Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses

The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course discharging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC-MS/MS and GC-MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p'-DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 microM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones.     

Removal of a broad range of surfactants from municipal wastewater--comparison between membrane bioreactor and conventional activated sludge treatment

Elimination of alkylphenol ethoxylates (APEO) and their degradation products (alkylphenols and alkylphenoxy carboxylates), as well as linear alkylbenzene sulfonates (LAS) and coconut diethanol amides (CDEA), was studied in a pilot plant membrane bioreactor (MBR) working in parallel to a full-scale wastewater treatment plant (WWTP) using conventional activated sludge (CAS). In the CAS system 87% of parent long ethoxy chain NPEOs were eliminated, but their decomposition yielded persistent acidic and neutral metabolites which were poorly removed. The elimination of short ethoxy chain NPEOs (NP(1)EO and NP(2)EO) averaged 50%, whereas nonylphenoxy carboxylates (NPECs) showed an increase in concentrations with respect to the ones measured in influent samples. Nonylphenol (NP) was the only nonylphenolic compound efficiently removed (96%) in the CAS treatment. On the other hand, MBR showed good performance in removing nonylphenolic compounds with an overall elimination of 94% for the total pool of NPEO derived compounds (in comparison of 54%-overall elimination in the CAS). The elimination of individual compounds in the MBR was as follows: 97% for parent, long ethoxy chain NPEOs, 90% for short ethoxy chain NPEOs, 73% for NPECs, and 96% for NP. Consequently, the residual concentrations were in the low mug/l level or below it. LAS and CDEA showed similar elimination in the both wastewater treatment systems that were investigated, and no significant differences were observed between the two treatment processes. Nevertheless, for all studied compounds the MBR effluent concentrations were consistently lower and independent of the influent concentrations. Additionally, MBR effluent quality in terms of chemical oxygen demand (COD), NH(4)(+) concentration and total suspended solids (TSS) was always superior to the ones of the CAS and also independent of the influent quality, which demonstrates high potential of MBRs in the treatment of municipal wastewaters.     

POPs in the Lagoon of Venice: budgets and pathways

Dioxins and furans (PCDD/Fs), polychlorobiphenyls (PCBs) and hexachlorobenzene (HCB) in the ecosystem of the Lagoon of Venice were studied, in order to provide a general picture of conditions in the lagoon in terms of contamination by persistent organic pollutants (POPs). We present here novel data on atmospheric deposition, water, sediment and clam samples collected in the lagoon during the period January 2001-December 2004. Atmospheric deposition was sampled monthly at six sites located both close and far from large industrial and urban sources. Water samples were collected monthly from fifteen stations, and twenty-five samples of sediments and clams (Tapes philippinarum) were collected in four areas where clams are farmed and harvested inside the lagoon. All samples were analysed for PCDD/Fs, PCBs and HCB by HRGC/HRMS in the same laboratory. All samples examined (atmospheric deposition and water) substantially confirmed the spatial pattern reported in previously published data on sediments and atmospheric deposition: the zone surrounding the Porto Marghera petrochemical plant always had the highest levels of POPs (i.e., PCDD/Fs: atmosphere approximately 6 pg of 2,3,7,8-TCDD equivalents (I-TE) m(-2)d(-1); water 0.37 pg I-TEl(-1); sediment: 300 ng kg(-1); clam 2.8 pg I-TE g(-1)), and the minima were found at points on the margins of the lagoon (PCDD/Fs: atmosphere approximately 1 pg I-TEm(-2)d(-1); water 0.05 pg I-TEl(-1); sediment: approximately 5 ng kg(-1); clam approximately 0.2 pg I-TE g(-1)). Intermediate values were often encountered in the historical city centre of Venice and in the central part of the lagoon. To confirm this, new data on correlation between levels of PCDD/F in sediments and clams are reported, both for absolute values and for the PCDD/F "fingerprint". There is always a clear fingerprinting signature (PCDF/PCDD>1) for samples collected near Porto Marghera, and the opposite (PCDF/PCDD<1) in the rest of the lagoon.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

Human intake of PCDDs, PCDFs, and dioxin like PCBs in Japan, 2001 and 2002

PCDDs, PCDFs, and dioxin like PCBs (dioxin) surveillance results derived from regular environmental monitoring as well as other dioxin surveys by national and local governmental bodies in Japan were collected and analyzed. Several thousand data for air and soil in fiscal year 2001 (from 01/04/2001 to 31/03/2002) and 2002, water (from the sea, rivers and lakes), sediment (from the sea, rivers and lakes), ground water, aquatic organisms, purified water from water purification plants, raw water from water purification plants, human breast milk, and human blood in fiscal 2001, and total diet study (TDS) and various kinds of foodstuff in fiscal 1998-2002 were collected. Average human uptake of dioxin in Japan in fiscal 2001 was estimated at 1.68 pg-TEQ/kg-bw/day, while uptake in fiscal 2002 was estimated at 1.52 pg-TEQ/kg-bw/day. Diet accounted for more than 90% of the total intake. Contributions of inhalation and soil ingestion were relatively small. Age-group-specific contribution of various foodstuff to total dietary intake was also estimated. The estimates of intake through fish and shellfish accounted for approximately 45-70% of total dietary intake in each age group. Monte Carlo simulation was conducted, using the data of the air and soil concentrations in fiscal 2001 and the total diet study data in fiscal 1998-2001, in order to obtain information on the variability of dioxin intake; The estimated average, median, 5th percentile and 95th percentile of the intake distribution were 1.78, 1.69, 0.95 and 2.91 pg-TEQ/kg-bw/day, respectively. This study found that the average total intake estimates in Japan in both fiscal 2001 and 2002 were estimated to be below tolerable daily intake level (TDI) defined by the Ministry of Health, Labour and Welfare, Japan (i.e. 4 pg-TEQ/kg-bw/day). The 95th percentile of the dioxin intake distributions estimated with Monte Carlo simulation using the data of the air and soil concentrations in fiscal 2001 and TDS data in fiscal 1998-2001 was also below the Japanese TDI.     

Application of microbial hot spots enhances pesticide degradation in soils

Through transfer of an active, isoproturon degrading microbial community, pesticide mineralization could be successfully enhanced in various soils under laboratory and outdoor conditions. The microbes, extracted from a soil having high native ability to mineralize this chemical, were established on expanded clay particles and distributed to various soils in the form of microbial "hot spots". Both, diffusion controlled isoproturon mass flow towards these "hot spots" (6microg d(-1)) as well as microbial ability to mineralize the herbicide (approximately 5microg d(-1)) were identified as the main processes enabling a multiple augmentation of the native isoproturon mineralization even in soils with heavy metal contamination. Soil pH-value appears to exert an important effect on the sustainability of this process.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Dissipation of sulfosulfuron in water - bioaccumulation of residues in fish - LC-MS/MS-ESI identification and quantification of metabolites

Dissipation study of sulfosulfuron in natural water and its bioaccumulation in fish was conducted at 25+/-2 degrees C and at two different concentration levels 1mgl(-1) and 2mgl(-1). The dissipation data in water showed the DT50 and DT90 values 67-76 and 222-253 days and followed first order kinetics. Bioaccumulation of sulfosulfuron in fish was conducted under static conditions exposing the fish at one-tenth of sub-lethal concentration 9mgl(-1) and at double the concentration 18mgl(-1), for a period of 56 days. On different occasions fish samples were collected and analyzed. A HPLC-RF method was used for the quantification of sulfosulfuron and aminopyrimidine with the limit of quantification 0.001microg ml(-1). Results showed the accumulation of residues of sulfosulfuron in fish over the concentration range 0.009-0.496microg g(-1). Both in water and fish samples, identified the presence of metabolites aminopyrimidine, desmethyl sulfosulfuron, guanidine, sulfonamide, ethyl sulfone and rearranged amine. The formations of these metabolites are confirmed by LC-MS/MS analysis. An LC-MS/MS electro spray ionization technique was used for this purpose. One of the metabolite Aminopyrimidine was identified at higher concentration levels (0.01-0.1microg ml(-1)) when compared with other metabolites. Subsequently dissipation of aminopyrimidine in water and its bioaccumulation was also studied at the concentration level 1mgl(-1) and 2mgl(-1). The calculated DT50 and DT90 values are 66-68 days and 218-226 days, respectively. This followed first order kinetics. Three hundred days after the exposure complete demineralization was observed.     

Influence of metal ion on sorption of p-nitrophenol onto sediment in the presence of cetylpyridinium chloride

Heavy metals and surfactants have a significant effect on the sorption of organic contaminants. In this study, batch equilibrium experiments were carried out to investigate the influence of Pb(NO(3))(2) on the sorption of p-nitrophenol (PNP) onto sediments in the presence of cationic surfactant cetylpyridinium chloride (CPC). Results indicated that in the complex system containing PNP, Pb(NO(3))(2) and CPC, the sorption of PNP decreased with increasing concentration of Pb(NO(3))(2) due primarily to competing for adsorption sites. Likewise, partitioning of PNP in adsorbed surfactant layers and micelles decreased with increasing level of Pb(NO(3))(2). Moreover, the influence of different metal ions (Pb(2+), Cd(2+), Zn(2+)) was examined and results indicated that the presence of heavy metals inhibited the sorption of PNP in the order: Pb(2+)>Cd(2+)>Zn(2+). The competitive effect of the heavy metals was in agreement with the hydration energy and hydrated radius. The results are believed to provide a useful insight into describing the transport and fate of PNP in natural environments.     

Measuring and modelling experimental densities and ultrasonic velocities of aromatic and halogenated environmental pollutants

The potential environmental impact of aromatic and halogenated chemicals from the petrochemical and steel industry is of growning concern. The present paper deals with the modelling and experimental determination of density and speed of sound at the range 278.15-323.15 of six aromatic and halogenated compounds (Benzene, Toluene, Ethylbenzene, Fluorobenzene, 2-Fluorotoluene and Chlorobenzene). Fitting equations were applied to the data in order to correlate for later computer based design. The estimation of the studied properties was made by the application of different theoretical procedures. The Mchaweh-Nasrifar-Moshfeghian model (MNM), an equation of state based on the generalized van der Waals theory which combines the Staverman-Guggenheim combinatorial term of lattice statistics with an attractive lattice gas expression and the Free Length Theory showed a good response at the studied conditions.