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.     

Ambient air monitoring of PCDD/Fs and co-PCBs in Gyeonggi-do, Korea

We started the monitoring for PCDD/Fs in ambient air and soil in August 2001, and co-PCBs in January 2002. Decreasing of PCDD/Fs and co-PCBs levels in ambient air were observed. The higher PCDD/Fs levels were found in winter and lower in autumn. We found that the industrial incinerators influenced the PCDD/Fs levels in ambient air. In the 2,3,7,8-substituted PCDD/Fs concentration profiles, the three major congeners occupied 67% of the total mass. In case of co-PCBs, PCB#118, #105 and #77 were observed as the main congeners. Five cluster groups discriminated by ratio of four components, O(8)CDD, 1,2,3,4,6,7,8-H(7)CDD, 1,2,3,4,6,7,8-H(7)CDF and O(8)CDF, were obtained from HCA (hierarchical cluster analysis).     

Influence of start-up on PCDD/F emission of incinerators

This study aims to evaluate the influence of start-up on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) concentration in the stack flue gas of incinerators and its contributing PCDD/F emission. The PCDD/F emission of the first sample among three consecutive stack flue gas samples of five intermittent incinerators, which sampled at a stable combustion condition after start-up, is 2-3 times higher than the mean of the others. For verifying the PCDD/F characteristics of incinerators during start-up, one continuous MSWI was investigated for two years. The elevated PCDD/F emissions of the MSWI during start-up could reach 96.9 ng I-TEQN m(-3) and still maintained a high PCDD/F emission (40 times higher than the Taiwan emission limit) even 18 h after the injection of activated carbon, indicating the memory effect. Taking the MSWI for example, which consists of four incinerators, the estimated annual PCDD/F emission from normal operational conditions was 0.112 g I-TEQ. However, one start-up procedure can generate approximately 60% of the PCDD/F emissions for one whole year of normal operations. And the PCDD/F emission, which is the result of the start-ups of four incinerators, was at least two times larger than that of a whole year's normal operations, without consideration for the PCDD/F emission contributed by the long lasting memory effect.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

Source apportionment of fine particulate matter in the southeastern United States

Particulate matter (PM) less than 2.5 microm in size (PM2.5) source apportionment by chemical mass balance receptor modeling was performed to enhance regional characterization of source impacts in the southeastern United States. Secondary particles, such as NH4HSO4, (NH4)2SO4, NH4NO3, and secondary organic carbon (OC) (SOC), formed by atmospheric photochemical reactions, contribute the majority (>50%) of ambient PM2.5 with strong seasonality. Source apportionment results indicate that motor vehicle and biomass burning are the two main primary sources in the southeast, showing relatively more motor vehicle source impacts rather than biomass burning source impacts in populated urban areas and vice versa in less urbanized areas. Spatial distributions of primary source impacts show that each primary source has distinctively different spatial source impacts. Results also find impacts from shipping activities along the coast. Spatiotemporal correlations indicate that secondary particles are more regionally distributed, as are biomass burning and dust, whereas impacts of other primary sources are more local.     

Identification and interpretation of representative ozone distributions in association with the sea breeze from different synoptic winds over the coastal urban area in Korea

To aid the studies of long-term impact assessment of cumulative ozone (O3) exposures, the representative 8-hr O3 pollution patterns have been identified over the Greater Seoul Area (GSA) in Korea. Principal component analysis and two-stage clustering techniques were used to identify the representative O3 patterns, and numerical and observational analyses were also used to interpret the identified horizontal distribution patterns. The results yielded three major O3 distribution patterns, and each of the three patterns was found to have strong correlations with local and synoptic meteorological conditions over the GSA. For example, pattern 1, accounting for 46% of O3 concentration distributions, mostly occurred under relatively weak westerly synoptic winds. The predominant features of this pattern were infrequent high O3 levels but a distinct gradient of O3 concentration from the western coastal area to the eastern inland area that was mainly induced by the local sea breeze. Pattern 2, accounting for 31% of O3 concentration distributions, was found with higher O3 levels in the western coastal area but lower in the eastern inland area. This is due to the modified sea breeze under the relatively stronger easterly opposing synoptic wind, affecting the high O3 occurrence in the western coastal area only. However, pattern 3, accounting for 21% of O3 concentration distributions, showed significantly higher O3 concentrations over the whole GSA mainly due to the retarded and slow-moving sea-breeze front under the weak opposing synoptic flow. Modeling study also indicated that local and synoptic meteorological processes play a major role in determining the high O3 concentration distribution patterns over the GSA.     

Background levels and dietary intake of PCDD/Fs in domestic and imported meat in South Korea

A survey was conducted in South Korea to determine residual levels and dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from meat. Altogether 119 domestic and 164 imported samples of beef, pork, and chicken were examined. The mean levels of PCDD/Fs in upper bound were 0.21, 0.22, and 0.04pg WHO-TEQ/g fat for beef, pork, and chicken, respectively. The low level of PCDD/Fs in chicken probably resulted from the low fat content in the samples used. The samples were separated into domestic and imported products in order to investigate the sources of contamination. PCDFs were the more dominant congeners in domestic beef and were similar to those found from emission of incineration. However, the congener profiles of domestic beef and incineration were difficult to compare because the environmental fate and animal metabolism were involved. The upper bound dietary intake of PCDD/Fs from beef, pork and chicken was calculated to be 0.04pg/WHO-TEQ/kgbw/day. The combined consumption of beef, pork, and chicken was found to be 84.8g per day for a person weighing 60kg and represented 5.7% of their total daily food intake.     

Characterization and optimization of long-term controlled release system for groundwater remediation: a generalized modeling approach

A well-based reactive barrier system using controlled-release KMnO4 has been recently developed as a long-term in situ treatment option for plumes of dense and non-aqueous phase liquids in groundwater. In order to take advantage of the merits of controlled release systems (CRS) in environmental remediation, the release behavior needs to be optimized for the hydrologic and environmental conditions of target treatment zone. Where release systems are expected to be operated over long times, like for the reactive barriers, it may only be practical to describe the long-term behavior numerically. We developed a numerical model capable of describing release characteristics associated with variable forms and structures of long-term CRS. Sensitivity analyses and illustrative simulations showed that the release kinetics and durations would be constrained by changes in agent solubility, bulk diffusion coefficients, or structures of the release devices. The generality of the numerical model was demonstrated through simulations for CRS with monolithic and double-layered matrices. The generalized model was then used for actual design and analyses of an encapsulated-matrix CRS, which can yield constant release kinetics for several years. A well-based reactive barrier system (4.05 x 10(3)m3) using the encapsulated-matrix CRS can release approximately 1.65 kg of active agent (here MnO4(-)) daily over the next 6.6 yr, creating prolonged reaction zone in the subsurface. The generalized model-based, target-specific approach using the long-term CRS could provide practical tool for improving the efficacy of advanced in situ remediation schemes such as in situ chemical oxidation, bioremediation, or in situ redox manipulation. Development of techniques for adjusting the bulk diffusion coefficients of the release matrices and facilitating the lateral spreading of the released agent is warranted.     

Phosphorus Load Reduction Goals for Feitsui Reservoir Watershed, Taiwan

The present paper describes an effort for developing the total maximum daily load (TMDL) for phosphorus and a load reduction strategy for the Feitsui Reservoir in Northern Taiwan. BASINS model was employed to estimate watershed pollutant loads from nonpoint sources (NPS) in the Feitsui Reservoir watershed. The BASINS model was calibrated using field data collected during a 2-year sampling period and then used to compute watershed pollutant loadings into the Feitsui Reservoir. The simulated results indicate that the average annual total phosphorus (TP) loading into the reservoir is 18,910 kg/year, which consists of non-point source loading of 16,003 kg/year, and point source loading of 2,907 kg/year. The Vollenweider mass balance model was used next to determine the degree of eutrophication under current pollutant loading and the load reduction needed to keep the reservoir from being eutrophic. It was estimated that Feitsui Reservoir can becoming of the oligotrophic state if the average annual TP loading is reduced by 37% or more. The results provide the basis on which an integrated control action plan for both point and nonpoint sources of pollution in the watershed can be developed.