Design and startup of a membrane-biological-reactor system at a Ford-engine plant for treating oily wastewater.

A wastewater-treatment facility at Ford (Dearborn, Michigan) was recently upgraded from chemical de-emulsification to ultrafiltration (UF) followed by a membrane-biological reactor (MBR). This paper describes the design, startup, and initial operational performance of the facility. Primary findings are as follows: (1) the MBR proved resilient; (2) the MBR removed approximately 90% of chemical-oxygen demand (COD) after primary UF; (3) the removal of total Kjeldahl nitrogen by MBR appeared to be more sensitive to operating conditions than COD removal; (4) nitrification and denitrification were established in one month; (5) the MBR removed oil and grease and phenolics to below detection levels consistently, in contrast to widely fluctuating concentrations in the past; (6) permeate fluxes of the primary and MBR UF were adversely affected by inadvertent use of a silicone-based defoamer; and (7) zinc concentrations in the effluent increased, which might have been a result of ethylenediaminetetraacetic acid used in membrane washing solutions and/or might have been within typical concentration ranges.     

Kinetics of phenol and chlorophenol utilization by Acinetobacter species

Although microbial transformations via cometabolism have been widely observed, the few available kinetic models of cometabolism have not adequately addressed the case of inhibition from both the growth and nongrowth substrates. The present study investigated the degradation kinetics of self-inhibitory growth (phenol) and nongrowth (4-chlorophenol, 4-CP) substrates, present individually and in combination. Specifically, batch experiments were performed using an Acinetobacter isolate growing on phenol alone and with 4-CP present. In addition, batch experiments were also performed to evaluate the transformation of 4-CP by resting, phenol-induced Acinetobacter cultures. The Haldane kinetic model adequately predicted the biodegradation of phenol alone, although a slight discrepancy was noted in cases of higher initial phenol concentrations. Similarly, a Haldane model for substrate utilization was also able to describe the trends in 4-CP transformation by the resting cell cultures. The 4-CP transformation by the Acinetobacter species growing on phenol was modeled using a competitive kinetic model of cometabolism, which included growth and nongrowth substrate inhibition and cross-inhibition terms. Excellent agreement was obtained between the model predictions using experimentally estimated parameter values and the experimental data for the synchronous disappearance of phenol and 4-CP.     

Modeling in situ ozonation for the remediation of nonvolatile PAH-contaminated unsaturated soils

Mathematical models were developed to investigate the characteristics of gaseous ozone transport under various soil conditions and the feasibility of in situ ozone venting for the remediation of unsaturated soils contaminated with phenanthrene. On the basis of assumptions for the mass transfer and reactions of ozone, three approaches were considered: equilibrium, kinetic, and lump models. Water-saturation-dependent reactions of gaseous ozone with soil organic matter (SOM) and phenanthrene were employed. The models were solved numerically by using the finite-difference method, and the model parameters were determined by using the experimental data of Hsu [The use of gaseous ozone to remediate the organic contaminants in the unsaturated soils, PhD Thesis, Michigan State Univ., East Lansing, MI, 1995]. The transport of gas-phase ozone is significantly retarded by ozone consumption due to reactions with SOM and phenanthrene, in addition to dissolution. An operation time of 156 h was required to completely remove phenanthrene in a 5-m natural soil column. In actual situations, however, the operation time is likely to be longer than the ideal time because of unknown factors including heterogeneity of the porous medium and the distribution of SOM and contaminant. The ozone transport front length was found to be very limited (< 1 m). The sensitivity analysis indicated that SOM is the single most important factor affecting in situ ozonation for the remediation of unsaturated soil contaminated with phenanthrene. Models were found to be insensitive to the reaction mechanisms of phenathrene with either gas-phase ozone or dissolved ozone. More study is required to quantify the effect of OH* formation on the removal of contaminant and on ozone transport in the subsurface.     

In vitro inhibition of hepatic cytochrome P450 and enzyme activity by butyltin compounds in marine mammals

The present study attempted to examine the in-vitro inhibition of hepatic microsomal P450 content and activity by butyltins in marine mammals and discussed on their possible effects in animals in the wild. Decreases in P450 content and the activities of ethoxyresorufin O-deethylase (EROD, catalyzed by CYPIA subfamily) and penthoxyresorufin O-depentylase (PROD, catalyzed by CYP2B subfamily) by tributyltin (TBT) were observed in in-vitro experiments using hepatic microsomes of a pinniped and a cetacean. Among P450 family, EROD activity is more sensitive to TBT than P450 content and PROD activity, indicating a specific mode of action of TBT on different P450 forms. On the other hand, dibutyltin and monobutyltin have no inhibitory effect on EROD activity at concentrations less than 0.5 mM, indicating that the inhibition of enzyme activity in hepatic microsome of marine mammal is mainly by TBT. TBT concentrations that affect P450 contents and activities are above 10 times higher than the values found in the liver of various marine mammals.     

Accumulation of butyl- and phenyltin compounds in starfish and bivalves from the coastal environment of Korea

Triphenyltin (TPT) and tributyltin (TBT) concentrations were determined in two starfish species (Asteria pectinifera and Asterias amurensis), bivalves (Crassostrea gigas or Mytilus edulis), and seawater samples from sites around the coasts of Korea. Both TPT and TBT concentrations in starfish ranged from 8 to 1560 ng/g and from <2 to 797 ng/g as Sn on a dry weight basis, respectively. TPT concentration accounted for 75.4% and 86.4% of total phenyltin concentration in A. pectinifera and A. amurensis, respectively, while monobutyltin, a degradation product of TBT, accounted for 86.3% and 57.2% of total butyltin, respectively. Triphenyltin concentrations in A. pectinifera were significantly correlated to water and bivalve TPT concentrations, which implies that dietary uptake of TPT from contaminated prey as well as direct uptake from surrounding water contribute to TPT body residues in the starfish. Starfish could be target organisms for monitoring TPT compound in the marine environment, due to their high accumulation and low degradation capacity towards TPT.     

DMS photochemistry during the Asian dust-storm period in the Spring of 2001: model simulations vs. field observations

This study examines the local/regional DMS oxidation chemistry on Jeju Island (33.17 degrees N, 126.10 degrees E) during the Asian dust-storm (ADS) period of April 2001. Three ADS events were observed during the periods of April 10-12, 13-14, and 25-26, respectively. For comparative purposes, a non-Asian-dust-storm (NADS) period was also considered in this study, which represents the entire measurement periods in April except the ADS events. The atmospheric concentrations of DMS and SO2 were measured at a ground station on Jeju Island, Korea, as part of the ACE-Asia intensive operation. DMS (means of 34-52 pptv) and SO2 (means of 0.96-1.14 ppbv) levels measured during the ADS period were higher than those (mean of 0.45 ppbv) during the NADS period. The enhanced DMS levels during the ADS period were likely due to the increase in DMS flux under reduced oxidant levels (OH and NO3). SO2 levels between the two contrasting periods were affected sensitively by some factors such as air mass origins. The diurnal variation patterns of DMS observed during the two periods were largely different from those seen in the background environment (e.g., the marine boundary layer (MBL)). In contrast to the MBL, the maximum DMS value during the ADS period was seen in the late afternoon at about sunset; this reversed pattern appears to be regulated by certain factors (e.g., enhanced NO3 oxidation). The sea-to-air fluxes of DMS between the ADS and NADS periods were calculated based on the mass-balance photochemical-modeling approach; their results were clearly distinguished with the values of 4.4 and 2.4 micromole m(-2) day(-1), respectively. This study confirmed that the contribution of DMS oxidation to observed SO2 levels on Jeju Island was not significant during our study period regardless of ADS or NADS periods.     

Specific accumulation of 20 trace elements in great cormorants (Phalacrocorax carbo) from Japan

This study is to elucidate the specific accumulation of 20 trace elements in tissues/organs of great cormorants from two different colonies (Lake Biwa and Mie) in Japan. In the body distribution of trace elements, some elements revealed tissue-specific accumulation such as most of the burden of Mo, Ag and Cd in liver, Tl and Cd in kidney, Cu, Rb and Cs in muscle, and V, Sr and Ba in bone. Gender-related variation was not observed in both populations for most of the trace elements, except for higher hepatic Sr in males from Lake Biwa. Hepatic V, muscular Hg and Tl, and Cd in liver, kidney and muscle increased with growth. Comparison of trace element levels in tissues between the two colonies showed that Cr, Rb, Sr, Cd, Cs, Ba and Tl levels were higher in Lake Biwa than in Mie, whereas Zn, Co and Hg in Mie samples were greater than Lake Biwa. Variations of elemental levels in stomach contents also showed similar patterns, thus, showing that dietary sources tended to be the main factor for these regional variations. Toxic Hg and Cd concentrations in the liver of cormorants from the two colonies were lower than those from other areas, implying relatively low exposure to these metals in the present study sites. Concentrations of V, Co, Ag, Cd, Cs, Hg, Tl, Pb and Bi in liver remained more or less at the same level between 1993 and 2003, while hepatic Cr, Mn, Cu, Zn, Se, Rb, Sr and Ba showed apparent decrease, which might be related to the biological factors.     

Combustion characteristics of spent catalyst and paper sludge in an internally circulating fluidized-bed combustor

Combustion of spent vacuum residue hydrodesulfurization catalyst and incineration of paper sludge were carried out in thermo-gravimetric analyzer and an internally circulating fluidized-bed (ICFB) reactor. From the thermo-gravimetric analyzer-differential thermo-gravimetric curves, the pre-exponential factors and activation energies are determined at the divided temperature regions, and the thermo-gravimetric analysis patterns can be predicted by the kinetic equations. The effects of bed temperature, gas velocity in the draft tube and annulus, solid circulation rate, and waste feed rate on combustion efficiency of the wastes have been determined in an ICFB from the experiments and the model studies. The ICFB combustor exhibits uniform temperature distribution along the bed height with high combustion efficiency (>90%). The combustion efficiency increases with increasing reaction temperature, gas velocity in the annulus region, and solid circulation rate and decreases with increasing waste feed rate and gas velocity in the draft tube. The simulated data from the kinetic equation and the hydrodynamic models predict the experimental data reasonably well.     

Leaching characteristics of polycyclic aromatic hydrocarbons (PAHs) from spiked sandy soil

In order to evaluate the factors affecting leachability of hydrophobic organic pollutants (HOPs), we performed leaching tests under a variety of conditions using sandy soil contaminated with phenanthrene and pyrene. The results obtained were: (1) the shaking time, temperature, and dissolved humic matter (DHM, as coexisting matter) increased leachability; (2) ionic strength reduced leachability; and (3) the liquid-to-solid ratio and pH level had no effect on leaching concentration of HOPs. In DHM-added leaching tests assuming equilibrium with HOPs, DHM, and solid matrix, the partitioning (binding) coefficient of HOPs to DHM was accurately calculated with the equations proposed in this study. While we recommend taking into consideration the coexistence of DHM, it is difficult to use universally because its properties differ according to origin and extracting method. It is therefore reasonable to use an alternative reagent having an effect similar to that of DHM.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.