Sample storage and extraction efficiencies in determination of polycyclic and nitro musks in sewage sludge

Analytical technology is continuously improving, developing better methods for isolating and concentrating trace compounds in environmental samples. Polycyclic and nitro musks (PNMs) are one group of emerging trace compounds detected in municipal wastewater. Differences in sample storage, preparation, and extraction methods for their measurement have led to variability in results. We analyzed 11 PNMs by GC/MS and compared the results of different storage times and extraction methods (supercritical fluid (SFE) or microwave-assisted (MAE)) for 202 samples of primary sludge, waste activated sludge (WAS), raw sludge, and aerobically/anaerobically digested biosolids collected from Canadian municipal wastewater treatment plants. Sixty-three air-dried samples were extracted by SFE, and 139 air-dried, centrifuged, or filtered samples were extracted by MAE. The mean surrogate recoveries were 89% (standard deviation (SD)=11%) for d(10)-anthracene by SFE and 88% (SD=14%) for d(10)-phenanthrene by MAE. Storage study results showed that PNM concentrations changed by a mean of 7% and 9% for primary sludge and WAS respectively after four weeks and decreased up to 25% after 13.5 months of storage in amber glass containers at -18 degrees C. Air-drying of sludge at room temperature caused losses of about 50% of PNM concentrations compared to centrifugation. The proportions of PNMs present in the liquid phase of sludge samples were less than 5% compared to proportions in the sludge solids. The most complete liquid-solid separation was achieved by filtration of frozen/thawed sludge samples, producing a liquid phase that contained less than 1% of the total musk content of the sample.     

Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery

The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.     

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.     

Sonochemical substrate selectivity and reaction pathway of systematically substituted azo compounds

The sonochemical degradation of the systematically substituted azo compound 2,7-dihydroxy-1-phenylazonaphthaline-3,6-disulfonic acid was investigated using a frequency of 850 kHz and an acoustic input power of 61 W. All derivatives were degraded completely within 6h by the ultrasonic treatment. Trifluoromethyl substituted azo compounds exhibited 2-3-fold higher degradation rates in comparison to the reference hydrogen substituted azo compound (k=0.54 h(-1)). In contrast to enzymatic processes (azoreductase or laccase), the ultrasonic treatment for these ortho-, meta-, and para-substituted azo compound showed 1.5-50-fold higher degradation rates. Additionally the ultrasound treatment was characterized by shorter reaction times. As a result of the detection and identification of specific intermediates using LC-MS a reaction pathway of the sonochemical degradation of the analysed azo compound is proposed indicating the formation of cyclohexadienone and naphthalene quinone derivatives.     

Biological denitrification of high strength nitrate waste using preadapted denitrifying sludge

Denitrification of synthetic high nitrate waste containing 9032 ppm NO(3)-N (40,000 ppm NO(3)) in a time period of only 6h has been achieved in our previous study using activated sludge. The activated sludge culture was acclimatized by a stepwise increase in the nitrate concentration of synthetic waste. In the present work, studies were carried out on the changing microbial population of the sludge and the physiology of nitrate metabolism during the various stages of adaptation process to high strength synthetic nitrate waste. During the course of adaptation, with an increase in the nitrate concentration, a sharp increase in the number of denitrifiers was found with an equally rapid decrease in the nitrifying community. Two key enzymes involved in the first two steps of the denitrification process were also studied during this period. The results of the study suggest that specific enzyme levels increase as the activated sludge adapts itself to higher nitrate concentrations. Biological denitrification of high nitrate waste is a slow process and to increase the rate of denitrification, parameters such as pH, temperature, C:N and biomass concentration of the process were optimized using orthogonal array method. Optimized conditions increased the specific nitrate reduction rate by 54% and specific nitrite reduction rate by 45%.     

Modeling in-situ uranium(VI) bioreduction by sulfate-reducing bacteria

We present a travel-time based reactive transport model to simulate an in-situ bioremediation experiment for demonstrating enhanced bioreduction of uranium(VI). The model considers aquatic equilibrium chemistry of uranium and other groundwater constituents, uranium sorption and precipitation, and the microbial reduction of nitrate, sulfate and U(VI). Kinetic sorption/desorption of U(VI) is characterized by mass transfer between stagnant micro-pores and mobile flow zones. The model describes the succession of terminal electron accepting processes and the growth and decay of sulfate-reducing bacteria, concurrent with the enzymatic reduction of aqueous U(VI) species. The effective U(VI) reduction rate and sorption site distributions are determined by fitting the model simulation to an in-situ experiment at Oak Ridge, TN. Results show that (1) the presence of nitrate inhibits U(VI) reduction at the site; (2) the fitted effective rate of in-situ U(VI) reduction is much smaller than the values reported for laboratory experiments; (3) U(VI) sorption/desorption, which affects U(VI) bioavailability at the site, is strongly controlled by kinetics; (4) both pH and bicarbonate concentration significantly influence the sorption/desorption of U(VI), which therefore cannot be characterized by empirical isotherms; and (5) calcium-uranyl-carbonate complexes significantly influence the model performance of U(VI) reduction.     

Transport of Sr2+ and SrEDTA2- in partially-saturated and heterogeneous sediments

Strontium-90 has migrated deep into the unsaturated subsurface beneath leaking storage tanks in the Waste Management Areas (WMA) at the U.S. Department of Energy's (DOE) Hanford Reservation. Faster than expected transport of contaminants in the vadose zone is typically attributed to either physical hydrologic processes such as development of preferential flow pathways, or to geochemical processes such as the formation of stable, anionic complexes with organic chelates, e.g., ethylenediaminetetraacetic acid (EDTA). The goal of this paper is to determine whether hydrological processes in the Hanford sediments can influence the geochemistry of the system and hence control transport of Sr(2+) and SrEDTA(2-). The study used batch isotherms, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core. Isotherms and repacked column experiments suggested that the SrEDTA(2-) complex was unstable in the presence of Hanford sediments, resulting in dissociation and transport of Sr(2+) as a divalent cation. A decrease in sorption with increasing solid:solution ratio for Sr(2+) and SrEDTA(2-) suggested mineral dissolution resulted in competition for sorption sites and the formation of stable aqueous complexes. This was confirmed by detection of MgEDTA(2-), MnEDTA(2-), PbEDTA(2-), and unidentified Sr and Ca complexes. Displacement of Sr(2+) through a partially-saturated undisturbed core resulted in less retardation and more irreversible sorption than was observed in the saturated repacked columns, and model results suggested a significant reservoir (49%) of immobile water was present during transport through the heterogeneous layered sediments. The undisturbed core was subsequently disassembled along distinct bedding planes and subjected to sequential extractions. Strontium was unequally distributed between carbonates (49%), ion exchange sites (37%), and the oxide (14%) fraction. An inverse relationship between mass wetness and Sr suggested that sandy sediments of low water content constituted the immobile flow regime. Our results suggested that the sequestration of Sr(2+) in partially-saturated, heterogeneous sediments was most likely due to the formation of immobile water in drier regions having low hydraulic conductivities.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

Identification of transport processes in column experiments using a frequency domain approach

When a solute transport process is viewed as a dynamic system with input and output, a system identification technique can be used to study it from input-output data. According to the design of excitation signals in the system identification approach, the commonly used rectangular pulse as input signal for column experiments is not optimum because it does not simultaneously meet the requirements for exciting the studied transport process, i.e., possessing frequency components with high enough amplitude and wide enough passband. In this article, stepped sine signals were proposed to replace the rectangular pulse because their amplitude and passband can be independently chosen. The stepped sine signals of concentration were generated by a High Performance Liquid Chromatography (HPLC) and used as the input for the column experiments to identify parameters of the convection-dispersion equation (CDE) and mobile-immobile model (MIM). In order to test the effect of noise on the identification of transport process, numerical experiments were carried out to identify the CDE under white noise when the input was designed as stepped sine functions and rectangular pulse. The results of the numerical experiments showed that the input signal of a sine function was more robust and accurate in process identification than that of a rectangular pulse.     

Effects of tributyltin on the energy metabolism of pen shell (Atrina pectinata japonica)

We examined the effects of tributyltin (TBT) on aerobic and anaerobic energy metabolism of pen shell (Atrina pectinata japonica). We exposed pen shells to TBT at nominal concentrations of 0 (control) and 1.0microg/l for 72h under aerobic condition. At the end of the exposure, half of the pen shells in each treatment were wrapped in plastic wrap to simulate exposure to hypoxia and held at 25 degrees C for another 12h. The concentrations of the products of energy metabolism, namely lactate, pyruvate, fumarate and succinate, in adductor muscle were measured. The exposure to TBT under aerobic condition significantly elevated lactate, pyruvate and fumarate concentrations (p<0.001). After subsequent exposure to anaerobic condition, the mean concentration of succinate in the TBT treatment group was 64% of that in the control group, but there were no significant differences. Our results suggest that the energy metabolism of pen shell is disrupted by exposure to TBT.