The modified BCR three-step sequential extraction procedure was used to examine the temporal dynamics of trace elements in soils contaminated by an accidental spill from an opencast mine in south-west Spain. Soils were mainly contaminated with pyritic sludge and acidic wastewater, whereas some soils were affected only by acidic wastewater. The distributions obtained for both some major (Ca, Fe and Mn) and trace elements (As, Cd, Cu, Pb and Zn) in the sludge and soil samples taken at different times after the accident, 1-3 months and 21 months, were compared. Sequential extractions were useful in identifying different sources of contamination, and in obtaining additional information on the solubility of secondary minerals formed by pyrite oxidation. Thus, the effectiveness of the BCR procedure has proved to be a useful tool for predicting short- and long-term mobility of trace elements, even in complex environmental scenarios. The modified BCR three-step sequential extraction procedure has proved a useful prediction tool for short- and long-term mobility of trace elements in contaminated soils.

Chemical extractions have been shown to measure the biodegradable fraction of aromatic contaminants in soil; however, there is little research on the chemical prediction of aliphatic hydrocarbon degradation. The aim of this study was to investigate the potential for cyclodextrin extractions to predict hexadecane biodegradation in soil. Soils were amended with 10 or 100 mg kg−1 of a model alkane n-hexadecane and 100 Bq g−1 14C-n-hexadecane. Correlations between the extents of mineralisation and extractions of the 14C-contaminant were determined. Solvent shake extractions and aqueous CaCl2 extractions were poor predictors of hexadecane bioaccessibility. However, the novel HP-α-CD shake extraction showed close correlation (r2 = 0.90, n = 36, p < 0.05) to the mineralisation data. This novel extraction technique has the potential to be used to assess the biodegradable aliphatic hydrocarbon fraction in contaminated soils. Cyclodextrin shake extractions have the potential to predict the bioaccessibility of aliphatic hydrocarbons in soil.

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1 + QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth. Kinetically defined metal fractions mimic mobility aspects of heavy metals.

The evaluation of microbial availability of contaminants is of high importance for better reflecting the processes governing contaminant fate in soil and for establishing the risk associated with contaminated sites. A sub-critical water extraction technique was assessed for its potential to determine the microbially degradable fraction of [14C]phenanthrene-associated activity in two dissimilar soils at three different ageing times (14, 28 and 49 days). For the majority of determinations, no significant (p > 0.05) difference between sub-critical water-extracted 14C-activity at 160 °C and the fraction mineralized by catabolically active Pseudomonas sp. was observed. Collectively, the results suggested that the sub-critical water extraction technique was an appropriate technique for predicting the biodegradable fraction of phenanthrene-associated 14C-activity in dissimilar soils following increasing soil-contaminant contact time. Sub-critical water extraction reflects phenanthrene bioaccessibility in the soil.

The effect of aeration rate on nutrient removal from slaughterhouse wastewater was examined in two 10-L laboratory-scale sequencing batch reactors (SBRs--SBR1 and SBR2) operated at ambient temperature. The contaminants in the slaughterhouse wastewater had average concentrations of 4,000 mg chemical oxygen demand (COD) L⁻¹, 350 mg total nitrogen (TN) L⁻¹ and 26 mg total phosphorus (TP) L⁻¹. The duration of a complete SBR operation cycle was 8 h and comprised four operational phases: fill (7 min), react (393 min), settle (30 min) and draw/idle (50 min). During the react phase, the reactors were intermittently aerated four times at 50-min intervals, 50 min each time. DO, pH and oxidation-reduction potential (ORP) in the reactors were real-time monitored. Four aeration rates--0.2 L air min⁻¹ in SBR1 for 70 days, 0.4 L air min⁻¹ in SBR1 for 50 days, 0.8 L air min⁻¹ in SBR2 for 120 days and 1.2 L air min⁻¹ in SBR1 for 110 days--were tested. When the aeration rate was 0.2 L air min⁻¹, the SBR was continuously anaerobic. When the aeration rate was 0.4 L air min⁻¹, COD and TP removals were 90% but TN removal was only 34%. When the aeration rates were 0.8 and 1.2 L air min⁻¹, average effluent concentrations were 115 mg COD L⁻¹, 19 mg TN L⁻¹ and 0.7 mg TP L⁻¹, giving COD, TN and TP removals of 97%, 95% and 97%, respectively. It was found that partial nitrification followed by denitrification occurred in the intermittently aerated SBR systems.

In 1997, total petroleum hydrocarbon (TPH) remediation started at a former Air Force Base, which operated from 1940 to 1991. TPH had been released to soil and groundwater at the site by military activities. The TPH was 70% jet fuel and the affected area covered 28 ha. Remediation involved a combination of technologies, including removal of volatile organic compounds using soil vapor extraction and air sparging, free product vacuum recovery and aerobic biodegradation of organics with oxygen supplied by the air sparging system, along with nutrient addition. The primary remedial method was found to be biodegradation, which has removed 93% of the contaminants from the site to date. A significant aspect of the remedial action was performance monitoring, including documentation of remediation efficiency. The goal of the research was to assess the relative accuracy of methods commonly used for monitoring in situ TPH remediation. Two such methods were selected for the research: monitoring change in soil TPH concentration (specified as non-polar extractable substances) and monitoring respiration activity in soil with a subsequent stoichiometric mass balance to estimate the mass of TPH destroyed. The study demonstrated that both of the methods provided comparable results regarding the effectiveness of in situ TPH remediation, despite the fact that their methodologies are very different.

Two series of laboratory-scale vertical flow systems (flooded and nonflooded columns) were designed to compare nitrogen removal performance, nitrous oxide emission, and ammonia volatilization under different water levels upon treating diluted digested livestock liquid. In these systems, influent was supplied at three hydraulic loading rates (HLRs of 1.25, 2.5, and 5 cm day⁻¹) during stage 1 and the rates were doubled during stage 2 when the water levels of nonflooded columns were elevated from zero to half the height of the soil column. After hydraulic loading rates doubled, the average removal rates of total nitrogen in flooded columns varied from 1.27 to 2.94 g⁻² day⁻¹ and those in nonflooded columns ranged from 1.23 to 3.88 g⁻² day⁻¹. The T-N removal at an HLR of 10 cm day⁻¹ in the nonflooded column with an elevated water table level had higher efficiency than that in the flooded column, suggesting T-N removal is enhanced in the nonflooded column probably due to the improved coupled nitrification–denitrification process under the elevated water table level condition. On the other hand, there was a significant correlation (r ² = 0.532, p < 0.001) between the N₂O flux and redox potential that mainly corresponded to water levels and HLRs, suggesting anoxic or aerobic conditions stimulate N₂O emission by enhancing the nitrification (nitrification–denitrification) process. In contrast, NH₃ volatilization had a high flux in the anaerobic condition mainly because of flooding. Based on the experimental results, it is hypothesized a nonflooded condition with higher water table level (Eh range of −160 to +260 mV) would be suitable to reduce N₂O emission and NH₃ volatilization peak value by at least half while maintaining relatively efficient nitrogen removal performance.

The arsenic bioavailability in the bed sediments from the Anllóns River (NW Spain) has been assessed by using several analytical approaches. A six-step sequential fractionation was compared to three general availability tests: the Toxicity Characteristic Leaching Procedure (TCLP) extraction, which estimates the leaching potential of As and its effect on the survival of microorganisms (Vibrio fischeri), an extraction with 1 M HCl extraction, which estimates the bioavailability to higher plants, and a physiologically based extraction test (PBET), which estimates the bioavailability to superior animals. Arsenic was found to be mainly associated to the least mobile fractions: bound to Fe-Al oxides and in the residual phase. Among the three single extractants considered, the PBET extracted the highest As concentrations (1-11% of the total As). The TCLP extracts showed toxicity to Vibrio fischeri whereas for the plants evaluated, aqueous extracts did not show adverse effects.

The present study explained the effect of pretreatments on the biosorption of Cr (III) and Cr (VI) by Cassia fistula biomass from aqueous solutions. For this purpose Cassia fistula biomass was pretreated physically by heating, autoclaving, boiling and chemically with sodium hydroxide, formaldehyde, gluteraldehyde, acetic acid, hydrogen peroxide, commercial laundry detergent, orthophosphoric, sulphuric acid, nitric acid, and hydrochloric acid. The adsorption capacity of biomass for Cr (III) and Cr (VI) was found to be significantly improved by the treatments of gluteraldehyde (95.41 and 96.21 mg/g) and benzene (85.71 and 90.81 mg/g) respectively. The adsorption capacity was found to depend on pH, initial metal concentration, dose, size, kinetics, and temperature. Maximum adsorption of both the Cr (III) and Cr (VI) was observed at pH 5 and 2. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. The kinetic studies showed that the sorption rates could be described better by a second order expression than by a more commonly applied Lagergren equation.

The removal of ⁶⁵Zn from tidal water by underlaying sediment cores collected in a mangrove forest and a tidal creek that drains this forest in Sepetiba Bay (SE Brazil) was investigated. After 30-h experiments in laboratory microcosms, the ⁶⁵Zn half-removal times from tidal creek and mangrove forest sediments were 8.7 ± 1.8 and 9.2 ± 0.9 h respectively. Depth penetration of ⁶⁵Zn was mainly restricted to the upper 3 cm in mangrove forest cores, while detectable ⁶⁵Zn activities were found in all layers (0-7 cm depth) of tidal creek cores. An unexpected ⁶⁵Zn release back to the overlaying water was observed for one of the tidal creek experiments in the 12-18 h interval (corresponding to a return of 17% of the initial ⁶⁵Zn activity in overlaying water), suggesting a reversibility of the ⁶⁵Zn removal process (e.g., by adsorption) in tidal creek sediments. The results indicate that mangrove-vegetated sediments allowed a lower vertical mobility of Zn than observed in creek sediments and mangrove sediments appear to be less susceptible to a reversion in the process of zinc removal from overlaying water, suggesting a greater capacity to retain this metal near the water-sediment interface. This first radiotracer approach on the mangrove sediments removal of Zn from tidal waters supports earlier experimental studies employing stable Zn, contributing for a better understanding of the metal uptake kinetics by such sediments and suggesting that these sediments act as active sinks for trace metals.