Trace metal speciation during dry and wet weather flows in the Tama River, Japan, by using diffusive gradients in thin films (DGT)

The labile species of Ni, Cu, Zn, Cd, and Pb in the Tama River, an urban river in Tokyo, Japan, were measured using diffusive gradients in thin films (DGT) method under dry and wet weather conditions, and the results were compared with total dissolved concentrations in hourly samples collected in parallel. A total of 10 DGT deployments were made and 251 hourly samples were collected during 2 rounds of sampling, conducted between August and October, 2006. Two types of diffusive gradients in thin films (DGT) devices-DGT-RG for labile inorganic and DGT-APA for total (inorganic and organic) labile species-were applied throughout the samplings. The proportions of metals measured by DGT, compared with the dissolved metal concentrations (filtered using a membrane of 0.5 microm pore size), were 38 +/- 5% (RG) and 45 +/- 8% (APA) for Ni and 45 +/- 22% (RG) and 53 +/- 23% (APA) for Zn. No labile Cu was detected throughout the sampling; Cu was assumed to be in stable complexed forms. Labile Pb was detected in 3 out of 10 deployments only; the rest were lower than the detection limit. Dissolved and labile Cd concentrations were below the detection limits. Three rain events encountered during the sampling periods were evaluated. Rains brought considerably higher loads of metals in dissolved form, and DGT measurements indicated that labile metal loads also increased. Selected DGT measurements were compared with the WHAM 6 speciation model and found to be similar to the model-computed results.     

Behaviour of selected endocrine-disrupting chemicals in three sewage treatment plants of Beijing, China

Occurrence and fate of eight kinds of selected endocrine-disrupting compounds (EDCs) in three sewage treatment plants (STPs) of Beijing, China was investigated. These EDCs, composed of 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), bisphenol A (BPA), estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2), in every step of STPs, were simultaneously analysed by gas chromatography/mass spectrometry after derivatisation. All the EDCs were detected in the influents of three STPs, and BPA was the most abundant compound. The concentrations of EDCs ranged from 36.6 ng/l of 17α-E2 (STP C) to 1342.3 ng/l of BPA (STP B) in the influent sewages and from below limits of detection of E2 and E3 (STP C) to 142.5 ng/l of E1 (STP B) in the effluent sewages. The STPs could not remove alkylphenols effectively from the aqueous phase with less than 40% reduction. BPA decreased over 90%, and steroid estrogens achieved considerable reductions from 64.8% of E2 to 94.9% of E3. Generally, biological treatment was more effective in removing alkylphenols, BPA and natural estrogens from the aqueous phase than primary treatment. However, the synthetic estrogen, EE2, was mostly removed by the primary treatment with about 63.5% reduction. It is the first time that the concentration of 17α-E2 in the sewage of China was reported in this paper. The compound might have a bearing with the waste effluents of dairy farms around urban area of Beijing.     

Separation, synthesis and estrogenic activity of 4-nonylphenols: two sets of new diastereomeric isomers in a commercial mixture

Two sets of new diastereomeric 4-nonylphenol (NP) isomers [4-(3,4-dimethylheptan-4-yl)phenol (344NP, NP-J, L) and 4-(3,4-dimethylheptan-3-yl)phenol (343NP, NP-K, P)] were separated from a commercial NP mixture. The mixture of these diastereomers was synthesized at the same time by a single Friedel-Crafts reaction of 3,4-dimethyl-4-heptanol and phenol, and the mixture was separated into individual NPs by HPLC equipped with Hypercarb column. For the first time, in this study the stereostructure-estrogenic activity relationship of NP diastereomers was investigated. The NP isomers (NP-L and NP-P) having the beta-methyl group over the benzene ring were found to be 2-4 times more estrogenic than their diastereomers (NP-J and NP-K). In the case of the other set of diastereomer [4-(3,5-dimethylheptan-3-yl)phenol, (353NP, NP-E, G)] containing gamma-methyl group in the molecule, the gamma-methyl proton signal (delta 0.49) in the more estrogenic isomer (NP-G) also appeared in a higher field than the corresponding methyl signal (delta 0.76) of the less estrogenic isomer (NP-E).     

Elemental composition of sediments in Lake Jinzai, Japan: Assessment of sources and pollution

Bottom sediments from Lake Jinzai in southwest Japan were analyzed to determine their chemical compositions and to assess the potential for ecological harm by comparison with sediment quality guidelines. The pollution status of lake sediments was evaluated by employing contamination factor (CF), pollution load index (PLI), and geoaccumulation index (I(geo)), focusing on a suite of elements in lakebed and core sediments. Elevated concentrations of As, Pb, Zn, Cu, TOC, N, and P were present in several layers of the upper core and other surface sediments. The elevated metal concentrations are likely related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter, and possibly minor non-point anthropogenic sources. Moreover, correlations between the concentrations of trace metals and organic carbon, nitrogen, phosphorus, and iron, suggest that these elements play a role in controlling abundances. Calculated CF, PLI, and I(geo) indicate that the sediments are strongly polluted with respect to As, moderately to strongly polluted with Zn, and moderately polluted with Pb and Cu. Metal concentrations exceed the New York State Department of Environmental Conservation (NYSDEC) lowest effect level and the Canadian Council of Ministers of the Environment (CCME) interim sediment quality guidelines that indicate moderate impact on aquatic organisms in the study area.     

Geochemical evaluation of present-day Tuul River sediments, Ulaanbaatar basin, Mongolia

The Tuul River flows through the Ulaanbaatar basin of Mongolia and is the main source of water for the capital city, Ulaanbaatar. The Tuul catchment can be divided into three parts around Ulaanbaatar (upper, middle, and lower), according to the extent of urbanization. Sixteen surface water and groundwater samples were collected to evaluate present-day water quality and 34 stream sediment samples taken to examine their geochemical composition in relation to provenance and to assess the impact of urban activity on heavy metal accumulation. Groundwater quality in the upper and central water sources was adequate, but high concentrations of NO ₃ ^? were found in the lower water source. Heavy metal concentrations in the sediments are evaluated by comparison with average upper continental crust (UCC) values, coupled with ecological risk assessment by reference to sediment quality guidelines (SQG). The results show average abundances of potentially toxic metals such as As, Pb, Zn, Cu, Ni, Cr, and V are higher in the middle part (within the city) than in the upper and lower parts. However, all three parts show depletion in some chalcophile and high field strength elements (Cu, Ni, Cr, Sr, Nb, Zr, Th, Sc) relative to UCC, indicating that the river sediments were derived from a highly felsic crustal source. The assessment using SQG shows As and Cr are present in levels that cause adverse aquatic biological effects. Although concentrations of Pb, Zn, Cu, and Ni are generally below their respective threshold effect levels, in the middle reaches, values increase and border on the probable effect level. This suggests significant anthropogenic contamination in the urban areas, increasing values above a naturally low regional background.     

PCDD/PCDF formation in the chlor-alkali process—laboratory study and comparison with patterns from contaminated sites

Studies on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) during the electrolysis of sodium chloride solution (brine) using graphite or titanium electrodes were carried out at a laboratory scale. High concentrations of PCDFs but no PCDDs were formed in tests using graphite electrodes. With titanium electrodes, PCDFs were only formed when tar pitch was added and mainly originated from the dibenzofuran present in the tar. For the first time, a detailed assessment of the formation of mono- to octachlorinated PCDD/PCDF from tar pitch was investigated. The assessment included of the chlorination steps proved that PCDFs were formed by successive lateral chlorinated from dibenzofuran to MonoCDFs, DiCDFs, and TriCDFs to form the typical known “chlorine pattern” of TetraCDF to OctaCDF with a dominance of 1,2,7,8- and 2,3,7,8-TetraCDFs, 1,2,3,7,8-PentaCDF, and 1,2,3,4,7,8-HexaCDF as marker congeners. The final homologue distributions depended on reaction time and reaction temperature. In addition, electrolysis with non-chlorinated dibenzo-p-dioxins, dibenzofuran, and biphenyl was carried out. As a result, PCDDs, PCDFs, and PCB were formed at comparable yields. Congener patterns in soil samples from a PCDD/F-contaminated site where chlor-alkali electrolysis had been operated for decades in Japan had identical isomer distribution demonstrating the source and contamination potential and risk of these processes. Therefore, sites where in the past 120 years chlor-alkali electrolysis has been operated or where residues from chlor-alkali production or other chlorine using industries have been disposed should be assessed for their pollution level and exposure relevance. The assessment of total organohalogen content revealed that PCDF is only a small fraction of organohalogens in the contaminated soils. For an appropriate risk assessment, also other chlorinated aromatic compounds such as PCBs or PCNs need to be considered.     

Multivariate analyses of the effect of an urban wastewater treatment plant on spatial and temporal variation of water quality and nutrient distribution of a tropical mid-order river

Freshwater resources are increasingly scarce due to human activities, and the understanding of water quality variations at different spatial and temporal scales is necessary for adequate management. Here, we analyze the hypotheses that (1) the presence of a wastewater treatment plant (WWTP) and (2) a polluted tributary that drains downstream from the WWTP change the spatial patterns of physicochemical variables (pH, turbidity, dissolved oxygen, and electrical conductivity) and nutrient concentrations (reactive soluble phosphorus, total phosphorus, nitrogen series, total nitrogen, and total dissolved carbon) along a mid-order river in SE Brazil and that these effects depend on rainfall regime. Six study sites were sampled along almost 4 years to evaluate the impacts of human activities, including sites upstream (1–3) and downstream (5–6) from the WWTP. The impacts were observed presenting an increasing trend from the source (site 1) towards Água Quente stream (site 4, the polluted tributary), with signs of attenuation at site 5 (downstream from both WWTP and site 4) and the river mouth (site 6). Input of nutrients by rural and urban runoff was observed mainly at sites 2 and 3, respectively. At sites 4 and 5, the inputs of both untreated and treated wastewaters increased nutrient concentrations and changed physicochemical variables, with significant impacts to Monjolinho River. Seasonal variations in the measured values were also observed, in agreement with the pluviometric indexes of the region. Univariate analyses suggested no effect of the WWTP for most variables, with continued impacts at sites downstream, but non-parametric multivariate analysis indicated that these sites were recovering to chemical characteristics similar to upstream sites, apparently due to autodepuration. Therefore, multivariate methods that allow rigorous tests of multifactor hypotheses can greatly contribute to determine effects of both point and non-point sources in river systems, thus contributing to freshwater monitoring and management.     

Advantages and risks of using steel slag in preparing composts from raw organic waste

It had been reported that iron and manganese oxides in steel slag enhanced the production of humic acid (HA) from low-molecular-weight compounds, such as phenolic acids, amino acids, and saccharides. In the present study, this function of steel slag was applied to the composting of raw organic wastes (ROWs). The degree of humification of HAs is an important factor in evaluating compost quality. Thus, HAs were extracted from the prepared composts and the humification parameters were determined, in terms of elemental compositions, acidic functional group contents, molecular weights, spectroscopic parameters from UV–vis absorption and ¹³C NMR spectra. The timing for adding steel slag affected the degree of humification of HAs in the composts. The weight average molecular weight of a HA when slag was added initially (29 kDa) was significantly higher than when slag was added after elevating the temperature of the compost pile (17–18 kDa). These results show that ROWs are decomposed to low-molecular-weight compounds after the pile temperature is elevated and the presence of slag enhances the polycondensation of these compounds to produce HAs with a higher degree of humification. Because the slag used in the present study contained several-tens ng g^?1 to several μg g^?1 of toxic elements (B, Cu, Cr, and Zn), leaching tests for these elements from the prepared composts were carried out. Levels for leaching boron from composts prepared by adding slag (0.2–0.4 mg L^?1) were obviously higher than the corresponding levels without slag (0.05 mg L^?1).     

Destruction of polychlorinated naphthalenes by a high-temperature melting treatment (GeoMelt process)

A series of treatment experiments were carried out to evaluate the applicability of a high-temperature melting treatment (GeoMelt process) to the destruction of polychlorinated naphthalene (PCN) formulation. We started with 10-kg-scale experiments in which a small melting furnace was used and then scaled up to a 1-t-scale experiment in which a melting furnace that resembled an actual treatment system was used. These runs were evaluated whether destruction efficiency (DE) of total PCNs was more than 99.999 % and whether concentrations of PCNs and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/DFs) in vitrified materials, emission gas, and scrubber water were below the target levels. Because DE values and the target levels of PCNs and PCDDs/DFs in these runs were satisfactory, then we carried out a demonstrative experiment using the actual treatment system and confirmed destruction of PCNs. Based on good results of the demonstrative experiment, stock of PCN formulation was successfully treated continuously.     

Spectroscopic analysis of NIR-dye sensitization in bulk heterojunction polymer solar cells

The photovoltaic conversion efficiency for near-infrared (NIR) sunlight is improved successfully by dye sensitization of bulk heterojunction polymer solar cells, in which the active layer was prepared by a ternary blend of poly(3-hexylthiophene), a fullerene derivative (1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-methanofullerene), and an NIR dye, silicon phthalocyanine bis(trihexylsilyl oxide). The mechanism of the NIR-dye sensitization is studied by femtosecond transient absorption spectroscopy.