Modeling remediation time using natural attenuation at a dry‐cleaner site

Contaminants from dry‐cleaning sites, primarily tetrachloroethene (PCE), trichloroethene (TCE), cis‐dichloroethene (cis‐DCE), and vinyl chloride (VC), have become a major concern because of the limited funds and regulatory programs to address them. Thus, natural attenuation and its effectiveness for these sites needs to be evaluated as it might provide a less costly alternative to other remediation methods. In this research, data from a site in Texas were analyzed and modeled using the Biochlor analytical model to evaluate remediation times using natural attenuation. It was determined that while biodegradation and source decay were occurring at the site, the resulting attenuation rates were not adequate to achieve cleanup in a reasonable time frame without additional source remediation or control strategies. Cleanup times exceeded 100 years for all constituents at the site boundary and 800 years at the source for PCE, assuming cleanup levels of 0.005 mg/L for PCE and TCE and 0.07 mg/L and 0.002 mg/L for cis‐DCE and VC, respectively. © 2005 Wiley Periodicals, Inc.     

MODELING FECAL COLIFORM CONTAMINATION IN THE RIO GRANDE1

This study examines sources of fecal coliform in Segment 2302 of the Rio Grande, located south of the International Falcon Reservoir in southern Texas. The watershed is unique because the contributing drainage areas lie in Texas and Mexico. Additionally, the watershed is mostly rural, with populated communities known as “colonias.” The colonias lack sewered systems and discharge sanitary water directly to the ground surface, thus posing an increased health hazard from coliform bacteria. Monitoring data confirm that Segment 2302 is not safe for contact recreation due to elevated fecal coliform levels. The goal of the study was to simulate the observed exceedences in Segment 2302 and evaluate potential strategies for their elimination. Fecal coliform contributions from ranching and colonia discharges were modeled using the Hydrologic Simulation Program‐Fortran (HSPF). Model results indicated that the regulatory 30‐day geometric mean fecal coliform concentration of 200 colony forming units (cfu) per 100 milliliters is exceeded approximately three times per year for a total of 30 days. Ongoing initiatives to improve wastewater facilities will reduce this to approximately once per year for 14 days. Best management practices will be necessary to reduce cattle access to streams and eliminate all exceedences. The developed model was limited by the relatively sparse flow and fecal coliform data.     

Escherichia coli Concentrations in Urban Watersheds Exhibit Diurnal Sag: Implications for Water‐Quality Monitoring and Assessment

The variability of indicator bacteria over a fine resolution time scale on the order of minutes has yet to be fully understood. In this study, we collected more than 700 Escherichia coli samples at a 10‐ and 30‐min resolution in an urban watershed in Houston. A Bacteria Diurnal Sag (BDS) marked with daytime exponential decay followed by an exponential nighttime regeneration was observed. This pattern was observed during all sampled events but varied depending on other variables. The concentrations during a 24‐h period varied 1 to 5 orders of magnitude and the fecal load was at least 10 times lower than what would be obtained using a single morning E. coli measurement, the typical sampling scheme in most monitoring programs. Decay rates, ranging from 3.67 to 24.7/day, decreased E. coli concentrations to below the water‐quality standards from 14:00 to 18:00 h and were strongly influenced by water temperatures and solar radiation intensities. Rapid regeneration occurred on the order of 9.41 to 64.1/day allowing E. coli concentrations to return to their pre‐decay levels. The data indicated that four to six samples taken between 06:00 and 18:00 h may be sufficient to define the BDS depending on stream conditions, and that a threshold concentration of approximately 100 MPN/dl (most probable number in a deciliter) existed for the studied urban watershed. These findings have significant implications for water‐quality monitoring, regulation, and compliance.     

Statistical investigation of polychlorinated dibenzo-p-dioxins and dibenzofurans in the ambient air of Houston, Texas

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (dioxins and furans) are persistent, bioaccumulative and highly toxic chemical constituents that appear in the environment at very low and difficult to measure levels. Although dioxins and furans are widely recognized as toxic contaminants needing regulation, their temporal and spatial concentration profiles and the factors impacting their partitioning and congener distribution are only moderately understood. This paper presents the results from one of the most extensive ambient air dioxin and furan sampling efforts conducted in a geographic area to date. The data consist of monthly ambient concentrations of 17 of the most toxic congeners of dioxins and furans collected at five locations in Houston, Texas over a calendar year. The results showed a total annual mean dioxin and furan congener concentration of 1047 fg/m3 and an annual mean summation operatorI-TEQ concentration of 15 fg I-TEQ/m3 (16 fg WHO-TEQ/m3). These results, when compared with proximate data from the USEPA National Dioxin Ambient Monitoring Network (NDAMN), revealed significant (at the P0.05 level) differences between Houston and the NDAMN sites, suggesting the existence of local dioxin sources. A temporal analysis of the data showed that the congener concentration distribution varies over time, depending on the level of chlorination, type of congener, and temperature. The results also suggested that the fluctuations of congener concentrations and I-TEQ concentrations are closely correlated with minimum relative humidity, mean temperature, and mean NOx concentration.     

Comparative distribution, sourcing, and chemical behavior of PCDD/Fs and PCBs in an estuary environment

PCDD/F and PCB field data (1041 samples) in five media (dissolved, suspended sediment, bed sediment, catfish, and blue crab) were studied to explore dual contaminant patterns in the Houston Ship Channel, Texas, USA. PCDD/Fs showed greater concentration than PCBs in suspended sediments while PCBs were higher in apparent dissolved (truly dissolved + DOC-associated), fish, and crab. PCDD/Fs at nearly all locations contributed more strongly to dioxin-like toxicity. The fraction of PCB TEQ was, however, enriched in biotic over abiotic media due in large part to the presence of PCB 126, which was mostly undetected in water and sediment and yet exhibited a BAF three times greater than 2,3,7,8-TCDD. Dissolved-suspended sediment and suspended-bed sediment relationships showed that (1) observed apparent dissolved concentration differences (as fraction of total water were mean 10% PCDD/Fs and 63% PCBs) can reasonably be explained by a four-phase partition model (truly dissolved, DOC-associated, suspended OC, and suspended BC) for PCBs but not for PCDD/Fs and (2) the contaminants behaved similarly in bed to suspended sediment concentration ratios (C_bed/C_susp) upstream of a major confluence but not downstream. PCA-cluster analysis pointed to the possibility that suspended sediment PCB contamination originates from resuspended bed sediment while PCDD/Fs in suspended sediment originates more probably from other sediment sources such as upstream wash load or air deposition. Finally, examinations of a congener marker ratio (PCB 209/206) seemed to indicate that a source of pure PCB 209 may exist in bed sediment near Patrick Bayou though the source was not completely localized.     

Mass balance modeling to elucidate historical and continuing sources of dioxin into an urban estuary

Polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) are typically found in sediment, water and tissue as in the case of the Houston Ship Channel and Upper Galveston Bay (HSC–UGB) in Texas studied in this research. While hydrodynamic and fate and transport models are important to understand dioxin distribution in the various media, it is difficult to assimilate modeling results into a decision framework without appropriate tools that can aid in the interpretation of the simulated data. This paper presents the development of a mass-balance modeling tool linked to RMA2 and WASP models of the HSC–UGB system for 2002–2005. The mass-balance tool was used to aggregate modeling results spatially and temporally and estimate the relative contribution of sediments to dioxin loading into the Channel in comparison to runoff, deposition, and permitted effluent discharges. The total sediment associated-dioxin load into the system calculated using the mass balance model was 2.34 × 10⁷ ng d⁻¹ (almost 86% of the toxic equivalent load), and the re-deposited load to the sediment from the water column was 1.48 × 10⁷ ng-TEQ d⁻¹, such that 8.6 × 10⁶ ng-TEQ d⁻¹ or approximately 69% of the average daily dioxin flux is transported between model segments as sediment. The external loads to the system contribute approximately 3.83 × 10⁶ ng-TEQ d⁻¹, a value that is an order of magnitude smaller when compared to the contribution from sediment. These findings point to the need for sediment remediation strategies that take into account the spatial locations within the system that serve as sediment sources to dioxin in the water column.     

Empirical Evaluation of Ambient Ozone Interpolation Procedures to Support Exposure Models

ABSTRACT

An intercomparison study has been performed with six empirical ozone interpolation procedures to predict hourly concentrations in ambient air between monitoring stations. The objective of the study is to use monitoring network data to empirically identify an improved procedure to estimate ozone concentrations at subject exposure points. Four of the procedures in the study are currently used in human exposure models (nearest monitors daily mean and maximum, regression estimate used in the U.S. Environmental Protection Agency's (EPA) pNEM, and inverse distance weighting), and two are being evaluated for this purpose (kriging in space and kriging in space and time). The study focused on spatial estimation during June 1-June 5, 1996, with relatively high observed ozone levels over Houston, Texas. The study evaluated these procedures at three types of locations with monitors of varying proximity. Results from the empirical evaluation indicate that kriging in space and time provides excellent estimates of ozone concentrations within a monitoring network, while the more often used techniques failed to capture observed pollutant concentrations. Improved estimation of pollutant concentrations within the region, and thus at subject locations, should result in improved exposure modeling.     

Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in suspended sediments, dissolved phase and bottom sediment in the Houston Ship Channel

Spatial distributions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the water column and bottom sediments of the Houston Ship Channel in Texas were measured three times over a 1-year period. Total TEQ concentrations in water ranged from 0.01 to 0.25 pg/l for the dissolved phase and from 0.09 to 2.91 pg/l for the suspended phase, while TEQ concentrations in bottom sediments varied from 0.9 to 139.8 ng/kg dry wt. The dissolved concentrations were lower than their respective suspended concentrations, with average dissolved/suspended ratios between 0.11 and 0.59 for individual congeners. More than 89% of the total concentration of 2378-substituted PCDD/PCDFs was attributable to OCDD but 2378-TCDD was the major contributor to total TEQ for the three sampled media. Average logs of organic carbon-normalized suspended sediment-dissolved partitioning coefficients (logK(oc)(obs)) varied between 4.92 and 8.59 l/kg-oc; while in the bottom sediment-dissolved interface, logK(oc)(obs) values ranged from 5.48 to 8.48 l/kg-oc. Observed logK(oc)values varied within a factor of 0.64-1.26 from equilibrium logK(oc) values, suggesting fluxes of PCDD/PCDFs across the interfaces. It was found that in the HSC, on average, the tendency of a compound to move from the particulate phase to the dissolved phase decreases with increasing K(ow).     

Groundwater monitoring plans at small-scale sites--an innovative spatial and temporal methodology

An innovative methodology for improving existing groundwater monitoring plans at small-scale sites is presented. The methodology consists of three stand-alone methods: a spatial redundancy reduction method, a well-siting method for adding new sampling locations, and a sampling frequency determination method. The spatial redundancy reduction method eliminates redundant wells through an optimization process that minimizes the errors in plume delineation and the average plume concentration estimation. The well-siting method locates possible new sampling points for an inadequately delineated plume via regression analysis of plume centerline concentrations and estimation of plume dispersivity values. The sampling frequency determination method recommends the future frequency of sampling for each sampling location based on the direction, magnitude, and uncertainty of the concentration trend derived from representative historical concentration data. Although the methodology is designed for small-scale sites, it can be easily adopted for large-scale site applications. The proposed methodology is applied to a small petroleum hydrocarbon-contaminated site with a network of 12 monitoring wells to demonstrate its effectiveness and validity.     

Transformation of sulfaquinoxaline by chlorine and UV light in water: kinetics and by-product identification

Sulfaquinoxaline (SQX) is an antimicrobial of the sulfonamide class, frequently detected at low levels in drinking and surface water as organic micropollutant. The main goal of the present study is the evaluation of SQX reactivity during chlorination and UV irradiations which are two processes mainly used in water treatment plants. The SQX transformation by chlorination and UV lights (254 nm) was investigated in purified water at common conditions used for water disinfection (pH =?7.2, temperature =?25 °C, [chlorine] =?3 mg L^?1). The result shows a slow degradation of SQX during photolysis compared with chlorination process. Kinetic studies that fitted a fluence-based first-order kinetic model were used to determine the kinetic constants of SQX degradation; they were equal to 0.7?×?10^?4 and 0.7?×?10^?2 s^?1corresponding to the half time lives of 162 and 1.64 min during photolysis and chlorination, respectively. In the second step, seven by-products were generated during a chlorination and photo-transformation of SQX and identified using liquid chromatography with electrospray ionization and tandem mass spectrometry (MS-MS). SO₂ extrusion and direct decomposition were the common degradation pathway during photolysis and chlorination. Hydroxylation and isomerization were observed during photodegradation only while electrophilic substitution was observed during chlorination process.