Methods for the analysis of PCBs in human food, faeces and serum.

A method was developed to determine trace concentrations of a range of individual PCB congeners in biological samples (serum, food and faeces) using GC-MS, to prepare a mass balance of PCBs in humans. A simple method for the analysis of PCBs in human serum, which excluded an extraction step, was first employed. Results indicated that the recoveries of 13C12 PCB spikes were variable. A soxhlet extraction step was added and was found to be efficient and reproducible. A quality control routine and method validation results are presented. In batch tests of the methods presented it was found that the serum analysis method gave within batch mean 13C12 spike recoveries of 98-120% and standard deviations between 6 and 20%. The food/faeces analysis method gave within-batch mean 13C12 spike recoveries of 88-100%, and within batch standard deviations between 4 and 12%. The batch to batch mean recovery for serum analysis was 100%, with an RSD of 9% for high spikes and 10% for low spikes. For food/faeces analysis the batch to batch average recovery was 110%, with an RSD of 5% for high spikes and 9% for low spikes.     

Evaluation of laboratory-made sludge for an anaerobic biodegradability test and its use for assessment of 13 chemicals

Laboratory-made sludge for a biogas based anaerobic biodegradability test was prepared as an alternative for digested sludge from wastewater treatment plants (WWTPs). Biodegradation activities and background gas productions of digested sludge from various WWTPs were found to vary significantly depending on the source, which adversely affected test reliability. Subsequently, test conditions such as sludge concentration and sludge washing were examined with the laboratory-made sludge and a sludge concentration of 1.0 g-SS/L without washing was determined to be most suitable. Under these conditions, biodegradability tests were conducted for 13 select chemicals and their relative toxicities to methanogenic bacteria were evaluated. The results of biodegradability tests showed that chemicals with -OH and -CH2OH radicals were readily biodegraded and those with -Cl, -NO2, -NH2, -SO3H and -CH3 had inhibited degradation responses m-nitriphenol and 2,4,6-trichlorophenol were highly toxic to methanogenic bacteria, with m-nitrophenol completely inhibiting methane fermentation as low as 20 mg/L.     

National estimates of outdoor air toxics concentrations

The Clean Air Act identifies 189 hazardous air pollutants (HAPs), or "air toxics," associated with a wide range of adverse human health effects. The U.S. Environmental Protection Agency has conducted a modeling study with the Assessment System for Population Exposure Nationwide (ASPEN) to gain a greater understanding of the spatial distribution of concentrations of these HAPs resulting from contributions of multiple emission sources. The study estimates year 1990 long-term outdoor concentrations of 148 air toxics for each census tract in the continental United States, utilizing a Gaussian air dispersion modeling approach. Ratios of median national modeled concentrations to estimated emissions indicate that emission totals without consideration of emission source type can be a misleading indicator of air quality. The results also indicate priorities for improvements in modeling methodology and emissions identification. Model performance evaluation suggests a tendency for underprediction of observed concentrations, which is likely due, at least in part, to a number of limitations of the Gaussian modeling formulation. Emissions estimates for HAPs have a high degree of uncertainty and contribute to discrepancies between modeled and monitored concentration estimates. The model's ranking of concentrations among monitoring sites is reasonably good for most of the gaseous HAPs evaluated, with ranking accuracy ranging from 66 to 100%.     

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.     

Effects of ozone and soil water deficit on roots and shoots of field-grown soybeans

Water-stressed and well-watered soybean (Glycine max cvs. Williams and Corsoy) plants were exposed to increasing seasonal doses of ozone (O(3)) using open-top field chambers and ambient air plots. Chamber O(3) treatments included charcoal filtered (CF) air, non-filtered (NF) air, NF + 0.03, NF + 0.06 and NF + 0.09 microl litre(-1) O(3). Soil water potentials measured at 25 and 45 cm averaged -0.40 MPa and -0.05 MPa, respectively, for the plots in the water-stressed and well-watered series. Total root length/core, root length densities, and biomasses (dry weights) were determined. With Williams, a very popular cultivar in recent years, total root length for all O(3) treatments averaged 58% more under water-stress conditions than in well-watered plots, but the range was from 136% to 11% more for NF air and NF + 0.09 microl litre(-1) O(3), respectively. Increasing the O(3) exposure dose did not affect root lengths or weights in the well-watered series. With Corsoy, water stress did not significantly increase root development. In both soil moisture regimes, with both cultivars, there was a linear decrease in seed yield and top dry weight as the O(3) exposure dose increased.     

Studies on transitory laxative effects of sorbitol and maltitol I: Estimation of 50% effective dose and maximum non-effective dose

The dose-response relationship between low-caloric sweetening agents, sorbitol and maltitol, administered orally in single doses, and the induction of diarrheal symptoms was investigated. Seven healthy male and 7 healthy female Japanese each in their twenties, thirties, and forties, respectively, or a total of 42 subjects were admitted to the study. The 50% laxative effective dose of sorbitol was estimated to be 0.4 g/kg for males and 1.0 g/kg for females and that of maltitol was estimated to be 0.8 g/kg for both males and females. The maximum non-effective dose of sorbitol was estimated to be 0.15 g/kg for males and 0.3 g/kg for females and that of maltitol was estimated to be 0.3 g/kg for both males and females.     

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.     

Outdoor/Indoor/Personal ozone exposures of children in Nashville, Tennessee

An ozone (O3) exposure study was conducted in Nashville, TN, using passive O3 samplers to measure six weekly outdoor, indoor, and personal O3 exposure estimates for a group of 10- to 12-yr-old elementary school children. Thirty-six children from two Nashville area communities (Inglewood and Hendersonville) participated in the O3 sampling program, and 99 children provided additional time-activity information by telephone interview. By design, this study coincided with the 1994 Nashville/Middle Tennessee Ozone Study conducted by the Southern Oxidants Study, which provided enhanced continuous ambient O3 monitoring across the Nashville area. Passive sampling estimated weekly average outdoor O3 concentrations from 0.011 to 0.O30 ppm in the urban Inglewood community and from 0.015 to 0.042 ppm in suburban Hendersonville. The maximum 1- and 8-hr ambient concentrations encountered at the Hendersonville continuous monitor exceeded the levels of the 1- and 8-hr metrics for the O3 National Ambient Air Quality Standard. Weekly average personal O3 exposures ranged from 0.0013 to 0.0064 ppm (7-31% of outdoor levels). Personal O3 exposures reflected the proportional amount of time spent in indoor and outdoor environments. Air-conditioned homes displayed very low indoor O3 concentrations, and homes using open windows and fans for ventilation displayed much higher concentrations.     

Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons

The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.     

Negative effects of humic acid addition on phytoremediation of pyrene-contaminated sediments by mangrove seedlings

Vegetated (with Kandelia candel seedlings) and non-vegetated mangrove microcosms were employed to remove pyrene from contaminated sediments, and the effects of adding 6.7% humic acid (HA) on such removal were investigated. At the end of 6-month treatment, residual pyrene concentrations in surface sediments (0-2 cm) of the contaminated microcosms reduced from an initial 5.82 to 0.63 microg g(-1) dw, and the reduction was less in HA amended microcosms with the residual pyrene concentration remained at 3.12 microg g(-1) dw. The pyrene removal percentages in microcosms with HA amendment were 29% for surface aerobic sediments and 41% for bottom (anaerobic) sediments, while the respective removal percentages in microcosms without HA amendment were 89% (surface sediments) and 53% (bottom sediments). Microcosms planted with K. candel seedlings had a significantly higher pyrene removal when compared to the non-vegetated ones, and the average removal percentages were 70.9% and 61.4%, respectively. However, when humic acid was added, no significant difference was found between vegetated and non-vegetated microcosms in pyrene removal, both had less than 40% removal, probably because plant growth in humic acid amended contaminated microcosms, in terms of total biomass, was reduced by 50%. Roots of K. candel could accumulate pyrene from contaminated microcosms, and pyrene concentrations in roots harvested from microcosms with and without humic acid addition were 6.01 and 3.46 microg g(-1) dw, respectively. These results suggest that the addition of HA to contaminated sediments decreased the mangrove microcosm's ability to remove pyrene as pyrene was more tightly bound to the organic matter and plant growth was reduced.