Changes in polycyclic aromatic hydrocarbon availability in River Tyne sediment following bioremediation treatments or activated carbon amendment

Bioremediation and activated carbon (AC) amendment were compared as remediation strategies for sediment from the River Tyne containing 16.4 ± 7.3 μg/g polycyclic aromatic hydrocarbons (PAHs) and approximately 5% coal particles by total dry sediment weight. Unamended, nutrient amended (biostimulated) and nutrient and Pseudomonas putida amended (bioaugmented) sediment microcosms failed to show a significant decrease in total sediment PAH concentrations over a one month period. Polyethylene passive (PE) samplers were embedded for 21 days in these sediment microcosms in order to measure the available portion of PAHs and accumulated 4.70 ± 0.25, 12.43 ± 1.78, and 23.49 ± 2.73 μg PAHs/g PE from the unamended, biostimulated, and bioaugmented microcosms, respectively. Higher PAH uptake by PE samplers in biostimulated and bioaugmented microcosms coincided with slower degradation of spiked phenanthrene in sediment-free filtrate from these microcosms compared to filtrate from the unamended microcosms. Microbial community analysis revealed changes in the bacterial community directly following the addition of nutrients, but the added P. putida community failed to establish itself. Addition of 2% by dry sediment weight activated carbon reduced PAH uptake by PE samplers to 0.28 ± 0.01 μg PAHs/g PE, a greater than 90% reduction compared to the unamended microcosms.     

Sorption of dichlorodiphenyltrichloroethane (DDT) and its metabolites by activated carbon in clean water and sediment slurries

Polyethylene-water partitioning coefficients (K_PE) and mass transfer coefficients (k_PE) for the ortho and para isomers of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT) and its metabolites dichlorodiphenyldichloroethane (DDD), dichlorodiphenyldichloroethylene (DDE) and, dichlorodiphenylmonochloroethylene (DDMU) were measured. These data were used to derive activated carbon (AC) sorption isotherms in clean water in the sub-nanogram per litre free aqueous concentration range for a virgin and a regenerated AC. The sorption strength of AC for DDT and its metabolites was very high and logarithmic values of the AC-water partitioning coefficients, log K_AC, ranged from 8.47 to 9.26. A numerical mass transfer model was calibrated with this data to interpret previously reported reductions in DDT uptake by semipermeable membrane devices after AC amendment of sediment from Lauritzen Channel, California, USA. The activated carbon-water partitioning coefficient values (K_AC) measured in clean water systems appear to overestimate the AC sorption capacity in sediment up to a factor 32 for DDT and its metabolites at long contact time with fine-sized AC. Modelling results show decreased attenuation of the AC sorption capacity with increased sediment-AC contact time. We infer that increased resistance in mass transfer of DDTs to sorption sites in the microporous region likely caused by deposits of dissolved organic matter in the macro- and mesopores of AC appears to be the most relevant fouling mechanism. These results suggest that DDTs may diffuse through possible deposits of dissolved organic matter over time, implying that the effects of sediment on the sorption of DDTs by AC may be more kinetic than competitive.     

Improvement of thermal reactivation of activated carbon for the removal of 2-methylisoborneol

Rapid small-scale column tests (RSSCTs) were employed to evaluate the impact of the dissolved oxygen (DO) concentration in the water used to create steam on the reactivation of spent granular activated carbon (GAC) using three novel thermal reactivation procedures: steam-curing, steam-curing with ramped temperature, and steam pyrolysis reactivation. Evaluation of the physical properties of the reactivated carbon showed a change in mass and volume loss with a change in DO. Performance testing of the carbons for removal of the taste- and odor-causing compound 2-methylisoborneol (MIB) showed that MIB uptake generally increased as the DO concentration decreased. Decrease in MIB removal with an increase in surface acidity, a phenomenon found in the literature, may be responsible for the changes in adsorption performance, as the higher DO concentrations yielded carbons with higher total surface acidity. In addition, the steam-curing process, which was implemented at 375 degrees C (i.e. about 400 degrees C lower than typical reactivation temperatures) with a low DO concentration (i.e. 3-4mg/L) had comparable performance to the virgin carbon counterpart, which could manifest cost-savings due to the low temperature associated with this protocol compared to conventional reactivation. Furthermore, since the mass loss associated with this steam-curing protocol was low, less virgin carbon make-up would be required also improving the economic viability of this reactivation protocol.     

Using silicone passive samplers to detect polycyclic aromatic hydrocarbons from wildfires in streams and potential acute effects for invertebrate communities

Silicone rubber passive samplers spiked with 4 deuterated performance reference compounds were deployed for 29-33 days to estimate the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in 9 streams in Victoria, Australia, following a wildfire. Silicone rubber strips of 2 thicknesses were used to obtain information on the status of uptake of the chemicals of interest at retrieval. In addition, we monitored the stream macroinvertebrate community for potential effects of PAHs or other fire organics. All selected PAHs were detected in the passive samplers and the sampling rates ranged from 0.5 to 50 L/day significantly varying between sites but not compounds, presumably due to differences in current velocity. The estimated water concentrations were 0.1-10 ng/L for total PAHs with phenanthrene, pyrene and fluoranthene accounting for 91% of the total concentration. All PAHs were a factor of 1000 or more below the reported 48-h median lethal concentrations (48-h LC50) for Daphnia magna. Two sites located closest to the fires exhibited elevated concentrations compared to the other sites and the passive samplers in these sites remained in the integrative uptake regime for all compounds, suggesting precipitation-associated PAH input. No acute toxic effects of PAHs or other fire organics on the invertebrate community were detected using a biotic index for organic toxicants (SPEAR), whereas a non-specific biotic index (SIGNAL) decreased in two sites indicating impacts from changes in other environmental parameters. We conclude (1) that silicone-based passive samplers with two different area-to-volume ratios represent a promising tool for determining organic toxicants and (2) that PAHs from wildfires are unlikely to be a common main cause for fire-related ecological effects in streams adjacent to burnt regions.     

The sequestration of PCBs in Lake Hartwell sediment with activated carbon

Recent laboratory studies with a marine sediment from a tidal mudflat in San Francisco Bay demonstrated that a low dose of activated carbon enhances the sequestration of PCBs and PAHs under well-mixed conditions. Here we compare activated carbon treatment for a freshwater sediment from a rural site, using PCB-contaminated sediment from Lake Hartwell, SC. An activated carbon dose of 2% of the dry sediment mass lowered total aqueous PCB concentrations by more than 95% after 1 month of treatment and more than 98% after 6 months. Aqueous PCB concentrations remained below detection limits following 18 months of sediment-carbon contact in slowly mixed systems. Uptake of PCBs into semipermeable membrane devices was reduced by 78%, 91% and 97% over 1, 6 and 18 months, respectively. These tests show that PCB sequestration with activated carbon improves with contact time and is not diminished by prolonged mixing with sediment. Desorption studies confirmed the sequestration, in which 74% of the total PCB mass could be desorbed from untreated Lake Hartwell sediment within 30 days as compared to only 7% after activated carbon treatment for 6 months. We compare these observations with marine sediment from San Francisco Bay and propose a conceptual model to rationalize how sediment properties relate to the reduction in aqueous PCB concentrations during activated carbon treatment.     

The impact of sampling techniques on soil pore water carbon measurements of an Icelandic Histic Andosol

The carbon in soil pore water from a Histic Andosol from Western Iceland was studied at three different scales; in the field, in undisturbed outdoor mesocosms and in laboratory repacked microcosms. Pore water was extracted using suction cup lysimeters and hollow-fibre tube sampler devices (Rhizon samplers). There were significant differences in all measured variables, dissolved inorganic carbon (DIC), dissolved organic carbon (DOC) and pH values between the scales of the experiment. Gaseous constituents of soil solution and pH were more susceptible to changes in scale and the type of sampling devices used. Dissolved inorganic carbon concentrations did not differ significantly between field and mesocosm solutions but where up to 14 times lower in microcosms compared to mesocosms solutions. Rhizon samplers yielded solutions with up to 4.7 times higher DIC concentrations than porous cup lysimeters. Mesocosm surface horizon DOC concentrations were 20 and 2 times higher than in field and microcosms respectively. There was difference in DOC concentration between sampling methods (up to 8 times higher in suction cups than rhizon samplers) above 50 cm depth. Soil solution pH values did not differ between field and mesocosms and mesocosms and microcosms respectively down to 80 cm depth. Direct comparison between field and microcosms was not possible due to the nature of sampling devices. Soil solutions sampled with Rhizon samplers yielded lower pH values (up to 1.3 pH units) than those sampled with suction cups. Twenty percent of annually bound organic carbon at the soils surface under field conditions was lost by leaching of DOC and through decomposition to DIC in disturbed non-vegetated microcosms. This percentage increased to 38% in undisturbed vegetated mesocosms highlighting the importance of surface vegetation in importing carbon to soils. Increased influx of nutrients will increase growth and photosynthesis but decrease carbon sequestration in near surface horizons. Although field studies considering long-term anthropogenic changes in pedogenesis require considerable experimental duration, more rapid experiments can be conducted with confidence in micro- and mesocosms as in this research.     

Experimental and modelling study on the uptake and desorption kinetics of 133Ba by suspended estuarine sediments from southern Spain

Dispersion of pollutants in aquatic environments depends on their uptake by suspended solids. This work deals with the uptake kinetics of 133Ba (gamma-emitter and a good analogue of 226Ra) by suspended estuarine sediments (which can be resuspended into the water column under certain conditions). This study presents a wide set of tracing experiments, including second tracing, decantation and desorption processes. The purpose is to characterize 133Ba uptake by sediments and to investigate the use and limitations of box models in order to describe the uptake kinetics. Water and sediment samples were collected in the Huelva estuary (Spain), where environmental 226Ra concentrations have been increased by two phosphate fertilizer industries. Samples were characterized by granulometric, organic carbon content, cation exchange capacity and XRF-EP analyses. Results revealed three-step kinetics, with characteristic times of minutes, hours and days. These results enabled the selection and calibration of a suitable box model and facilitated the testing of its use as a fully predictive tool.     

Bioaccumulation of pollutants in the zebra mussel from hazardous industrial waste and evaluation of spatial distribution using GAMs

In the Flix Reservoir (Ebro River, Spain), ca. 300,000 tons of industrial waste were dumped because of the activity of a factory plant in Flix. Within the recovery program implemented, this exceptional situation provides a unique opportunity to test the value of zebra mussel as sentinel organism. Ten metal concentrations were measured in mussels from different sites to assess spatial redistribution of metals and bioavailability to the food web. Our results showed an important metal uptake by mussels; metal concentrations (except As) measured in impacted sites were up to 10 times higher than in control sites, and Mn and Hg exceeded several times the levels previously reported for polluted waters. Concentrations increased downstream showing the metal mobilization from polluted sediments in Flix Reservoir. The higher metal concentrations measured in zebra mussel individuals clearly indicated their bioavailability to the food web, allowing the toxics transfer to predators and occasionally to humans. Thus, zebra mussel is a valuable sentinel organism to identify highly polluted waters, transport routes and trophic transfer.     

Modeling PAH mass transfer in a slurry of contaminated soil or sediment amended with organic sorbents

A three-compartment kinetic partitioning model was employed to assess contaminant mass transfer and intraparticle diffusion in systems comprising dense slurries of polluted soil or aquifer sediment with or without sorbent amendments to sequester polycyclic aromatic hydrocarbons (PAHs). The model was applied to simulate temporal changes in aqueous and particle-bound PAH concentrations comparing different pollution sources (heavy oil or tar sludge) and various sorbent amendments (polyoxymethylene (POM), coke breeze, and activated carbon). For the model evaluation, all the parameters needed were directly measured from a series of experiments, allowing full calibration and verification of model predictions without parameter fitting. The numerical model reproduced two separate laboratory-scale experiments reasonably: PAH uptake in POM beads and PAH uptake by semipermeable membrane devices. PAH mass transfer was then simulated for various scenarios, considering different sorbent doses and mass transfer rates as well as biodegradation. Such model predictions provide a quick assessment tool for identifying mass transfer limitations during washing, stabilization, or bioslurry treatments of polluted soil or sediment in mixed systems. It appears that PAHs would be readily released from materials contaminated by small oil droplets, but not tar decanter sludge. Released PAHs would be sequestered rapidly by activated carbon amendment but to a much lesser extent by coke breeze. If sorbing black carbon is present in the slurries, POM pellets would not be effective as a sequestration amendment. High first-order biodegradation rates in the free aqueous phase, e.g., in the order of 0.001 s(-1) for phenanthrene, would be required to compete effectively with adsorption and mass transfer for strong sorbents.     

Adsorption of dissolved natural organic matter by modified activated carbons

Adsorption of dissolved natural organic matter (DOM) by virgin and modified granular activated carbons (GACs) was studied. DOM samples were obtained from two water treatment plants before (i.e., raw water) and after coagulation/flocculation/sedimentation processes (i.e., treated water). A granular activated carbon (GAC) was modified by high temperature helium or ammonia treatment, or iron impregnation followed by high temperature ammonia treatment. Two activated carbon fibers (ACFs) were also used, with no modification, to examine the effect of carbon porosity on DOM adsorption. Size exclusion chromatography (SEC) and specific ultraviolet absorbance (SUVA(254)) were employed to characterize the DOMs before and after adsorption. Iron-impregnated (HDFe) and ammonia-treated (HDN) activated carbons showed significantly higher DOM uptakes than the virgin GAC. The enhanced DOM uptake by HDFe was due to the presence of iron species on the carbon surface. The higher uptake of HDN was attributed to the enlarged carbon pores and basic surface created during ammonia treatment. The SEC and SUVA(254) results showed no specific selectivity in the removal of different DOM components as a result of carbon modification. The removal of DOM from both raw and treated waters was negligible by ACF10, having 96% of its surface area in pores smaller than 1 nm. Small molecular weight (MW) DOM components were preferentially removed by ACF20H, having 33% of its surface area in 1--3 nm pores. DOM components with MWs larger than 1600, 2000, and 2700 Da of Charleston raw, Charleston-treated, and Spartanburg-treated waters, respectively, were excluded from the pores of ACF20H. In contrast to carbon fibers, DOM components from entire MW range were removed from waters by virgin and modified GACs.     

Biomonitoring of mercury in polluted coastal area using transplanted mussels

The Kastela Bay is heavily polluted with inorganic mercury originated from direct discharges from the chlor-alkali plant, which operated in the period from 1950 to 1990. Even though the plant was closed 15 years ago, elevated levels of total mercury are still evident in surface sediments of the bay. In order to assess the availability of remobilized mercury to marine organisms, cultured mussels (M. galloprovincialis) were transplanted from pristine area to Kastela Bay, in the period from September 2000 to March 2001. Mussel samples were collected for the analysis of THg and MeHg in whole soft tissue, gills and digestive gland. Surface sediments and suspended matter were collected for the analysis of THg. Digestive gland was the target organ for the accumulation of THg, while concentrations of MeHg were similar in all analyzed tissues. The percentage of MeHg in mussel tissues (4-27%) was characteristic for the areas contaminated with inorganic mercury. A significant negative correlation was observed between the THg concentration in the tissues and the percentage of MeHg. Concentrations of THg in mussel tissues, which were decreasing from the source of contamination in an anticlockwise direction towards the exit of the bay, were significantly positively correlated to THg content in sediment and suspended particles. Spatial distribution of mercury species (THg and MeHg) in different environmental compartments was in accordance with the prevailing circulation in the bay. Data obtained through 6 months of biomonitoring experiment indicated that digestive gland was more sensitive indicator of THg concentrations in the environment than the whole organism or gills. As for MeHg, all tissues were equally suitable as biomonitors of MeHg concentrations in the environment.     

The phosphorus budget of the Thame catchment,Oxfordshire: 2. Modelling

The phosphorus budget of the River Thame was modelled at a daily time scale, using estimates of diffuse and point source contributions of discharge. The model simulated suspended sediment (SS), soluble unreactive phosphorus (SUP), soluble reactive phosphorus (SRP) and particulate phosphorus (PP) concentrations within the main river and major tributaries. Diffuse source estimates of phosphorus loads were based on characteristic losses from identified main landscape classes, with hydrology described by a simple conceptual storage model. In-stream flow was modelled using a kinematic wave equation. Transfer of suspended sediment and phosphorus components was approximated by advection. In-stream sources and sinks included uptake and release of soluble reactive phosphorus by bed sediment, instant equilibration between SRP and the PP concentration on suspended sediment, and flow-related entrainment and deposition of suspended sediment. Simulations at sites within the catchment were compared with measurements made in 1998–1999. Results showed the P budget is dominated by mixing of diffuse and point source water, but some within-river processes have been shown to be capable of significantly influencing SRP concentrations. The development of a sediment entrainment and deposition component of the model has proved particularly valuable in emulating the hysteretic relationship between discharge and suspended sediment concentration in the river. It also provides a measure of available bed sediment.     

Organochlorine insecticides and PCB'S in sediments of Lake St. Claire (1970 and 1974) and Lake Erie (1971).

Sediments were collected on a grid from Lake St. Clair in 1970 and 1974 and from Lake Erie in 1971 and analysed for organochlorine insecticides and PCBs. Suspended solids were centrifuged from pumped water in the Detroit River in 1974. Residues of DDE, TDE and DDT were highest in sediment from the Western Basin (70.3 ppb) Lake Erie and lowest in sediment from Lake St. Clair (6.6 ppb in 1970 and 2.6 ppb in 1974). The Central and Eastern Basins of Lake Erie contained residues that fell about mid-way between these means. TDE was the predominant component of ΣDDT and was followed by DDE at approximately half this residue. While DDT represented the lowest component in lake sediments, it was the highest component in suspended solids from the Detroit River.HEOD was present in the entire lake system but at only a fraction of the level of ΣDDT. The mean residue in Lake St. Clair was only 0.1 ppb while Lake Erie sediments contained 1–2 ppb. The highest mean residue (3.6 ppb) was in suspended solids in the Detroit River. Other organochlorine insecticides were only occasionally identified.PCB residues in sediment were approximately 3 times higher than the total organochlorine insecticide residue, being highest in the Western Basin (252 ppb) and lowest in Lake St. Clair (19 ppb in 1970 and 10 ppb in 1974). The Detroit River and Central and Eastern Basins of Lake Erie had intermediate residues.Residues in Lake St. Clair indicated a decline in ΣDDT, HEOD, and PCB residues between 1970 and 1974, and this coincided with the restrictions on the materials. A core sample from the Western Basin of Lake Erie indicated that ΣDDT, HEOD and PCB began to accumulate in sediments in 1958, 1953, and 1956, respectively. This appeared to indicate a lag period of 2–5 years after wide-spread use occurred.     

Nitrous acid interference with passive NO2 measurement methods and the impact on indoor NO2 data

Recent research has demonstrated that nitrous acid (HONO) is produced in indoor environments by NO2 reacting with interior surfaces, and is also emitted directly by some combustion sources. We have recently characterized the interference by HONO to NO2 measurements made by several commonly used continuous NO2 monitors. This paper reports on the effect of HONO on NO2 measurements made by passive sampling devices. The objective of this study was to evaluate this interference, and the accuracy and precision of passive samplers used for indoor NO2 measurements. We report that HONO interferes quantitatively with three of the four NO2 passive samplers tested.     

Determination of biodegradable dissolved organic carbon in waters: comparison of batch methods

An effect of different types of bacterial inocula upon the final biodegradable dissolved organic carbon (BDOC) result was investigated in samples of both low and high BDOC concentrations. Stream water and leaf leachate samples were incubated either with free, suspended bacteria or with bacteria attached to the stream sediment particles or attached to artificial substrata. The time course of dissolved organic carbon (DOC) decomposition was observed using absorbance analysis of DOC. BDOC determination by means of commonly used suspended bacteria as the inoculum made for an underestimation of BDOC between 5% and 25%, compared with attached bacterial community (biofilm). The reason for these findings could be the higher microbial diversity, higher metabolic activity of attached bacteria and abiotic adsorption of organic molecules to inorganic support and biofilm matrix surfaces. Adsorbed DOC is easily hydrolyzed and utilized by biofilm bacteria.     

Residual effects of lead and zinc mining on freshwater mussels in the Spring River Basin (Kansas, Missouri, and Oklahoma, USA)

Concentrations of selected trace elements in surface water and fluvial sediment were investigated as possible factors limiting the distribution and abundance of freshwater mussels in the Spring River Basin, a 6600 km(2) watershed overlapping a former Pb and Zn mining and ore processing district in the central USA. Mussel taxa richness surveys and supporting physical habitat assessments were performed in 23 stream reaches dispersed throughout the basin and above and below former mining sites. Quantitative mussel density surveys were performed in the Spring River at one upstream reference location and one downstream location. Concentrations of 16 trace elements in the soft tissues of mussels and Asian clams (Corbicula fluminea) were determined at most survey sites. Comparable analyses were performed on surface water samples collected during base flow and peak flow synoptic surveys and sediment samples collected during base flow periods. Sites on the Spring River immediately upstream of heavily mined areas supported at least 21-25 species of mussels, whereas sites near the lower terminus of the river yielded evidence of 6-8 extant species. Between the upper and lower quantitative survey sites, mean mussel and clam densities declined by 89% and 97%, respectively. Tributary reaches below heavily mined areas lacked evident bivalve communities and contained concentrations of Cd, Pb, and Zn that continually or sporadically exceeded hardness-dependent water quality criteria and consensus-based sediment quality guidelines (probable effect concentrations). In less contaminated stream reaches supporting bivalves, concentrations of Cd, Pb, and Zn in mussels and clams were correlated spatially with the levels occurring in surficial sediment (0.50 < or = tau < or = 0.64, p < or = 0.03). In non-headwater perennial stream reaches, sediment Cd, Pb, and Zn levels were related inversely to mussel taxa richness (-0.80 < or = tau < or = -0.64, p < or = 0.004). Metal contaminant burdens in mussels and clams fluctuated measurably in association with variable stream flow conditions and accompanying changes in surface water and sediment chemistry. Concentrations of Cd, Pb, and Zn in mussels approximately paralleled the levels measured in composite clam samples (0.74 < or = tau < or = 0.79, p<0.001), implying C. fluminea could serve as a possible surrogate for native mussels in future metal bioaccumulation studies. Overall, streams draining heavily mined areas exhibited depauperate (or fully extirpated) mussel assemblages and correspondingly elevated concentrations of Cd, Pb, and Zn in water, sediment, and bivalve tissue. Other evaluated environmental chemistry parameters, and physical habitat conditions assessed at the stream reach scale, demonstrated little general relationship to the degraded status of these assemblages. We conclude that pollution attributable to former mining operations continues to adversely influence environmental quality and impede the recovery of mussel communities in a large portion of the Spring River Basin.     

Correlations, partitioning and bioaccumulation of heavy metals between different compartments of Lake Balaton

Correlations between trace metals in dissolved and particulate phases, zooplankton, mussels and sediments in Lake Balaton were investigated. The degree of correlation between the various metals was different in each of the investigated compartments. Particulate metal concentrations (microg g(-1)) were anti-correlated with suspended particulate matter (SPM) (mg l(-1)), indicating a dilution effect, while total metal concentrations in the water column (microg l(-1)) were highly correlated with SPM, implying a major influence of the turbidity on the total metal concentrations. Between compartments, not many significant correlations were recognized. Only Ba, Ca, Sr and Mg are correlated in the sediments and in the particulate phase, suggesting common sources for both compartments. Partitioning coefficients (Kd) of trace metals between dissolved and particulate phases are generally low, typical for natural water and fairly stable over the lake. Most of the trace metals (Zn, Co, Cd and Pb) exist in the particulate phase (for about 70% of the total metal load). Cu and Ni are exceptions, showing a more equal distribution. Bioconcentration factors (BCF) of zooplankton and mussels were comparable to those of other natural waters. A negative biomagnification from suspended particulate matter to zooplankton and from sediment to mussel was recognized for all trace metals, except a small enrichment of Zn in zooplankton and Cd in mussel. Four factors were recognized in SPM and in sediments but they did not contain the same group of metals. Cluster analysis showed that metal accumulations in the sediments were different between northern and southern shores and in SPM between western and eastern areas.     

The stability of marine sediments at a tidal basin in San Francisco Bay amended with activated carbon for sequestration of organic contaminants

Recent laboratory studies show that adding activated carbon to marine sediments reduces the bioavailability of persistent organic contaminants, such as polychlorinated biphenyls, to benthic organisms. The present work investigates how mixing activated carbon into cohesive sediment affects the stability of sediment obtained from the intertidal zone at the Hunters Point Naval Shipyard Superfund site in South Basin, San Francisco Bay, CA. Our results show for these sediments that mixing activated carbon into sediment does not significantly affect stability of surface sediments, as measured by sediment erosion rate and critical shear stress for incipient motion, thus supporting the potential field application of this technique for in situ stabilization of persistent organic contaminants. Hydrodynamic modeling was used to estimate the maximum bottom shear stress encountered during high-wind storm events at the estuarine inlet from which the sediments were obtained. Comparison of estimated bottom shear stresses with measured critical shear stresses shows that surface sediments will not erode under normal, non-storm conditions. Bottom shear stresses caused by large waves under infrequent high-wind storm conditions may erode surface sediments for short periods of time. We conclude from sediment stability tests and hydrodynamic modeling that mixing activated carbon amendment with cohesive sediment at selected locations within South Basin will not reduce surface sediment stability nor result in significant erosion of treated sediments.     

Comparative toxicity assessment of ozone and activated carbon treated sewage effluents using an in vivo test battery

Wastewater treatment plants do not eliminate micropollutants completely and are thus important point sources for these substances. Ozonation and activated carbon treatment might be beneficial for ecosystem health as these techniques provide effective barriers to organic contaminants. However, a toxicity evaluation is required to investigate toxicity reduction and to assess the potential formation of toxic oxidation byproducts during ozonation.Therefore a comparative toxicity evaluation of different treated wastewater effluents was performed on site at a half scale treatment plant equipped with an ozonation step and an activated carbon treatment step in parallel subsequent to conventional activated sludge treatment. For this purpose four invertebrate and one higher plant toxicity test were selected to assess potential biological effects on whole organisms.The reproduction test with the mudsnail Potamopyrgus antipodarum exhibited a decreased reproductive output after advanced treatment compared to conventional treatment. This indicates an effective estrogenicity removal by ozonation and activated carbon treatment and is confirmed by results of the yeast estrogen screen with a reduction of in vitro estrogenic activity by >75%. The Lumbriculus variegatus test revealed a significantly enhanced toxicity after ozonation compared to conventional treatment whereas this effect was reduced following subsequent sand filtration. When ozonation was applied, a significantly increased genotoxicity was observed, detected with the comet assay using haemolymph of the zebra mussel. Again, this effect was removed by subsequent sand filtration to the level of conventional treatment. Activated carbon treatment even resulted in a significant reduction of genotoxicity.Adverse effects after the ozone reactor are possibly a result of the formation of toxic oxidation byproducts. Biologically active sand filtration obviously is an effective barrier to such compounds.     

Removing low ppb level perchlorate, RDX, and HMX from groundwater with cetyltrimethylammonium chloride (CTAC) pre-loaded activated carbon

Perchlorate contaminates vast amounts of groundwater throughout the United States which could potentially be used as potable water. Activated carbon pre-loaded with cetyltrimethylammonium chloride has been shown in this research to be an effective adsorbent for removing perchlorate from three low conductivity (50-66 microS/cm) groundwaters containing perchlorate (ClO(4)(-)) concentrations of 0.85, 1.0, and 5.6 parts per billion (ppb), respectively. In rapid small-scale column tests (RSSCTs), the virgin granular activated carbon (GAC) (used as a control) treated between 20,000 and 40,000 bed volumes (BV) of water. In contrast, the activated carbon that was pre-loaded with CTAC processed 170,000-270,000 BV before perchlorate was detected above 0.25 ppb in the effluent. Though this pre-loading significantly increased the capacity for perchlorate, it also diminished the GAC's capacity to remove organics. The groundwater containing 1 ppb ClO(4)(-) also contained the nitro-organics HMX (0.6 ppb) and RDX (5.5-6.6 ppb). RDX was detected in the effluent from the CTAC-pre-loaded bed after only 8000 BV had been processed whereas 308,000 BV could be processed through the virgin bed before RDX was detected. Likewise, HMX breakthrough was observed after 116,000 BV in the CTAC-pre-loaded bed while the virgin RSSCT exhibited no breakthrough of HMX during a test that was operated for 309,000 BV. However, by combining a CTAC-pre-loaded bed followed by a virgin GAC bed in series, both perchlorate and RDX could be removed for the same length of time.