Determination of halogenated organic compounds and mutagenicity testing of spent bleach liquors.

The content of organohalogenated compounds in spent bleach liquor from different bleaching stages in a sulphate and a sulphite plant has been determined by a combination of glass capillary gas chromatography, gas-liquid chromatography/mass spectrometry and neutron activation analysis. Several compounds which have not been reported before have been identified including halogenated derivatives of dimethyl-propylnaphthalenes and alkylated catechols. The unconcentrated effluents, non-polar and total extracts were tested for mutagenic activity with Ames' Salmonella test. Spent bleach liquors from most bleaching stages as well as the total effluents contained mutagenic compounds. Addition of liver microsomes for metabolic activation reduced the mutagenic activity in all stages except for the first chlorination stage in the sulphate plant. Two isomers of chloro-, bromo-, and dichloro-p-cymene previously determined in effluents from bleaching plants were synthesized from the parent molecule. Both bromo- and dichloro-p-cymene exhibited weak mutagenic activity in the Salmonella test system. Liver microsomes reduced the effect slightly. The chlorinated cymenes were found to account for up to 18% of the total organically-bound chlorine in the non-polar extracts.     

Nanofiltration removal of chlorinated organic compounds from alkaline bleaching effluents in a pulp and paper plant

Three commercial nanofiltration membranes were used for the removal of chlorinated organic compounds from the first alkaline extraction effluent originated from a kraft mill, using eucalyptus wood as raw material. The assays were carried out at the following operating conditions: pressure = 20 bar, TEMPERATURE = 20°C and circulation VELOCITY = 2 m/s. The results show the nanofiltration feasibility. For the three membranes the rejection factors of chlorinated organic compounds are greater than 95% and two of them present permeate fluxes of approx. 42 kg/hm². Several reference solutes with a wide range of molecular weights and functional groups were also permeated. Their results compared with those of mill effluent allow us to conclude that the effluent tannic compounds are not in a fouling form and that the majority of the organochlorinated matter has a molecular weight greater than 500 Da.     

Swinging-bell resonances and their cancellation identified by dynamical testing in a modern bell tower

The occurrence of the resonance phenomenon causes high amplitude dynamic vibrations in slender structures. This paper presents an archetypal example, including analysis and mitigating intervention, based on the real case study of a bell tower. Resonances between the multi-harmonic swinging motion of five oscillating bells and the first natural frequency of the supporting system, namely a modern tower realized in reinforced concrete, are clearly demonstrated. Using ambient vibration acceleration measurements, the modal parameters of the tower are identified consistently by two different output-only procedures: the first, based on the Complex Mode Identification Function, exploits a frequency representation of the response; the second, based on the Stochastic Subspace Identification Method, works in the time domain. The frequency characteristics of the bell-swinging action are determined through spectral analyses of the structure forced response signals, measured during the swinging motion of each bell separately. The closeness of the tower’s first natural frequency with the third harmonic of the dynamic horizontal force transmitted to the structure by the two heaviest swinging bells is recognized as the source of large oscillations. A finite element model is developed and manually updated to accurately reproduce the tower’s spectral properties and to design a structural intervention for the vibration mitigation. The resonance cancellation obtained through the introduction of a stiffening strut is demonstrated to limit the bell-induced oscillations effectively, as verified by a post-intervention dynamic test campaign.     

Evaluation of extracellular products and mutagenicity in cyanobacteria cultures separated from a eutrophic reservoir

The algal extracellular products (ECPs) in three cultures of cyanobacteria species (Anabaena, Microcystis, and Oscillatoria) dominating the eutrophic reservoir populations and their toxins have been investigated in the present work. Using gas chromatography coupled with high-resolution electron-impact mass spectrometry (GC/EI-MS) and high performance anion-exchange chromatography (HPAEC) techniques, more than 20 compounds were found in the algal culture (including cells and filtrates) extracts. The main identified ECPs were classified to polysaccharides, hydrocarbons, and aldehydes. Odor causing substances such as trans-1,10-dimethyl-trans-9-decalol (geosmin) and 2-methylisoborneol (2-MIB)were also found in the algal cultures. The potential mutagenicity of the algal suspensions was also studied with the Ames test. The organic extracts of the algal suspension from the axenic cultures were mutagenicity in TA98 without S9 mix and in TA100 with and without S9 mix. The results indicate that the ECPs of three algae species dominating the eutrophic reservoir were mutagenic clearly in the bacterial test.     

The identification of highly chlorinated ethers and diethers in river sediment near an epichlorohydrin plant

In harbour sediment samples taken near an epichlorohydrin production plant, a series of highly chlorinated ethers and diethers were detected viz. three isomeric bis(dichloropropyl)ethers, several structurally closely related ethers with 9 carbon atoms (C₉ ethers), a number of C₁₂ ethers and diethers, and finally several C₁₅ ethers. The formation of this new class of ether compounds can be explained on the basis of the chemistry of the addition of HOCl to allylchloride. After initial addition of Cl⁻, a reactive intermediate is formed which may react with the product dichloropropanol, to give the C₆ ethers, or may polymerize with the starting compound allylchloride followed by reaction with the product, to give the C₉, C₁₂ and C₁₅ ethers.     

Chemical characterization of individual particles (PM10) from ambient air in Guiyang City, China

PM10 samples were collected during 5 days in Guiyang, China in July 2003. A total of about 2300 particles was analyzed by an automated Scanning Electron Microscope with Energy-Dispersive Spectrometer (SEM-EDS). Hierarchical cluster analysis (HCA) was used to identify different particle types that occurred in the aerosol. Seventeen particle types were identified and presented in the order of decreasing number abundance as: silicomanganese slag, soil and fly ash, coal burning, silicomanganese, quartz, syngenite, S-bearing iron, calcium rich, gypsum, sphalerite, dolomite, iron, alloy, lead sulfate, zinc rich, sulfur-rich particles and aluminum manufacturing dust. The majority of the particles in the studied size range are of anthropogenic origin, especially from metallurgical industry. The study illustrates the complexity of particle pollution in air of an industrial Chinese city and the results should be useful in planning mitigation measures.     

Low-temperature formation and degradation of chlorinated benzenes, PCDD and PCDF in dust from steel production

Dust from thermal processes may catalytically enhance the formation of chlorinated aromatic compounds under oxygen-rich conditions. The activities of two dust samples from electric arc furnaces and one from iron ore-based steelmaking (oxygen converter) were investigated in a laboratory experiment. The dust samples were heated at 300 degrees C for 2 h in an air atmosphere. The concentrations of chlorinated benzenes did not change greatly upon heating, while the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans decreased. The addition of copper in parallel runs resulted in a substantial increase in the concentration of chlorinated benzenes, thus indicating that the experimental setup was suitable for the evaluation of low-temperature catalysis. The outcome of the experiment seems to suggest that results cannot easily be extrapolated between different thermal and metallurgical processes. Some measures to reduce emissions, such as inhibition of catalytic activity and rapid cooling, could possibly be counterproductive when applied to off-gases from the steelmaking processes investigated here.     

Occurrence, molecular characterization and antibiogram of water quality indicator bacteria in river water serving a water treatment plant

Water pollution by microorganisms of fecal origin is a current world-wide public health concern. Total coliforms, fecal coliforms (Escherichia coli) and enterococci are indicators commonly used to assess the microbiological safety of water resources. In this study, influent water samples and treated water were collected seasonally from a water treatment plant and two major water wells in a Black Belt county of Alabama and evaluated for water quality indicator bacteria. Influent river water samples serving the treatment plant were positive for total coliforms, fecal coliforms (E. coli), and enterococci. The highest number of total coliform most probable number (MPN) was observed in the winter (847.5 MPN/100 mL) and the lowest number in the summer (385.6 MPN/100 mL). Similarly E. coli MPN was substantially higher in the winter (62.25 MPN/100 mL). Seasonal variation of E. coli MPN in influent river water samples was strongly correlated with color (R² = 0.998) and turbidity (R² = 0.992). Neither E. coli nor other coliform type bacteria were detected in effluent potable water from the treatment plant. The MPN of enterococci was the highest in the fall and the lowest in the winter. Approximately 99.7 and 51.5 enterococci MPN/100 mL were recorded in fall and winter seasons respectively. One-way ANOVA tests revealed significant differences in seasonal variation of total coliforms (P < 0.05), fecal coliforms (P < 0.01) and enterococci (P < 0.01). Treated effluent river water samples and well water samples revealed no enterococci contamination. Representative coliform bacteria selected by differential screening on Coliscan Easygel were identified by 16S ribosomal RNA gene sequence analysis. E. coli isolates were sensitive to gentamicin, trimethoprim/sulfamethazole, ciprofloxacin, vancomycin, tetracycline, ampicillin, cefixime, and nitrofurantoin. Nonetheless, isolate BO-54 displayed decreased sensitivity compared to other E. coli isolates. Antibiotic sensitivity pattern can be employed in microbial source tracking.     

Geographic variation of chlorinated pesticides,toxaphenes and PCBs in human milk from sub-arctic and arctic locations in Russia

The concentrations of HCB, alpha-, beta- and gamma-HCH, 3 chlordanes (CHLs), p,p'-DDE, p,p'-DDD, p,p'-DDT, and 30 PCBs (polychlorinated biphenyls) were determined in 140 human milk samples from Kargopol (n=19), Severodvinsk (n=50), Arkhangelsk (n=51) and Naryan-Mar (n=20). Pooled samples were used for determination of three toxaphenes (chlorobornanes, CHBs). The concentrations of HCB, beta-HCH and p,p'-DDE in Russian human milk were 2, 10 and 3 times higher than corresponding levels in Norway, respectively, while concentrations of sum-PCBs and sum-TEQs (toxic equivalent quantities) of the mono-ortho substituted PCBs were in the same range as corresponding levels in Norway. The PCB-156 contributed most to the sum-TEQs. Highest mean concentrations of HCB (129 microg/kg milk fat) and sum-PCBs (458 microg/kg milk fat) were detected in Naryan-Mar, while highest mean concentrations of sum-HCHs (408 microg/kg milk fat), sum-CHLs (48 microg/kg milk fat), sum-DDTs (1392 microg/kg milk fat) and sum-toxaphenes (13 microg/kg milk fat) were detected in Arkhangelsk. An eastward geographic trend of increasing ratios of alpha/beta-HCH, gamma/beta-HCH, p,p'-DDT/p,p'-DDE and PCB-180/28 was observed. In all areas the levels of sum-HCHs decreased with parity (number of children born). Considerable variation in levels of the analysed organochlorines (OCs) was found in all the studied areas. Breast milk from mothers nursing their second or third child (multiparas) in Naryan-Mar showed a significant different PCB profile compared to mothers giving birth to their first child (primiparas) from the same area and to primi- and multiparas in the other areas. Both p,p'-DDE and p,p'-DDT showed a significant, but weak, negative correlation with the infants birth weight.     

Preclinical toxic effects of manganese in workers from a Mn salts and oxides producing plant

The results of the present epidemiological study among 141 workers (mean age: 34 years) from a Mn salts and oxides producing plant in Belgium suggest that preclinical perturbations (lung function, CNS, biological parameters) may occur in subjects exposed to airborne Mn levels (7 years on the average) usually lower (total dust, geometric mean about 1 mg/m3, 95th percentile 3.3 mg/m3) than the levels actually (5 mg/m3) tolerated.     

Bioaccumulation of PCBs and chlorinated pesticides in seals,fishes and invertebrates from the White Sea,Russia

Persistent organochlorines (OC) contaminants, including polychlorinated biphenyl (PCB) congeners, Dichlorophenyltrichloroethane (DDT)- and chlordane (CHL) related compounds, hexachlorocyclohexanes (HCH) isomers and chlorobenzenes (CBz) were determined in blubber of harp seals (Phoca groenlandica), ringed seals (Phoca hispida) and bearded seals (Eringnathus barbatus) as well as in fishes and invertebrates from the White Sea, in northwest Russia. Highest summation operator PCB and summation operator DDT concentrations were found in samples from two male bearded seals (means of 4150 ng/g lw and 3950 ng/g lw, respectively). Female harp seals had mean summation operator PCB and summation operator DDT concentrations of 1070+/-504 ng/g lw and 619+/-328 ng/g lw, respectively. Male and female adult ringed seals had similar mean summation operator PCB concentrations as harp seals (955+/-385 ng/g lw and 999+/-304 ng/g lw, respectively). summation operator CHL concentrations ranged from 63+/-29 ng/g lw in blubber of female adult ringed seals, to 322+/-156 ng/g lw in adult harp seals and averaged 465 ng/g lw in bearded seals. HCH isomers, mirex and chlorobenzenes were detected in all seal samples but were present at lower levels than summation operator CHL, summation operator DDT and summation operator PCB. Concentrations of summation operator CHL, summation operator DDT and summation operator PCB in ringed seals from the White Sea were within the range reported for the Barents Sea but lower than in ringed seals from the Kara Sea. Temporal trends were investigated by comparing concentrations of OCs in blubber of harp seal pups collected in 1992 with pups of the same age collected in 1998. The declines over the 6 year period ranged from approximately 33% for summation operator DDT to 60% for summation operator PCB. These declines are consistent with reports of declining concentrations summation operator DDT in seawater from the White Sea and inflowing rivers in the 1980's and early 1990s. The major OC contaminants in fishes from the White Sea were DDT-related compounds and PCBs. Navaga (Eleginus navaga) had the highest concentrations of the 5 fish species studied with mean summation operator PCB of 41+/-6 ng/g wet wt. while lowest mean concentrations were present in cod muscle (16+/-8 ng/g ww). Concentrations of hexachlorobenzene (HCB), DDT, CHL-related compounds and PCB congeners were strongly correlated with trophic level of the organisms assigned using delta(15)N values, while beta-HCH, gamma-HCH and cis-chlordane showed no relationship with trophic level. Food web magnification factors (FWMFs) for p,p'-DDE, alpha-HCH, oxychlordane and trans-nonachlor the White Sea were similar to those from marine food webs in the Barents Sea and the Canadian arctic, while FWMFs for HCB and PCBs were generally lower. Overall the results suggest that the White Sea marine food differs in terms of the availability of contaminants in comparison to studies of open ocean arctic food webs due to proximity to urban/industrial areas and greater importance of benthic food sources.     

Soil migration, plant uptake and volatilisation of radio-selenium from a contaminated water table

The properties of (79)Se make it of likely potential importance in safety studies for geological disposal of radioactive wastes. Despite a substantial literature on toxic and nutritional aspects of selenium in the environment little consideration has been given to the behaviour of radioactive selenium and its potential transfer from a radioactive waste repository to the biosphere. Column experiments (15 x 50 cm), using a sandy loam soil, indicated that the upwards migration of (75)Se (as a surrogate for (79)Se) from a contaminated water table was dependent upon the redox status of the soil. Low redox conditions within the water table strongly limited upwards (75)Se soil migration, presumably due to the immobilisation of reduced Se species. Under natural conditions, (79)Se from a radioactive waste repository is therefore likely to accumulate at considerable depth. As a consequence, its absence from the rooting zone is likely to limit its transfer into plants. Nevertheless, the column experiments indicated that when an overlap between roots and soil contamination occurs, uptake into the plant is observed. Quantification of (75)Se volatilisation from the column surfaces suggested that this is a significant pathway by which (79)Se may move either directly from soil to the atmosphere, or from soil to plants and then to the atmosphere.     

Assessment of in situ degradation of chlorinated ethenes and bacterial community structure in a complex contaminated groundwater system

The occurrence of in situ degradation of chlorinated ethenes was investigated using an integrated approach in a complex groundwater system consisting of several geological units. The assessment of hydrogeochemistry and chlorinated ethenes distribution using principal component analysis (PCA) in combination with carbon stable isotope analysis revealed that chlorinated ethenes were subjected to substantial biodegradation. Shifts in isotopic values up to 20.4 per thousand, 13.9 per thousand, 20.1 per thousand and 31.4 per thousand were observed between geological units for tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cDCE) and vinyl chloride (VC), respectively. The use of specific biomarkers (16S rRNA gene) indicated the presence of Dehalococcoides sp. DNA in 20 of the 33 evaluated samples. In parallel, the analysis of changes in the bacterial community composition in the aquifers using canonical correspondence analysis (CCA) indicated the predominant influence of the chlorinated ethene concentrations (56.3% of the variance, P=0.005). The integrated approach may open new prospects for the assessment of spatial and temporal functioning of bioattenuation in contaminated groundwater systems.     

Chemical composition of suspended sediments in World Rivers: New insights from a new database

The aim of this paper is to present a new database on the chemical composition of suspended matter in World Rivers, together with the associated elemental fluxes. There is a lack of any recent attempt in the literature to update the pioneering work of Martin and Meybeck [Martin, J.-M., Meybeck, M., 1979. Elemental mass balance of material carried by major world rivers. Mar. Chem. 7, 173-206.] and Martin and Whitfield [Martin, J.-M., Whitfield, M., 1983. The significance of the river input of chemical elements to the ocean. Trace metals in sea water Wong, Boyle, Bruland, Burton, Goldberg (Eds) Plenum Publishing Corporation.] regarding the worldwide average major and trace element chemistry of riverine particulate matter.Apart from compiling a new database on particulate matter, this paper also aims to give a “snap-shot” of elemental fluxes for each continent. This approach should allow us to obtain new insights on weathering conditions in different environments and assess the influence of human activities on natural geochemical cycles. Finally, this study demonstrates the large uncertainties currently associated with estimating the flux of sediments transported by rivers.By comparing the riverine suspended sediment fluxes of some metals (Cd, Zn, Ni, Cu, Cr and Pb) given in this study with estimates of the anthropogenic fluxes of these metals to the atmosphere, soils and waters (natural ecosystems) [Nriagu, J.O., 1988. A silent epidemic of environmental poisoning. Environ. Pollut. 50, 139-161.], we can see that riverine fluxes are similar to anthropogenic fluxes. This casts light on the effect of human activities on the cycles of trace elements at the Earth's surface.     

Physical and chemical properties of pond waters receiving warm-water effluent from a thermal power plant

The effects of cooling water discharge from one small thermal power plant on the physical and chemical properties of the water in a natural closed pond in central Finland were studied over a 2 year period. The principal changes in the pond caused by the warm water discharge into the surface water layer were (1) a shortened duration of winter ice cover (ice cover only during short periods from December to March) and (2) the early and prolonged chemical and thermal stratification of the pond water (April–October). This prolonged stratification resulted in a strong hypolimnetic oxygen depletion along with other consequences associated with anoxic bottom waters. Increased phytoplankton growth was evident in February causing a rapid decrease in silica, phosphate and total phosphorus concentrations. The depth of euphotic layer decreased rapidly from 4 to 1 m following early ice-out as the phytoplankton and rotifer densities increased.     

Isolation and characterization of a bacterium capable of removing taste- and odor-causing 2-methylisoborneol from water

2-Methylisoborneol (MIB), a metabolite of blue-green algae, has been implicated in causing unpalatable drinking water throughout the world. Current non-biological water treatment technologies are ineffective in removing MIB from potable water or are cost-prohibitive, and biological applications may address these problems. We have isolated and characterized a bacterium derived from lake water and capable of aerobically degrading MIB. Light microscopy and transmission electron microscopy revealed that this strain is a spore-forming, flagellated bacterium that is bacilloid in shape, and 16S rRNA phylogenetic analysis determined that it is most closely related to Bacillus fusiformis and Bacillus sphaericus, both members of the Bacillus sphaericus senso lato taxon. While the growth and oxidation potential of this strain was shown to be affected beyond certain MIB concentrations in the mg/l range, it was capable of depleting MIB at mg/l and ng/l concentrations and of removing MIB to concentrations yielding no observed odor.     

青岛某污水处理厂AB工艺改造为MSBR工艺实践

青岛市某污水处理厂原AB处理工艺,由于设计处理能力无法满足城市发展和日益增长的污水水量处理要求,该污水处理厂对现有工艺进行改造,改造后采用MSBR改良型序批反应器,处理水量由80 000m3/d预计提高到160 000m3/d,出水水质由CODCr≤150mg/L、BOD5≤40mg/L、SS≤40mg/L提高到CODCr≤50mg/L、BOD5≤10mg/L、SS≤10mg/L、TN≤15mg/L、NH3-N≤5(8)mg/L、TP≤0.5mg/L,改造后CODCr,BOD5,SS,TN,NH3-N,TP的平均处理效率分别达到90%,94%,93%,72%,97.4%,80%,达到《城镇污水处理厂污染物排放标准》(GB 18918—2002)的一级A排放标准.     

污水处理厂出水氨氮异常的分析与控制

针对某污水处理厂出水氨氮异常的突发事件,分别对该事件发生的可能原因进行了分析,分别为进水氨氮突然升高和硝化菌流失所致,并根据分析结果采取了针对性的控制措施,取得了良好的效果,可为国内其他污水处理厂应对该类异常现象提供参考.     

Effects of storage and conservation on the determination of ammonia in water samples from four lake types and a sewage plant

Measurements of the concentration of ammonia at the time of sampling require immediate filtration and addition of ammonia reagents. Studies were made of (a) three methods of storage, (b) the effect of preserving the sample with H₂SO₄ or HgCl₂, and (c) the effect of filtration through GF/C or 0.2 μm Nuclepore filters, in samples from different types of freshwater. Stored or preserved samples filtered through both types of filter showed similar, unsystematic changes in concentration of ammonia compared with the concentration measured in samples fixed with ammonia reagents at the sampling site.     

Binding, distribution, and plant uptake of mercury in a soil from Oak Ridge, Tennessee, USA

A large amount of mercury has been discharged on the U.S. Department of Energy's Oak Ridge Site (Tennessee) as a part of the U.S. nuclear weapon program during the 1950s through the early 1960s. Increases in mercury concentration in fish and in lower East Fork Poplar Creek of Oak Ridge have been recently reported. This is an experimental study mimicking the initial stage of transformation and redistribution of mercury in soils, which are comparable to those of the Oak Ridge site. The objectives of this study were to investigate potential transformation, distribution, and plant uptake of mercury compounds in soils. Results show that the H(2)O(2)-oxidizable mercury fraction (organically bound mercury) was the major solid-phase fraction in soils freshly contaminated with soluble mercury compounds, while cinnabar fraction was the major solid phase fraction in soils contaminated with HgS. Langmuir relationships were found between mercury concentrations in plant shoots and in soil solid-phase components. Mercury in HgS-contaminated soils was to some extent phytoavailable to plants. Mercury transformation occurred from more labile fractions into more stable fractions, resulting in strong binding of mercury and decreasing its phytoavailability in soils. In addition, high mercury losses from soils contaminated with soluble mercury compounds were observed during a growing season through volatilization, accounting for 20-62% of the total initial mercury in soils.