Polycyclic aromatic hydrocarbons in the surface sediments from Yellow River, China

Fourteen surface sediment samples were collected from Lanzhou Reach of Yellow River, China in July 2005. The concentrations of 16 priority polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography equipped with a mass spectrometry detector (GC-MS). Total concentrations of the PAHs ranged from 464 to 2621 ng/g dry weight. Sediment samples with the highest PAH concentrations appeared at the downstream of Lanzhou City, where there was the biggest wastewater discharge pipeline from Lanzhou Oil Refinery Factory and Lanzhou Chemical Industry Company. Municipal sewage also contributed to the PAH contamination in the sediments. A correlation existed between the sediment organic carbon content (f(oc)) and the total PAH concentrations (r(2)=0.57), suggesting that sediment organic carbon content played an important role in controlling the PAHs levels in the sediments. According to the observed molecular indices, PAHs contamination in Lanzhou Reach of Yellow River originated both from the high-temperature pyrolytic processes and from the petrogenic source, showing a mixed PAH input pattern, which was also confirmed by the results of a principal component analysis (PCA). According to the numerical effect-based sediment quality guidelines (SQGs) of the United States, the levels of PAHs at most studied sites in Lanzhou Reach of Yellow River should not exert adverse biological effects. Although at some sites (such as S10, S12, etc.) one PAH may exceed the effects range low (ERL), individual PAH did not exceed the effects range median (ERM). The results indicated that sediments in all sites should have potential biological impact, but should have no impairment.     

Inactivation of Escherichia coli in the electrochemical disinfection process using a Pt anode

Recently, the electrochemical disinfection has gained a great interest as one of the alternatives to conventional chlorination due to its high effectiveness and environmental compatibility. Despite the extensive reports on electro-chlorination disinfection, few researches were reported on the systems without generating chlorine. This study mainly focused on the potential disinfecting ability of electro-generated oxidants other than chlorine with using an inert medium (chloride-free phosphate buffer solution), which was intended to exclude the formation of chlorine during the electrolysis, as the Escherichia coli as an indicator bacterium was disinfected by applying the current to a platinum anode. The electrochemical inactivation of E. coli without chlorine production was demonstrated to occur in two distinct stages. The first stage inactivation takes place rapidly at the beginning of electrolysis, which appears to be achieved by the electrosorption of negatively charged E. coli cells to the anode surface, followed by a direct electron transfer reaction. As the electrolysis continues further, the inactivation becomes slower but steady, in contrast to the first stage of inactivation. This was attributed to the action of reactive oxidants generated from water discharge, such as hydroxyl radical. Overall, this study suggests that the electrochemical disinfection could be successfully performed even without producing chlorine, recommending the potential application for disinfecting water that does not allow including any chloride ions (such as the production of ultra-pure sterilized water for semiconductor washing).     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic Bromeliad species as biomonitor and measuring total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

Polybrominated diphenyl ether in sewage sludge in Germany

Sewage sludge samples from 11 municipal waste water treatment plants in Germany were collected from March 2002 to June 2003. Total Tri- to HpBDE concentrations (sum of significant congeners BDE 28, 47, 99, 153, 154 and 183) ranged from 12.5 to 288 (median 108) and DeBDE (BDE 209) concentrations from 97.1 to 2217 (median 256) ng/gd.m. BDE 209 dominated the congener profile. A significant change of the Tri- to HpBDE congener profile (% of total BDE 28, 47, 99, 153, 154, 183 without 209) in sludge from different stages of the waste water treatment process (primary sludge, secondary excess sludge and (dewatered) digested sludge), indicating a degradation of DeBDE to these congeners, was not observed.     

Copper extraction effectiveness and soil dissolution issues of EDTA-flushing of artificially contaminated soils

Ethylenediaminetetraacetic acid (EDTA) was used as a reference chelating agent in column experiments to investigate the effectiveness of chelant-enhanced flushing of soils artificially contaminated under various conditions (low/high Cu loading, and aging). The associated soil dissolution issues were of particular concern. Dissolution of indigenous Fe/Al oxides, Ca carbonates and organic matter was monitored over the course of flushing. Regardless of contamination condition, above 85% extraction efficiency could be accomplished by 10(-2) and 10(-3)M EDTA-flushing, but not 10(-4)M. The Cu extraction kinetics positively correlated to EDTA concentration but inversely to Cu loading in soils. In addition to extraction from weakly sorbed fractions, a large portion of Cu was extracted from oxide, organic matter and residual fractions, which appears to derive from soil dissolution. Cumulative dissolved amounts of Fe, Al, and Ca were found to reach as high as hundreds of mgkg(-1), which were comparable to Cu contamination. Soil organic matter, which is known to strongly interact with Fe and Al oxides, was also mobilized. The rate and extent of these soil dissolutions were also positively correlated to EDTA concentration. Therefore, the co-extraction of soil minerals and organic matter during chelant-enhanced flushing, which would alter both physical structure and chemical properties of the soils, is detrimental to future land use and deserves greater attention. The concentration of chelating agent is the most crucial factor for an effective soil flushing with minimal damage.     

Spectroscopic investigation of magnetite surface for the reduction of hexavalent chromium

The reduction of Cr(VI) to Cr(III) by magnetite in the presence of added Fe(II) was characterized through batch kinetic experiments and the effect of Fe(II) addition and pH were investigated in this study. The addition of Fe(II) into magnetite suspension improved the reductive capacity of magnetite. Eighty percent of Cr(VI) was reduced by magnetite (6.5 g l(-1)) with Fe(II) (80 mg l(-1)) within 1 h, while 60% of Cr(VI) was removed by magnetite only. However, the extent of improved reductive capacity of magnetite with Fe(II) was less than that predicted by the summation of each reduction capacity of magnetite and Fe(II). The reduction of Cr(VI) in the magnetite suspension with Fe(II) increased with the increase of molar ratio of Fe(II) to Cr(VI) (0.6, 1, 1.5, 2.3) in the range of 0-2.3 and with the decrease of pH in the range of pH 8.0-5.5. The speciation of chromium, iron, and oxygen on the surface of magnetite was investigated by X-ray photoelectron spectroscopy. Cr 2p3/2, Fe 2p3/2, and O 1s peaks were mainly observed at 576.7 and 577.8 eV, at 711.2 eV, and at 530.2 and 531.4 eV, respectively. The results indicates that Cr(III) and Fe(III) were the dominant species on the surface of magnetite after reaction and that the dominant species covered the magnetite surface and formed metal (oxy)hydroxide.     

Effects of long-term alachlor exposure on hepatic antioxidant defense and detoxifying enzyme activities in crucian carp (Carassius auratus)

Alachlor has been widely used in agriculture all over the world. It is suggested that it may be a carcinogen and also an environmental estrogen. In this paper, the physiological and biochemical perturbations of crucian carp (Carassius auratus) exposed to alachlor at different concentrations over 60 days were investigated. The gonadosomatic index (GSI) and hepatosomatic index (HSI) were measured. The activity of hepatic antioxidant defense and detoxifying enzymes, superoxide dismutase (SOD), catalase (CAT) and glutathione S-transferase (GST) and the content of glutathione (GSH) were determined and compared with the control group. The result showed that GSI and HSI decreased significantly (P<0.05) in almost all treatments. The activities of SOD, CAT and GST were induced continuously (P<0.05), while the content of reduced glutathione (GSH) was inhibited on the whole. These changes reflect that the antioxidant systems of the tested fishes were affected. The possible defense mechanistic implications about the changes were thus discussed. Furthermore, hepatic SOD and GST were sensitive to alachlor at low concentration, indicating that they might be potential biomarkers in early detection of alachlor contamination in aquatic ecosystems.     

Enhancement of biodegradation of oil adsorbed on fine soils in a bioslurry reactor

Techniques for enhancing the biodegradation of oil-contaminated fine soils in a slurry-phase bioreactor were investigated. Using a model system consisting of kaolin particles containing adsorbed n-dodecane as a diesel fuel surrogate, we investigated how increasing the temperature and adding a surfactant and various hydrophobic support media affected the biodegradation rate of n-dodecane. Increasing the temperature from 25 to 35 degrees C decreased the time required for complete degradation of n-dodecane by 30%, from 110h to 80h. Addition of the surfactant polyethylene glycol p-1,1,3,3-tetramethylbutylphenyl ether decreased the degradation time to less than 48h at 35 degrees C, although a high concentration of the surfactant (3000mgl(-1)) was required. We suspect that the surfactant increased the degradation rate by solubilizing the n-dodecane into the solution phase in which the microorganisms were suspended. We tested five types of organic polymers as support media for the microorganisms and found that the biodegradation time could be reduced by approximately 50% with a support medium made from polyurethane; in the presence of this medium, only 36h was required for complete decomposition at 35 degrees C. The reduction in the degradation time was probably due to transfer of the n-dodecane from the soil to the support medium, which improved contact between the n-dodecane and the microorganisms. The polyurethane support medium bearing the microorganisms was stable and could be reused.     

Role of dissolved organic carbon in the cosorption of copper and phthalate esters onto Yellow River sediments

Although the sorption mechanism of hydrophobic organic pollutants on soils or sediments has been widely studied, the effects of coexisting heavy metals are seldom reported, especially the role of dissolved organic carbon (DOC) in sorption interactions involving heavy metals. This paper investigates the sorption interactions of phthalate esters (diethyl phthalate, DEP, and di-n-butyl phthalate, DnBP) and copper on Yellow River sediment in the presence of DOC. The results indicate that the sorption hardly varies for DEP but increases up to 20% for DnBP as the copper concentration increases in a water-sediment system with extremely low concentration of DOC. The copper-induced sorption of DnBP could be due to its complexation with copper, as well as its hydrophobicity. In a water-sediment system with the addition of 6.34 mg l(-1) of commercial humic acid (HA), the sorption of DEP is decreased by up to 37%, and that of DnBP is enhanced by up to 41%, as copper is gradually added. This finding is also consistent with the results for a river water-sediment system containing 8.1 mg l(-1) natural DOC. The copper-influenced sorption of DEP and DnBP are found to be due to the binding of copper to DOC that leads to the configuration change of DOC and thus to its enhanced sorption to sediment. By using polarograph and fluorescence spectrograph techniques, the complexation competition among coexisting phthalates, copper and DOC is examined. The resulting data confirm the significant role of DOC in sorption interactions.     

Investigating interactions of phenanthrene with dissolved organic matter: limitations of Stern-Volmer plot

Although linear binding isotherms of hydrophobic organic chemicals (HOCs) with dissolved organic matter (DOM) are widely reported, several studies showed nonlinear HOC-DOM interactions. This study pointed out that fluorescence static quenching modeling (FSQM), which often uses a Stern-Volmer type plot to process the data from fluorescence quenching experiments, is conceptually different from the classic Stern-Volmer equation. We also emphasized that although linear Stern-Volmer plots are generally observed in literature, it does not necessarily indicate a linear HOC-DOM interaction. According to both mathematical simulation and laboratory sorption experiments in this study, nonlinear interactions could be concealed by the use of Stern-Volmer plot. Moreover, this study tested the two assumptions for applying FSQM to process binding data. Our results showed that binding coefficient (K(DOC)) for phenanthrene is neither independent of free solute concentration, nor DOM concentration, which is a critical limitation for using FSQM in a form of Stern-Volmer equation to examine HOC-DOM interactions. Therefore, the true characteristics of HOC-DOM interactions need to be examined using different ways of experimental design and data processing.