Air-surface exchange of mercury with soils amended with ash materials

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing -10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing -10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, -0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, -20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O3 concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m2 day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m2 day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m2 day and for soil with pads constructed of ash ranged from -50 to 90 ng/m2 day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Air-Surface Exchange of Mercury with Soils Amended with Ash Materials

Abstract

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing ～10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing ～10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, ～0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, ～20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O₃ concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m² day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m² day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m² day and for soil with pads constructed of ash ranged from ?50 to 90 ng/m² day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.     

Denitrification with carbon addition--kinetic considerations

The Blue Plains Advanced Wastewater Treatment Plant (Washington, D.C.) uses methanol as an external carbon source in a postdenitrification process, to achieve low effluent total nitrogen concentrations. This becomes more difficult in winter, at lower mixed liquor temperatures and higher flows, as a consequence of the kinetic behavior of the methanol-utilizing heterotrophs. The paper reports on an experimental batch test study conducted on Blue Plains postdenitrification sludge to investigate (1) the maximum specific growth rate of methanol-utilizing heterotrophs (Mu(METH)); (2) the temperature dependency of the growth rate; and (3) the efficacy of alternate substrates (ethanol, acetate, and sugar). A limited number of tests were conducted on sludge from two other treatment plants with methanol addition.     

Interactions of uranium with polyphosphate

Inorganic polyphosphates (PolyP) are simple linear phosphate (PO(4)(3-)) polymers which are produced by a variety of microorganisms. One of their functions is to complex metals resulting in their precipitation. We investigated the interaction of phosphate and low-molecular-weight PolyP (1400-1900Da) with uranyl ion at various pHs. Potentiometric titration of uranyl ion in the presence of phosphate showed two sharp inflection points at pHs 4 and 8 due to uranium hydrolysis reaction and interaction with phosphate. Titration of uranyl ion and PolyP revealed a broad inflection point starting at pH 4 indicating that complexation of U-PolyP occurs over a wide range of pHs with no uranium hydrolysis. EXAFS analysis of the U-HPO(4) complex revealed that an insoluble uranyl phosphate species was formed below pH 6; at higher pH (> or = 8) uranium formed a precipitate consisting of hydroxophosphato species. In contrast, adding uranyl ion to PolyP resulted in formation of U-PolyP complex over the entire pH range studied. At low pH (< or = 6) an insoluble U-PolyP complex having a monodentate coordination of phosphate with uranium was observed. Above pH 6 however, a soluble bidentate complex with phosphate and uranium was predominant. These results show that the complexation and solubility of uranium with PO(4) and PolyP are dependent upon pH.     

Remediating dicamba-contaminated water with zerovalent iron

Dicamba (3,6-dichloro-2-methoxybenzoicacid) is a highly mobile pre- and post-emergence herbicide that has been detected in ground water. We determined the potential of zerovalent iron (Fe0) to remediate water contaminated with dicamba and its common biological degradation product, 3,6-dichlorosalicylic acid (DCSA). Mixing an aqueous solution of 100 microM dicamba with 1.5% Fe0 (w/v) resulted in 80% loss of dicamba within 12 h. Solvent extraction of the Fe0 revealed that dicamba removal was primarily through adsorption; however when the Fe0 was augmented with Al or Fe(III) salts, dicamba was dechlorinated to an unidentified degradation product. In contrast to dicamba, Fe0 treatment of DCSA resulted in removal with some dechlorination observed. When DCSA was treated with Fe0 plus Al or Fe(III) salts, destruction was 100%. Extracts of this Fe0 treatment contained the same HPLC degradation peak observed with the Fe0 + Al or Fe(III) salt treatment of dicamba. Molecular modeling suggests that differences in removal and dechlorination rates between dicamba and DCSA may be related to the type of coordination complex formed on the iron surface. Experiments with 14C-labeled dicamba confirmed that Fe-adsorbed dicamba residues are available for subsequent biological mineralization (11% after 125 d). These results indicate that Fe0 could be potentially used to treat dicamba and DCSA-contaminated water.     

Identification of barley genotypes with low grain Cd accumulation and its interaction with four microelements

The variation in grain cadmium (Cd) concentrations was evaluated among 600 barley genotypes grown in the same field condition to select low Cd accumulating genotypes. The results showed that there is considerable genotypic variation in grain Cd concentrations in barley grain samples, with the mean concentration of 0.16 mg kg(-1) DW and the variation of 0 (not detected) to 1.21 mg kg(-1) DW, and 47.2% of the grain samples exceeded the maximum permissible concentration (MPC) for Cd in cereal grains. In addition, differences between genotypes over the two years were fairly consistent, and Beitalys and Shang 98-128 showed the lowest grain Cd concentration, being 97.5% lower than that in the two highest Cd accumulators E-barley 6 and Zhenong 8 in the second harvest year. The great genotypic differences in Cd concentrations indicated that it is possible to lower Cd content of barley through cultivar selection and breeding for use at sites where Cd concentration in grain exceeds the MPC. Significant genotypic difference was also found in microelement concentrations. Correlation analysis showed that only Mn accumulation is synergetic with Cd accumulation, despite slightly positive relationship between Cd and Zn, Cu, or Fe in accumulation in barley grains.     

Co-inoculation with beneficial microorganisms enhances tannery sludge bioleaching with Acidithiobacillus thiooxidans

Environmental Science and Pollution Research - Bioleaching of tannery sludge is an efficient and environmentally friendly way for chromium (Cr) removal, which supports the sustainable development...     

Dissolution studies on TiO2 with organics

In this work the effect of organic reducing reagents, namely, ascorbic acid, oxalic acid and L-cysteine on dissolution of commercial TiO(2) has been investigated. Kinetic studies showed that a maximum of about 45% of TiO(2) was dissolved by ascorbic acid in 4h when oxide:acid molar ratio was kept at 1:2. The dissolution of TiO(2) increased with increase in ascorbic acid and oxalic acid concentration up to 0.15M in 4h (corresponding to molar ratio of oxide to acid of 1:3) and further addition did not affect the dissolution. Nearly 45% TiO(2) dissolution was obtained with ascorbic acid alone while oxalic acid yielded 40% dissolution. When oxalic acid was added along with ascorbic acid in equi-molar concentrations, dissolution of TiO(2) was enhanced to 60% in 2.5h but when cysteine was added to ascorbic acid the dissolution was about 50% in just 1h.     

Biomonitoring of airborne mercury with perennial ryegrass cultures

A biomonitoring network with grass cultures was established near a chlor-alkali plant and the mercury concentration in the cultures were compared with the average atmospheric total gaseous mercury (TGM). Biomonitoring techniques based on different exposure periods were carried out. When comparing the mercury concentration in the grass cultures, both the average atmospheric TGM concentration during exposure and the exposure time determined to a large extent the accumulation rate of TGM. The maximum tolerable level of mercury in grass (approximately equal to 110 microg kg(-1) DM) corresponds with an average TGM concentration of 11 ng m(-3) for 28 days exposure. The background concentrations in grass were on an average 15 microg kg(-1) DM and the effect detection limit (EDL) was 30 microg kg(-1) DM. This value corresponds with an average TGM concentration of 3.2 and 4.2 ng m(-3) for 28 and 14 days exposure, respectively, which is in turn the biological detection limit (BDL) of ambient TGM. Exposures for 7 days were less appropriate for biomonitoring.     

Enhanced nitrogen removal of coal pyrolysis wastewater with low COD to nitrogen ratio by partial nitrification-denitrification bioprocess assisted with polycaprolactone

The purpose of this study is to investigate the enhancement of polycaprolactone (PCL) on total nitrogen (TN) removal of coal pyrolysis wastewater (CPW) with low COD to nitrogen ratio by partial nitrification-denitrification bioprocess (PNDB) in one single reactor. With the innovative combination of PCL and PNDB, the TN removal efficiency in the experimental reactor (signed as R1) was 10.21% higher than control reactor (R2). Nitrite accumulation percentage (NAP) in R1 was 82.02%, which was 17.49% higher than R2 at the dissolved oxygen (DO) concentration of 0.9–1.5 mg/L, for the reason that the extra DO was consumed by PCL biodegradation at the aerobic period. Gel permeation chromatography (GPC) results demonstrated that organics with the molecular weight of 185 Da, which could serve as additional carbon sources for denitrifiers, were generated during the PCL hydrolysis process at the anoxic period. PCL was hydrolyzed by extracellular enzymes with the break of the ester bond which was confirmed by FT-IR spectrometer. Microbial community analysis revealed that Ferruginibacter was the dominant hydrolysis bacteria in R1. Nitrosomonas were the main ammonium-oxidizing bacteria (AOB) and Hyphomicrobium were the denitrifiers in this study.

     

Cytochrome c adducts with PCB quinoid metabolites

Polychlorinated biphenyls (PCBs) are a group of 209 individual congeners widely used as industrial chemicals. PCBs are found as by-products in dye and paint manufacture and are legacy, ubiquitous, and persistent as human and environmental contaminants. PCBs with fewer chlorine atoms may be metabolized to hydroxy- and dihydroxy-metabolites and further oxidized to quinoid metabolites both in vitro and in vivo. Specifically, quinoid metabolites may form adducts on nucleophilic sites within cells. We hypothesized that the PCB-quinones covalently bind to cytochrome c and, thereby, cause defects in the function of cytochrome c. In this study, synthetic PCB quinones, 2-(4′-chlorophenyl)-1,4-benzoquinone (PCB3-pQ), 4-4'-chlorophenyl)-1,2-benzoquinone (PCB3-oQ), 2-(3′, 5′-dichlorophenyl)-1,4-benzoquinone, 2-(3′,4′, 5′-trichlorophenyl)-1,4-benzoquinone, and 2-(4′-chlorophenyl)-3,6-dichloro-1,4-benzoquinone, were incubated with cytochrome c, and adducts were detected by liquid chromatography-mass spectrometry (LC-MS) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI TOF). Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was employed to separate the adducted proteins, while trypsin digestion and liquid chromatography-tandem mass spectrometry (LC-MS/MS) were applied to identify the amino acid binding sites on cytochrome c. Conformation change of cytochrome c after binding with PCB3-pQ was investigated by SYBYL-X simulation and cytochrome c function was examined. We found that more than one molecule of PCB-quinone may bind to one molecule of cytochrome c. Lysine and glutamic acid were identified as the predominant binding sites. Software simulation showed conformation changes of adducted cytochrome c. Additionally, cross-linking of cytochrome c was observed on the SDS-PAGE gel. Cytochrome c was found to lose its function as electron acceptor after incubation with PCB quinones. These data provide evidence that the covalent binding of PCB quinone metabolites to cytochrome c may be included among the toxic effects of PCBs.     

Maximum ground-level concentrations with downwash--analysis

Equations derived previously for critical downwind distance xc' wind speed uc' and plume rise zc' the values that produce maximum ground-level concentrations (MGLC) chi c under downwash conditions, have been solved. Tables of chi c' xc' uc' and zc' and graphs of the relationships among uc and zc, for a range of stack heights hs' and building heights hb' are presented. Results for two types of sources--a turbine and a reciprocating engine--are discussed. Some comparisons are made to the U.S. Environmental Protection Agency's (EPA) SCREEN3 model.     

Molecular study of concentrated copper pollutant with a compost

Humic substance in compost contains various organic functional groups that can sorb metal ions through ionic force. This study used thermal treatment technology to concentrate copper in the heated residues while destroying the humic substance of copper-sorbed kitchen compost. Scanning electron microscopy (SEM) results show that copper clusters were formed in the heated residues. Information from both X-ray diffraction (XRD) patterns and Cu K-edge X-ray absorption spectroscopy (XAS) spectrum indicates that about 30% of the doped Cu(II) was chemically reduced to Cu(I) and Cu(0) when the sample was heated at 500 and 900 degrees C for 2h. The XAS results indicate that after 500 degrees C thermal treatment, the loaded Cu(NO(3))(2) was transformed into CuO (ca. 54%), Cu (ca. 18%), Cu(OH)(2) (ca. 15%), and Cu(2)O (ca.13%). Heating at 900 degrees C caused more transformation into elemental Cu probably due to more release of oxygen.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

5-fluorouracil and curcumin with pectin coating as a treatment regimen for titanium dioxide with dimethylhydrazine-induced colon cancer model

Environmental Science and Pollution Research - Colorectal cancer was inducted in Wister rats using titanium dioxide nanoparticles (TiO2NPs) and dimethylhydrazine (DMH) and treatment using...     

Fractionation of technical p-nonylphenol with preparative capillary gas chromatography

A fractionation procedure for technical p-nonylphenol using preparative capillary gas chromatography (pcGC) was developed and evaluated for its potential applicability in effect-directed analysis (EDA). The instrument is composed of (1) a preparative unit equipped with a cold injection system (CIS), two preparative fraction collectors (PFCs) with six fraction traps each, and a flame ionization detector (FID) and (2) an analytical unit sharing the same GC oven and equipped with another CIS and mass spectrometric detection (MSD) for isomer identification. The pcGC methodology used in this study is characterized by a high reproducibility of retention times and peak areas. This provides the fractionation of nonylphenol isomers into 11 fractions containing 77-552microg of isomers collected after 600 single injections. This yield is sufficient to allow subsequent biotesting in the E-screen assay.     

Hydrocarbon-utilizing microorganisms naturally associated with sawdust

Sawdust, one of the materials used as sorbent for removing spilled oil from polluted environments was naturally colonized by hydrocarbon-utilizing fungi, 1 × 10⁵-2 × 10⁵ colony forming units (CFU) g⁻¹, depending on the hydrocarbon substrate. This sorbent was initially free of hydrocarbon-utilizing bacteria. Incubating wet sawdust at 30 °C resulted in gradually increasing the fungal counts to reach after 6 months between 5 × 10⁶ and 7 × 10⁶ CFU g⁻¹, and the appearance of hydrocarbon-utilizing bacteria in numbers between 8 × 10⁴ and 3 × 10⁵ cells g⁻¹. The fungi belonged to the genera Candida (32% of the total), Penicillium (21%), Aspergillus (15%), Rhizopus (12%), Cladosporium (9%), Mucor (7%) and Fusarium (4%). Based on their 16S rRNA gene sequences the bacteria were affiliated to Actinobacterium sp. (38%), Micrococcus luteus (30%), Rhodococcus erythropolis, (19%) and Rhodococcus opacus (13%). Individual pure fungal and bacterial isolates grew on a wide range of individual pure aliphatic (n-alkanes with chain lengths between C₉ and C₄₀) and aromatic (benzene, biphenyl, anthracene, naphthalene and phenanthrene) hydrocarbons as sole sources of carbon and energy. Quantitative determinations revealed that all fungal and bacterial isolates could consume considerable proportions of crude oil, phenanthrene (an aromatic hydrocarbon) and n-hexadecane (an aliphatic hydrocarbon) in batch cultures. It was concluded that when sawdust is used as a sorbent, the associated microorganisms probably contribute to the bioremediation of oil and hydrocarbon pollutants in the environment.     

Fractionation of fulvic acids: characteristics and complexation with copper

Two fulvic acid samples isolated from Suwannee river (International Humic Substance Society) and Feeitsuey reservoir were subjected to gel filtration chromatography (GFC) for molecular size fractionation. The GFC-eluted samples were separated into three groups corresponding to the molecular weight ranges: < 220, 220-1000, and 1000-4000. Fluorescence quenching techniques were employed for determining the conditional stability coefficient and kinetic parameters of copper complexation with the three fractions of fulvic acids. Experimental conditions were pH 6, 5 x 10(-5)m total copper and 5 mg C litre(-1) of fulvic acids. The conditional stability coefficients of the fulvic acid fractions were in the order of 0.9-3.3 x 10(5)m(-1), and the forward and reverse rate constants were in the order of 6.9-12.4 x 10(3)m(-1) s(-1) and 3.5-8.0 x 10(-2) s(-1). Information could be useful in modelling copper transport in the hydrosphere.     

Nitrate reduction by fluoride green rust modified with copper

Nitrate reduction by the fluoride form of green rust modified with copper (GR-F(Cu)) was investigated using a batch reactor system. The extent of nitrate reduction was measured by measuring the increase in concentration of ammonia, which is the final product of nitrate reduction by GR. This approach was required, because nitrate could be removed from solution by ion exchange without reduction. The rate of ammonium production was investigated over the range of pH 7.8-11. The fastest reaction was achieved at pH 9 when GR was present at a concentration of 0.083M as Fe(II) and 1mM of Cu(II) was added. The rate at pH 9 was enhanced by a factor of 2.5 compared to that at pH 7.8 by comparing the time elapsed to transform all nitrate to ammonium. Kinetics of nitrate reduction by GR-F at pH 7.8 were affected by the concentration of Cu(II) added. The rate constants for ammonium production increased from 0.012 to 1.52h(-1) as Cu(II) additions increased from 0 to 2.5mM, but the reaction rate at 5mM was slightly decreased to 1.25h(-1). The mechanism of enhanced rates of nitrate reduction by addition of Cu(II) could not be fully determined in this study. However, XRD results showed that magnetite was produced in the reaction of Cu(II) and GR-F and SEM shows the production of nano-size particles which were not fully identified in this study. In addition, the concentration of Fe(II) in GR was observed to linearly decrease with concentration of Cu(II) added.