Municipal wastewaters with industrial discharges typically contain heavy metals which may inhibit the biological processes in wastewater treatment plants. In this study, copper inhibition on strict nitrifiers in a suspended growth (SG) reactor and a combined attached and suspended growth (A''SG) reactor was compared. Both reactors were subjected to a continuous copper input of 5 mg/L. When the accumulated total copper concentration in the reactor were approximately 25 mg/L (due to sorption to the biomass), a sharp decrease in nitrification (increase in inhibition) were observed in the SG reactor while nitrification remained the same for the A''SG reactor indicating that attached growth systems were more robust against copper toxicity than suspended growth systems. Using MINTEQA2, the concentrations of various chemical species were estimated and, of the different species present, adsorbed copper in the biomass and aqueous Cu(NH₃)₄ ⁺² were found to positively correlate with percent inhibition of nitrification. Based on the changes in the concentrations of the two species, Cu(NH₃)₄ ⁺² was probably the main chemical species responsible for inhibition of nitrification. This study has implications for wastewater treatment plants treating wastewaters with high ammonia and copper present.

The goal of this work was to study quantitatively lead bioaccumulation from a lead-doped nutrient medium by using a living aquatic macrophytes Pistia stratiotes. Several sets of aquatic plants with approximately 30 g weight were grown in greenhouse conditions and in hydroponic solutions supplied with a non-toxic Pb²⁺ concentration. The synchrotron radiation total X-ray fluorescence spectrometry was used to determine the metal concentrations in dry plants and hydroponic media as a function of time. Four different non-structural bioaccumulation models were applied to describe the process dynamics and to estimate the accumulated lead maximum capacity and rate constants. According to the experimental data, both biosorption and bioaccumulation mechanisms can be considered. Due to the low desorption rate constant, the experimental data were well described by the irreversible kinetic model. The results concerning modeling of living macrophytes' metal bioaccumulation kinetics can be used to predict the heavy metal removal dynamics from wastewaters in artificial wetlands.

Wastewater contains varieties of carbonaceous and nitrogenous compounds that undergo complicated biodegradation processes in wastewater treatment plants. How these different compounds are degraded by activated sludge in aerobic conditions is still a mystery. Researchers have been trying to interpret it using the oxygen uptake rate (OUR) derived from the respirograms of respective substrates. Several models have been proposed to interpret the substrate removal mechanisms using the experimental observations. Have we succeeded in understanding the messages by activated sludge correctly using these models? In this paper, the distinctive nature of the respirograms when activated sludge is fed with different substrates and the biokinetic models that have been developed to explain the substrate removal mechanisms using derived OUR profiles are reviewed. In addition, a sensitivity study was conducted on the recently evolved simultaneous storage and growth model to investigate the influence of key parameters on OUR profiles during the biodegradation process.

Airborne particulate matter (PM) extracts were investigated for their content of organic compounds and for the direct and oxidative DNA damage induced on lung epithelial cells A549. PM₁₀ was seasonally collected at two monitoring sites (Stations 1 and 2), characterized by different traffic loads. The cells were exposed for 30 min to extracts of PM₁₀ diluted at 0.025%, 0.05%, and 0.1% for summer samples, and at 0.05%, 0.1%, and 0.15% for winter samples. Oxidative and direct DNA damage were evaluated by formamidopyrimidine glycosylase (fpg) comet assay analyzing tail moment (TM) values from fpg-enzyme-treated cells (TMenz) and enzyme untreated cells (TM) respectively and by comet percentage analysis. Measurements relating to Station 2 showed higher levels of polycyclic aromatic hydrocarbons (PAHs), and their methyl-(methyl-PAHs) and nitro-(nitro-PAHs) derivatives in both the seasons. Nitro-PAH concentrations were higher in summer than in winter at both the stations. We found a significant increase of comet percentages at the highest dose of extract from both stations in summer and from Station 2 in winter. The TM and TMenz values relative to the summer sampling showed an early oxidative DNA damage induction also followed by direct DNA damage more evident at Station 2, that seems to correlate with the presence of higher nitro-PAH concentrations during the warm season. At both monitoring stations, the results from winter sampling campaign showed a direct DNA damage induction at 0.1% of extract and oxidative-direct DNA damage at the highest dose (0.15%).

In this biological oxygen demand (BOD) study, the manometric respirometric BOD OxiTop® method was used to monitor the biodegradation of two summer grade (SFO 1 and 2) and two winter grade light fuel oils (WFO 1 and 2) in OECD 301 F conditions, in groundwater, and in two different Finnish forest soils (mineral-poor and mineral-rich). The biodegradation measurements in the OECD 301 F conditions were carried out in two nutrient solutions for 28 days. In both solutions WFO 1 reached the highest biodegradation degree, 32% in the solution OECD 301 F, and 70% in a solution containing additional ammonium chloride. In groundwater conditions all the biodegradation degrees of fuel oils remained below 2% within the 28-day period. SFO 1 reached the highest 30 day biodegradability (4%) in mineral-poor soil, 18% in mineral-rich soil. In a 189-day measurement in a mineral-rich soil, the biodegradation degree for the SFO 1 was 94%. The manometric respirometric method proved to be a very suitable and practicable measurement method for the purpose of biodegradation studies of highly volatile light fuel oils, because in this method samples are treated to a lesser degree than in conventional methods, and dilutions are not needed. Results also indicated a considerable effect of conditions on the biodegradability in both water and soil environments. The results of these biodegradation studies could be used when planning in situ treatment methods based on natural biodegradation. In situ treatment methods are eco-efficient, and are especially suitable for sparsely populated sites.

Understanding wetland hydrogeology is important as it is coupled to internal geochemical and biotic processes that ultimately determine the fate of potential contaminant inputs. Therefore, there is a need to quantitatively understand the complex hydrogeology of wetlands. The main objective of this study was to improve understanding of saturated groundwater flow in a forested riparian wetland located on a golf course in the Lower Pee Dee River Basin in South Carolina, USA. Field observations that characterize subsurface wetland flow critical to solute transport originating from storm-generated runoff are presented. Monitoring wells were installed, and slug tests were performed to measure permeabilities of the wetland soil. A field-scale bromide tracer experiment was conducted to mimic the periodic loading of nutrients caused by storm runoff. This experiment provided spatial and temporal data on solute transport that were analyzed to determine travel times in the wetland. Furthermore, a 3-D numerical, steady-state flow model (MODFLOW) was developed to simulate subsurface flow in the wetland. A particle tracking model was subsequently used to calculate solute travel times from the wetland inlet to the outlet based on flow modeling results. It was evident that observed tracer breakthrough times were not typical of these measured wetland soil matrix conductivity values. Based on surface water sampling results at the wetland outlet, tracer arrival time was about 9 h after the injection of the tracer. These results implied an apparent mean K value of 2,050 m/day, which is 152 times larger than the mean of the measured values using slug tests (13.4 m/day). Modeling efforts clearly demonstrated this implied preferential flow behavior; particle travel times resulting from the calibrated flow model were in the order of hundreds of days, while actual travel times in the wetland were in the order of hours to a few days. This significant difference in travel times was attributed to the presence of macropores in the form of dead root channels and cavities forming a pipe-flow network. The analyses presented in this study resulted in an estimate of the ratio of matrix permeability to matrix plus macropore permeability of approximately 1/150. Eventually, the tracer test and resulting travel times between various points in the wetland were critical to understanding the true wetland flow dynamics. The final conceptual model of the hydraulic properties of the wetland soils comprised a low permeability matrix containing a web of high K macropores. Simulation of tracer transport in this system was possible using a flow model with significantly elevated K values.

The concentrations of As and Zn in 100 georeferenced soils uniformly distributed throughout the area affected by the spill from the Aznalcóllar mine (April 1998) were analysed at three depths (0-10, 10-30, and 30-50 cm) and on four dates (autumn-winter 1998, 1999, 2001, and 2004). For an estimate of the geochemical background, 30 unaffected soils near the edge of the spill were also analysed at the same depths. The soils were contaminated before the spill and, the accident seriously increased the concentration of As and Zn in the first 10 cm of almost all the affected soils. After the enormous efforts of cleaning up the tailings, around 45% of the soils had a concentration higher than 100 mg As kg⁻¹ dry soil, and some 35% had a concentration higher than 1,000 mg Zn kg⁻¹ dry soil. Both As and Zn penetrated between 10 and 30 cm in 25% and 45% of the soils, respectively, but reached 30 cm in only 12% of the soils. The remediation actions, especially the tilling and homogenisation of the uppermost 25 cm of the all soils, caused the As and Zn concentrations to decline in the soils, but this change was not very effective from the standpoint of pollution. Thus, 6 years after the spill, the uppermost 10 cm of 30% of the soils continued to have an As concentration higher than 100 mg As kg⁻¹, while the Zn concentration diminished considerably on the surface due to its greater mobility, accumulating between 10 and 30 cm in depth, where 20% of the soils continued to register more than 1,000 mg Zn kg⁻¹ dry soil.

The objective of this study was to improve the ability to model the air quality impacts of biomass burning on the surrounding environment. The focus is on prescribed burning emissions from a military reservation, Fort Benning in Georgia, and their impact on local and regional air quality. The approach taken in this study is to utilize two new techniques recently developed: (1) adaptive grid modeling and (2) direct sensitivity analysis. An advanced air quality model was equipped with these techniques, and regional-scale air quality simulations were conducted. Grid adaptation reduces the grid sizes in areas that have rapid changes in concentration gradients; consequently, the results are much more accurate than those of traditional static grid models. Direct sensitivity analysis calculates the rate of change of concentrations with respect to emissions. The adaptive grid simulation estimated large variations in O₃ concentrations within 4 x 4-km² cells for which the static grid estimates a single average concentration. The differences between adaptive average and static grid values of O₃ sensitivities were more pronounced. The sensitivity of O₃ to fire is difficult to estimate using the brute-force method with coarse scale (4 x 4 km²) static grid models.

This study was performed on 21 soils with the aim of establishing whether Pb and Ni adsorption/desorption parameters could be considered as good indicators of the risk of groundwater pollution. Results showed that high pH values in soil caused a totally irreversible Pb adsorption, thus excluding any risk of Pb groundwater pollution. Sorption/desorption studies, quantified by the desorption index (DI), showed that Ni retention was only partly affected by the basic pH values but it was also due to the electrostatic attraction processes occurring on soil surfaces, as demonstrated by the partial reversibility of the Ni sorbed. This justifies possible risks of Ni groundwater pollution. The results of a monitoring research confirmed these findings. Results suggested that the adsorption/desorption parameters, namely DI, are promising indicators to predict the risk of groundwater pollution from metals in calcareous soils.

For bioremediation of copper-contaminated soils, it is essential to understand copper adsorption and chemical forms in soils related to microbes. In this study, a Penicillium strain, which can tolerate high copper concentrations up to 150 mmol l⁻¹ Cu²⁺, was isolated from a copper mining area. The objective was to study effects of this fungus on copper adsorptions in solutions and chemical forms in soils. Results from lab experiments showed the maximum biosorptions occurred at 360 min with 6.15 and 15.08 mg g⁻¹ biomass from the media with Cu²⁺ of 50 and 500 mg l⁻¹, respectively. The copper was quickly adsorbed by the fungus within the contact time of the first 60 min. To characterize the adsorption process of copper, four types of kinetics models were used to fit the copper adsorption data vs. time. Among the kinetics models, the two-constant equation gave the best results, as indicated by the high coefficients of determination (R ² = 0.89) and high significance (p < 0.01). The addition of the fungal strain to autoclaved soil facilitated increases in concentrations of acid-soluble copper, copper bound to oxides, and of copper bound to organic matter (p < 0.05). However, the inoculation of Penicillium sp. A1 led to a decrease of water-soluble copper in the soil. The results suggested that Penicillium sp. A1 has the potential for bioremediation of copper-contaminated soils.