The spatial pattern and magnitude of mass fluxes at the stream-aquifer interface have important implications for the fate and transport of contaminants in river basins. Integral pumping tests were performed to quantify average concentrations of chlorinated benzenes in an unconfined aquifer partially penetrated by a stream. Four pumping wells were operated simultaneously for a time period of 5 days and sampled for contaminant concentrations. Streambed temperatures were mapped at multiple depths along a 60 m long stream reach to identify the spatial patterns of groundwater discharge and to quantify water fluxes at the stream-aquifer interface. The combined interpretation of the results showed average potential contaminant mass fluxes from the aquifer to the stream of 272 μg m-2 d-1 MCB and 71 μg m-2 d-1 DCB, respectively. This methodology combines a large-scale assessment of aquifer contamination with a high-resolution survey of groundwater discharge zones to estimate contaminant mass fluxes between aquifer and stream. We provide a new methodology to quantify the potential contaminant mass flux from an aquifer to a stream.

A geologic classification scheme was combined with elevation to test hypotheses regarding watershed sensitivity to acidic deposition using available regional spatial data and to delimit a high-interest area for streamwater acidification sensitivity within the Southern Appalachian Mountains region. It covered only 28% of the region, and yet included almost all known streams that have low acid neutralizing capacity (ANC ≤20 μeq l⁻¹) or that are acidic (ANC ≤0). The five-class geologic classification scheme was developed based on recent lithologic maps and streamwater chemistry data for 909 sites. The vast majority of the sampled streams that had ANC ≤20 μeq l⁻¹ and that were totally underlainby a single geologic sensitivity class occurred in the siliceous class, which is represented by such lithologies as sandstone and quartzite. Streamwater acid-base chemistry throughout the region was also found to be associated with a number of watershed features that were mapped for the entire region, in addition to lithology and elevation, including ecoregion, physiographic province, soils type, forest type and watershed area. Logistic regression was used to model the presence/absence of acid-sensitive streams throughout the region.

Numerous studies have shown that Steamboat Creek in Nevada is highly contaminated with mercury, with aqueous mercury concentrations more than two orders of magnitude greater than nearby mountain streams. One objective of this study was to determine if the new Spreadsheet-based Ecological Risk Assessment for the Fate of Mercury (SERAFM) model could be calibrated to the concentrations of unfiltered and dissolved total mercury, and unfiltered and dissolved MeHg in the water column for a reach on SBC and a related constructed wetland mesocosm for different seasons and residence times. SERAFM is a new U.S. Environmental Protection Agency steady state, single segment, mass balance mercury model that has been applied to lakes, and this study also examined the model’s applicability for modeling an arid flowing water environment in different seasons. The average combined error between observed and model-estimated mercury concentrations was 12% and 17% for the reach and mesocosm, respectively. Some recommendations are proposed that may allow SERAFM to better model flowing systems.

Fluvial bed sediments are widely used for characterizing anthropogenic contaminant signals in urban watersheds. This study presents the first preliminary examination of sequentially extracted Pb from grain size fractionated bed sediments using the optimized (standardized) BCR procedure. Baseline sediment samples and samples from the vicinity of three storm-sewer outlets in Nuuanu Stream, Honolulu, Hawaii, were examined. The weighted average Pb liberated from four sequentially extracted phases was 144 ± 26 mg/kg (±SD). These Pb concentrations are high compared to 3 mg/kg leached by a 0.5 M HCl solution, and 13 mg/kg from a 4-acid total digestion of baseline sediments. Over a 1.8 km section of stream channel, land use variations and traffic density differences had little impact on the magnitude of Pb in specific phases for each of the six grain size fractions examined. Regardless of grain size or spatial location, Pb in the reducible phase exceeded that in oxidizable, residual and acid extractable phases. Weighted reducible Pb concentrations for three sewer outlet sites ranged from 69 to 92 mg/kg, and this phase typically accounted for 70-80% of all labile Pb. The <63 μm grain size class did not exhibit the highest Pb concentration, instead this was found in either the 125-250 μm or 500-1,000 μm fractions. Examining bed sediment phase associations of Pb over a smaller length dimension (i.e., 40 m) centered around one sewer outlet, indicated higher concentrations at the outlet (180 mg/kg) compared to upstream (132 mg/kg) or downstream (150 mg/kg). The differences were primarily associated with higher Pb concentrations in the reducible and oxidizable phases of the coarse sand fractions (500-2,000 μm) at the outlet. Overall, all data point to a significant anthropogenic signal for Pb in bed sediments in the urbanized section of Nuuanu Stream.

A powerful 7.3 magnitude earthquake struck Taiwan on September 21, 1999. The stream water chemistry (pH, total alkalinity, conductivity, sodium, potassium, calcium, magnesium, ammonium, fluoride, chloride, sulfate, and nitrate) has been monitored since 1995 at the Guandaushi forestry riparian zone in central Taiwan. Collected data was used as a basis for comparing pre- and post-earthquake impacts. The pH, conductivity, and concentrations of Na, Ca, Mg, SO₄, and HCO₃ in stream water were lowest during the summer season, when stream water discharge was highest. On the other hand, the lowest concentrations of Cl, NH₄, and NO₃ in stream water occurred during the winter season, when stream water discharge was lowest. Also, K and F showed very little seasonal fluctuation in concentration. Downward trends in K and Ca were found 14 months prior to the earthquake; although, an upward trend occurred in NH₄ at the same time.

The structural features and O₂ consumption of the epipelic biofilm in streams of the Pampean plain were explored. The study was conducted in three lowland streams subjected to different anthropic disturbances. Three sampling sites were selected in different sectors of these streams considering land use intensity (high, moderate, and low). Samples of the water and of the epipelic biofilm were taken seasonally. El Pescado stream is subjected to a low level of human impact and showed lower organic matter and nutrient contents than the Rodríguez and Don Carlos streams which are subjected to moderate and high levels of human impact. The biofilm composition of the three streams was represented by cyanophytes and diatoms but with different species composition and dominance; protozoans and nematodes were the characteristic heterotrophic groups in the three streams. The Rodríguez and Don Carlos streams showed the highest abundance of organisms. Multiple regression showed that O₂ consumption, chlorophyll a and trophic index were significantly correlated with the oxygen demands. On the other hand, the Rodríguez and Don Carlos streams exhibited significant differences with the El Pescado stream in O₂ consumption, trophic index, and chlorophyll a content. Our results demonstrated that the different biological descriptors responded to environmental variables that are influenced by the different land use intensities, being chlorophyll a, abundance of organisms, and O₂ consumption the most sensitive variables to the changes water quality.

Former mining activities lasting 140 years in the Ducktown Mining District, Tennessee, USA, has contaminated the streams draining the district with acid-mine drainage (AMD). North Potato Creek and its major tributary, Burra Burra Creek, are two of the most heavily AMD-impacted streams in the district. The removal of dissolved metals from the water in these creeks is largely attributable to the sorption of Cu, Zn, Co, Al, and Mn on suspended hydroxide precipitates of Fe. The fraction of trace metals remaining in solution decreases with increasing pH in the sequence Pb < Cu < Zn < Co. The concentration of Fe in solution also decreases with increasing pH due to the formation of ferric hydroxide precipitates which accounted for up to 81.4% by weight of the total suspended sediment. The concentration of suspended sediment substantially decreases as the water of North Potato Creek flows through a large settling basin, where 1.3 (±0.3) x 10⁶ kg/year of trace-metal-laden suspended sediment would be annually deposited. In spite of this attempt to purify it, the water discharged into the river is acidic (pH 3.6) and still contains high concentrations of dissolved trace metals, which would resorb on to suspended sediment and be ultimately transported to a downstream reservoir, Ocoee No. 3 Lake.

Mn biogeochemistry was studied from 1994 to 2003 in a small forested catchment in the central Czech Republic using the watershed mass balance approach together with measurements of internal stores and fluxes. Mn inputs in bulk deposition were relatively constant during a period of sharply decreasing acidic deposition, suggesting that the Mn source was terrestrial, and not from fossil fuel combustion. Mn inputs in bulk deposition and Mn supplied by weathering each averaged 13 mg m-² year-¹ (26 mg m-² year-¹ total input), whereas Mn export in streamwater and groundwater averaged 43 mg m-² year-¹. Thus an additional Mn source is needed to account for 17 mg m-² year-¹. Internal fluxes and pools of Mn were significantly greater than annual inputs and outputs. Throughfall Mn flux was 70 mg m-² year-¹, litterfall Mn flux was 103 mg m-² year-¹, and Mn net uptake by vegetation was 62 mg m-² year-¹. Large pools of labile or potentially labile Mn were present in biomass and surficial soil horizons. Small leakages from these large pools likely supply the additional Mn needed to close the watershed mass balance. This leakage may reflect an adjustment of the ecosystem to recent changes in atmospheric acidity.

Naturally high total dissolved solids and upstream agricultural runoff often mask the influence of urban land cover on stream chemistry and biology. We examined the influence of headwater urbanization on the water chemistry, microbiology, and fish communities of the Big Brushy Creek watershed, a 96 km² drainage basin in the piedmont of South Carolina, USA. Concentrations of most major anions and cations (especially nitrate, sulfate, chloride, sodium, potassium, and calcium) were highest in the urban headwaters and decreased downstream. Generally, the highest concentrations of suspended coliform bacteria occurred in the urban headwaters. In contrast, stream habitat quality and the abundance, species richness, and species diversity of fishes did not differ significantly between urban and rural sites. Discharge of wastewater treatment plant effluent at one rural location caused an increase in concentrations of many solutes and possibly the abundance of benthic algae. We hypothesize that atmospheric dry deposition and domestic animal wastes are important sources of stream solutes and of coliform bacteria, respectively, in the urban headwaters. The lack of significant differences in fish abundance and diversity between urban and rural sites may indicate that urban development in the Big Brushy Creek watershed has not yet degraded habitat conditions greatly for stream fishes. Alternatively, agriculture or other land uses may have degraded stream habitat quality throughout the watershed prior to urbanization.

BACKGROUND: There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged river, harbor or estuary due to the accumulated toxic organics such as dioxins and inorganics particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result to reusable residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species particularly Cr ions was studied.METHODS: Laboratory scale pyrolysis experiments were conducted using a special horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura Harbor were pyrolyzed in the reactor under nitrogen gas at 800°C and different retention times of 30, 60 and 90 min. A constant heating rate of 10°C min-1 was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxins content of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted.RESULTS: The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580 % increase in Cr6+ observed during thermal oxidation (with air).DISCUSSION: Pyrolysis also remove toxic organics particularly dioxins from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxine (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g-1 of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal.CONCLUSION: Some heavy metals particularly Pb and Zn can be volatilized under N2 pyrolysis at 800oC. Pyrolysis also prevented the formation of more toxic Cr6+ ions and at the same time resulted to its reduction by around 42.2% contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800°C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found sufficient for its maximum removal. RECOMMENDATIONS AND PERSPECTIVE: . With the above results, a temperature of 800oC at a retention time of 30 min is sufficient for the removal of total dioxins and some heavy metals by volatilization. It is however necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating to establish the feasibility of our proposed large scale pyrolysis system for sediment treatment.