ng L⁻¹ respectively. Monthly analysis showed a mean removal efficiency for estrogens of 95.2%, corresponding to an average residual concentration of 3.2 ng L⁻¹ 17β-estradiol equivalent (EEQ), below the proposed lowest observable effect concentration (LOEC) of 10 ng L⁻¹. However, for one month a peak EEQ concentration of 115 ng L⁻¹ was only reduced to 18.8 ng L⁻¹. The mean androgenic activity peaked at 360 ng L⁻¹ and a removal efficiency of 92.1% left an average residual concentration of 32.3 ng L⁻¹ testosterone equivalent (TEQ).The results obtained demonstrate that this type of CWS is an efficient system for the treatment of hormones in dairy wastewater. However, additional design improvements may be required to further enhance removal efficiency of peak hormone concentrations.     

Environmental occurrence, fate and transformation of benzodiazepines in water treatment

Benzodiazepine derivatives are prescribed in large quantities globally and are potentially new emerging environmental contaminants. Unfortunately, a dearth of data exists concerning occurrence, persistence and fate in the environment. This paper redresses this by reviewing existing literature, assessing the occurrence of selected benzodiazepine anxiolytics (diazepam, oxazepam and bromazepam) in wastewater influent and effluent and surface water from Slovenia, evaluating their removal during water treatment and identifying the transformation products formed during water treatment. Their occurrence was monitored in hospital effluent, river water and in wastewater treatment plant influent and effluent. The study reveals the presence of benzodiazepine derivatives in all samples with the highest amounts in hospital effluents: 111 ng L⁻¹, 158 ng L⁻¹ and 72 ng L⁻¹ for diazepam, bromazepam and oxazepam, respectively. Removal efficiencies with respect to biological treatment of diazepam were 16-18% (oxic), 18-32% (anoxic → oxic), 53-76% (oxic → anoxic) and 83% (oxic → anoxic → oxic → anoxic cascade bioreactors), while the removal oxazepam was 20-24% under anoxic conditions. Coupled biological and photochemical treatment followed by the adsorption to activated carbon resulted in a removal efficiency of 99.99%. Results reveal the recalcitrant nature of benzodiazepine derivatives and suggest that only combinational treatment is sufficient to remove them. In addition, eight novel diazepam and four novel oxazepam transformation products are reported.     

Measurement and source identification of polycyclic aromatic hydrocarbons (PAHs) in the aerosol in Xi'an, China, by using automated column chromatography and applying positive matrix factorization (PMF)

In this study, we measured polycyclic aromatic hydrocarbons (PAHs) in aerosols in Xi'an, China from 2005 to 2007, by using a modified Soxhlet extraction followed by a clean-up procedure using automated column chromatography followed by HPLC/fluorescence detection. The sources of PAHs were apportioned by using the positive matrix factorization (PMF) method. The PM₁₀ concentration in winter (161.1 ± 66.4 μg m^− 3, n = 242) was 1.5 times higher than that in summer (110.9 ± 34.7 μg m^− 3, n = 248). ΣPAH concentrations, which are the sum of the concentrations of all detected PAHs, in winter (344.2 ± 149.7 ng m^− 3, n = 45) was 2.5 times higher than that in summer (136.7 ± 56.7 ng m^− 3, n = 24) in this study. These strong seasonal variations in atmospheric PAH concentration are possibly due to coal combustion for residential heating. According to the source apportionment with PMF method in this study, the major sources of PAHs in Xi'an are categorized as (1) mobile sources such as vehicle exhaust that constantly contribute to PAH pollution, and (2) stationary sources such as coal combustion that have a large contribution to PAH pollution in winter.     

Behavior, mass inventories and modeling evaluation of xenobiotic endocrine-disrupting chemicals along an urban receiving wastewater river in Henan Province, China

Historically, the locations of cities mainly depend on the available water source and the urban river not only supplies the fresh water to city but also receives its wastewaters. To analyze the influences of urban zone on its receiving water river, the Jialu River in Henan Province, China, a typical urban river was chosen. Water and sediment samples were collected along the river in 2007 to analyze the concentrations of xenobiotic endocrine-disrupting chemicals (XEDCs) including nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA) in surface water and sediment. The results showed that the concentrations of OP, NP and BPA in surface water were 20.9-63.2 ng L⁻¹ (mean 39.8 ng L⁻¹), 75.2-1520 ng L⁻¹ (mean 645 ng L⁻¹), 410-2990 ng L⁻¹ (mean 1535 ng L⁻¹), respectively. The lowest and highest concentrations of XEDCs in surface water were found in the upper stream and downstream of Zhengzhou urban zone, which was regarded as the major discharge source of these chemicals to this river. The concentrations of OP, NP and BPA in the sediment were 15.9-31.1 ng g⁻¹, 145-349 ng g⁻¹ and 626-3584 ng g⁻¹ with the average concentrations of 21.4 ng g⁻¹, 257 ng g⁻¹ and 2291 ng g⁻¹, respectively. The results of in situ sediment-water partition of XEDCs showed that the partition coefficients (log K_oc′) in the downstream were higher than that in the upstream, which was mainly caused by the retransfer of surface sediment from the upper stream to the downstream. Comparison of measured and theoretical inventories of XEDCs in sediment indicated that the residual time of XEDCs in sediment in the river was about 5 years, which was in the same order of magnitude with its big flood frequency. In order to predict concentration variances of XEDCs in surface water, a fugacity-hydrodynamic model was developed according to the concept of in series completely stirred tank reactors (CSTR). The model results showed that about 29-65% of XEDCs derived from the urban zone (about 2.0 t yr⁻¹) would finally dissipate from aqueous phase in the 170 km downstream of the river. Assuming the discharge amount of XEDCs from the urban zone remaining constant, the predicted concentrations of the total XEDCs in the over 90% river reach would be higher than 1.0 μg L⁻¹ under all normal, high water and low water season in 2007.     

Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China

The occurrence and removal of 13 pharmaceuticals and 2 consumer products, including antibiotic, antilipidemic, anti-inflammatory, anti-hypertensive, anticonvulsant, stimulant, insect repellent and antipsychotic, were investigated in four wastewater treatment plants (WWTPs) of Beijing, China. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Most of the target compounds were detected, with the concentrations of 4.4 ng L⁻¹-6.6 μg L⁻¹ and 2.2-320 ng L⁻¹ in the influents and secondary effluents, respectively. These concentrations were consistent with their consumptions in China, and much lower than those reported in the USA and Europe. Most compounds were hardly removed in the primary treatment, while their removal rates ranging from −12% to 100% were achieved during the secondary treatment. In the tertiary treatment, different processes showed discrepant performances. The target compounds could not be eliminated by sand filtration, but the ozonation and microfiltration/reverse osmosis (MF/RO) processes employed in two WWTPs were very effective to remove them, showing their main contributions to the removal of such micro-pollutants in wastewater treatment.     

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.     

Evidences of non-reactive mercury-selenium compounds generated from cultures of Pseudomonas fluorescens

This work was designed to determine chemically inert mercury-selenium (Hg-Se) compounds formed in a culture of Pseudomonas fluorescens exposed to Hg²⁺ and Se^IV (selenite). To isolate these compounds, different digestion methods were studied and sodium dodecyl sulfate (SDS) lysis was selected. The Hg⁰ and non-reactive Hg were determined in two series of cultures containing 0.0-6.00 μg L⁻¹ Se^IV (0.0-76.0 μmol L⁻¹) in combination with low 5.00 μg L⁻¹ (0.025 μmol L⁻¹) or high 100 μg L⁻¹ (0.500 μmol L⁻¹) Hg²⁺. It was found that Hg⁰ formed in the culture decreased with the increase of initial Se^IV, while the non-reactive Hg increased with the Se^IV. In cultures with low initial [Hg²⁺], a median Se^IV (2.0 μg L⁻¹ or 25.3 μmol L⁻¹) resulted in about 70% of the added Hg²⁺ sequestered as non-reactive Hg, and in culture with high initial Hg²⁺, about 40% was sequestered. P. fluorescens was proved to be indispensible for the formation of the non-reactive Hg-Se compounds. The Hg:Se molar ratio in the non-reactive Hg-Se compounds was close to 1, suggesting the existence of mercuric selenide in cells. Mechanisms for the formation of the non-reactive Hg-Se compounds are proposed.     

Biological removal of 17α-ethinylestradiol by a nitrifier enrichment culture in a membrane bioreactor

Increasing concern about the fate of 17α-ethinylestradiol (EE2) in the environment stimulates the search for alternative methods for wastewater treatment plant (WWTP) effluent polishing. The aim of this study was to establish an innovative and effective biological removal technique for EE2 by means of a nitrifier enrichment culture (NEC) applied in a membrane bioreactor (MBR). In batch incubation tests, the microbial consortium was able to remove EE2 from both a synthetic minimal medium and WWTP effluent. A maximum EE2 removal rate of 9.0 μg EE2 g⁻¹ biomass-VSS h⁻¹ was achieved (>94% removal efficiency). Incubation of the heterotrophic bacteria isolated from the NEC did not result in a significant EE2 removal, indicating the importance of nitrification as driving force in the mechanism. Application of the NEC in a MBR to treat a synthetic influent with an EE2 concentration of 83 ng EE2 L⁻¹ resulted in a removal efficiency of 99% (loading rates up to 208 ng EE2 L⁻¹ d⁻¹; membrane flux rate: 6.9 L m⁻² h⁻¹). Simultaneously, complete nitrification was achieved at an optimal ammonium influent concentration of 1.0 mg NH₄⁺-N L⁻¹. This minimal NH₄⁺-N input is very advantageous for effluent polishing since the concomitant effluent nitrate concentrations will be low as well and it offers opportunities for the nitrifying MBR as a promising add-on technology for WWTP effluent polishing.     

Characterization of copper bioreduction and biosorption by a highly copper resistant bacterium isolated from copper-contaminated vineyard soil

Copper is an essential but toxic heavy metal that negatively impacts living systems at high concentration. This study presents factors affecting copper bioremoval (bioreduction and biosorption) by a highly copper resistant monoculture of Pseudomonas sp. NA and copper bioremoval from soil. Seven bacteria resistant to high concentration of Cu(II) were isolated from enrichment cultures of vineyard soils and mining wastes. Culture parameters influencing copper bioreduction and biosorption by one monoculture isolate were studied. The isolate was identified by 16S rRNA gene sequence analysis as a Pseudomonas sp. NA (98% similarity to Pseudomonas putida, Pseudomonas plecoglossicida and other Pseudomonas sp.). The optimal temperature for growth was 30 °C and bioremoval of Cu(II) was maximal at 35 °C. Considerable growth of the isolate was observed between pH 5.0 and 8.0 with the highest growth and biosorption recorded at pH 6.0. Maximal bioreduction was observed at pH 5.0. Cu(II) bioremoval was directly proportional to Cu(II) concentration in media. Pseudomonas sp. NA removed more than 110 mg L^− 1 Cu(II) in water within 24 h through bioreduction and biosorption at initial concentration of 300 mg L^− 1. In cultures amended with 100 mg L^− 1, 20.7 mg L^− 1 of Cu(II) was biologically reduced and more than 23 mg L^− 1 of Cu(II) was biologically removed in 12 h. The isolate strongly promoted copper bioleaching in soil. Results indicate that Pseudomonas sp. NA has good potential as an agent for removing copper from water and soil.     

Effects of zinc on molting and body weight of the estuarine crab Neohelice granulata (Brachyura: Varunidae)

The semiterrestrial burrowing crab Neohelice granulata is one of the main inhabitants of the supratidal and intertidal zones of brackish salt marshes, estuaries and coastal lagoons from South America's Atlantic littoral. A large population of this species spreads out Mar Chiquita coastal lagoon (in Argentina) and its corresponding wetlands, and is considered as a key species within this system.Since high values of dissolved heavy metals (including Zn) have been recently reported within Mar Chiquita coastal lagoon, with levels unusually higher than those from other coastal systems within Argentina, it has been explored that the existence of a risk of environmental conditions endanger these populations. So, juveniles of this estuarine crab were experimentally exposed to increasing concentrations of dissolved Zn (i.e., 0, 0.5 and 1 mg Zn²⁺ L^− 1) during six months, the time involved between two successive molts; in addition, both the size and weight reached after each molt were also studied in this assay. It can be concluded that zinc can be toxic to crabs only at high concentrations. Considering that levels up to 1 mg Zn L^− 1 were recently reported in Mar Chiquita coastal lagoon waters, the potential occurrence of mean chronic effects on the crab population within the coastal lagoon is discussed.     

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.     

Environmental impact of mining activities in the Lousal area (Portugal): chemical and diatom characterization of metal-contaminated stream sediments and surface water of Corona stream

Lousal mine is a typical “abandoned mine” with all sorts of problems as consequence of the cessation of the mining activity and lack of infrastructure maintenance. The mine is closed at present, but the heavy metal enriched tailings remain at the surface in oxidizing conditions. Surface water and stream sediments revealed much higher concentrations than the local geochemical background values, which the “Contaminated Sediment Standing Team” classifies as very toxic. High concentrations of Cu, Pb, Zn, As, Cd and Hg occurred within the stream sediments downstream of the tailings sites (up to: 817 mg kg⁻¹ As, 6.7 mg kg⁻¹ Cd, 1568 mg kg⁻¹ Cu, 1059 mg kg⁻¹ Pb, 82.4 mg kg⁻¹ Sb, 4373 mg kg⁻¹ Zn). The AMD waters showed values of pH ranging from 1.9 to 2.9 and concentrations of 9249 to 20,700 mg L⁻¹ SO₄⁻², 959 to 4830 mg L⁻¹ Fe and 136 to 624 mg L⁻¹ Al. Meanwhile, the acid effluents and mixed stream waters also carried high contents of SO₄^2−, Fe, Al, Cu, Pb, Zn, Cd, and As, generally exceeding the Fresh Water Aquatic Life Acute Criteria. Negative impacts in the diatom communities growing at different sites along a strong metal pollution gradient were shown through Canonical Correspondence Analysis: in the sites influenced by Acid Mine Drainage (AMD), the dominant taxon was Achnanthidium minutissimum. However, Pinnularia acoricola was the dominant species when the environmental conditions were extremely adverse: very low pH and high metal concentrations (sites 2 and 3). Teratological forms of Achnanthidium minutissimum (Kützing) Czarnecki, Brachysira vitrea (Grunow) Ross in Hartley, Fragilaria rumpens (Kützing) G. W. F. Carlson and Nitzschia hantzschiana Rabenhorst were found. A morphometric study of B. vitrea showed that a decrease in size was evident at the most contaminated sites. These results are evidence of metal and acidic pollution.