Exudation of low molecular weight organic acids by fungi was studied in a project focusing on bioremediation of metal-contaminated soils. The production of acids (mainly oxalic and citric acid) as a response to nutrient variations and presence of metals has recently been reported (Arwidsson et al. 2009). A significant release of metals was observed and was related not only to the production of organic acids but also to the resulting pH decrease in the systems. The processes governing the release and redistribution of metals in the soil–water fungus system were the focus of the present continuation of the project, based on observations of Aspergillus niger, Penicillium bilaiae, and a Penicillium sp. The release of lead was 12% from the soil with the second highest initial load (1,600 mg kg−1), while the release of copper was 90% from the same soil (140 mg kg−1). The dominating mechanism behind the release and subsequent redistribution was the change in pH, going from near neutral to values in the range 2.1–5.9, reflecting the production of organic acids. For some of the systems, the formation of soluble complexes is indicated (copper, at intermediate pH) which favors the metal release. Iron is assumed to play a key role since the amount of secondary iron in the soils is higher than the total load of secondary heavy metals. It can be assumed that most of the heavy metals are initially associated with iron-rich phases through adsorption or coprecipitation. These phases can be dissolved, or associated metals can be desorbed, by a decrease in pH. It would be feasible to further develop a process in technical scale for remediation of metal-contaminated soil, based on microbial metabolite production leading to formation of soluble metal complexes, notably with copper.

The effect of in situ immobilization of lead (Pb) and arsenic (As) in soil with respectively phosphate and iron is well recognized. However, studies on combined Pb and As-contaminated soil are fewer, and assessment of the effectiveness of the immobilization on mobility and bioaccessibility is also necessary. In this study, a Pb and As-contaminated soil was collected from an abandoned lead/zinc mine in Shaoxing, Zhejiang province of China, which has been treated with three phosphates, i.e., calcium magnesium phosphate (CMP), phosphate rock, and single super-phosphate (SSP) for 6 months in a field study. The ferrous sulfate (FeSO₄) at 20 g kg⁻¹ was then amended to the soil samples and incubated for 8 weeks in a greenhouse. The solubility and bioaccessibility tests were used to assess the effectiveness of the in situ immobilization. The result showed that phosphates addition decreased the concentrations of CaCl₂-extractable Pb; however, the concentrations of water-soluble As increased upon CMP and SSP addition. With the iron addition, the water-soluble As concentrations decreased significantly, but CaCl₂-extractable Pb concentrations increased. The bioaccessibility of As and Pb measured in artificial gastric and small intestinal solutions decreased with phosphate and iron application except for the bioaccessibility of As in the gastric phase with SSP addition. Combined application of phosphates and iron can be an effective approach to lower bioaccessibility of As and Pb, but has opposing effects on mobility of As and Pb in contaminated soils.

Alkanolamines in the wastewater from gas treating plants are not readily biodegradable. In this work, we have investigated the effectiveness of the Fenton's reagent (H₂O₂-Fe²⁺) to treat monoethanolamine (MEA) as a model compound in simulated wastewater. Degradation studies were carried out in a jacketed glass reactor. The effects of concentrations of ferrous sulfate, hydrogen peroxide, and the pH of a solution on the rate of reaction were determined. A pH of 3 was found to be the optimum. The degradation reaction proceeds very fast at the beginning but slows down significantly at a longer time. A larger fractional degradation of the organics in solution was observed if the initial chemical oxygen demand (COD) of the feed solution was high. Gradual addition of H₂O₂ to the reaction mixture increased the COD removal by about 60% compared to one-time addition of the reagent at the beginning of the process. A rate equation for mineralization of the amine was developed on the basis of a simplified mechanistic model, and the lumped value of the rate constant for COD removal was determined. A partially degraded MEA solution as well as “pure” MEA was subjected to biological oxidation by activated sludge. The former substrate degraded much faster. The degradation rate and biomass generation data could be fitted by the Monod kinetic equations.

Single-particle analysis of short-term aerosol samplings can provide unique information on the rapid evolution of size distribution and chemical composition of industrial aerosols. In this work, the potential of scanning electron microscopy equipped with energy-dispersive X-ray spectrometry (SEM-EDX) for the time-resolved description of physicochemical properties of individual aerosol particles is investigated. Two sampling campaigns were carried out at a densely populated and industrialised coastal site. The first sampling campaign corresponded to low and stable atmospheric particle loads. Low temporal variations in PM₁₀ and PM₂.₅ mass concentrations during the preceding hours and during samplings were observed. In these conditions suitable to evaluate the accuracy of our sampling and analytical methodologies, very low temporal variation of physicochemical characteristics of atmospheric particles were observed, as expected. During the second sampling campaign, the ability of automated SEM-EDX to describe short temporal variation in PM₁₀ and PM₂.₅ chemical composition was demonstrated. We report the tracking of a steelworks emission plume transported over an urban area by means of short-term aerosol samplings and explore how this transient industrial emission contributed to ambient particulates. Steelworks are important point-source emitters of metallic pollutants such as iron, manganese, and zinc species. Detailed assessment of the microphysical and chemical properties of aerosols collected in the vicinity of steelworks enables to precisely describe how industrial aerosols affect the composition of urban particulate matter. The studied pollution event caused dramatic changes in the composition of urban aerosols by an input of fine metallic particles containing Fe, Mn or Zn oxides and mixed particles (Mn-Fe, Zn-Mn, Zn-Fe oxides). Metal-rich particles were often found internally mixed with marine and/or continental compounds, demonstrating how industrial aerosols efficiently coagulate with particles from other sources, thereby acting as carriers of heavy metals.

Linear anionic polyacrylamide (LA-PAM) is being considered as a soil amendment to reduce seepage and infiltration in unlined earthen canals. While polyacrylamides have been extensively used for potable water treatment, dewatering sewage sludge, coal and mine processing, paper manufacturing, and agriculture, little is known about its ecological impact to aquatic ecosystems. Acute toxicity (LC₅₀, 24 and 48 h) and chronic exposure tests (limited and continuous exposures) were conducted on Daphnia magna. In the chronic limited exposure experiments, Daphnia were exposed to LA-PAM for only 24 h whereas for the chronic continuous exposure the concentrations of 0, 0.5, 1, 5, 10, and 100 mg/L were tested and the endpoints of growth, onset to reproduction, fecundity, and mortality were measured for the duration of 32 days. There was no significant difference among the chronic, limitedly exposed organisms. The acute toxicity for LA-PAM was measured at 100, 150, 200, 250, and 300 mg/L. The acute test showed that the LC₅₀ for LA-PAM was at 152 mg/L. Overall in the chronic, continuous exposure test, D. magna was negatively impacted by LA-PAM at levels as low as 1 mg/L. Growth was reduced by 37% and 89% at 1 and 100 mg/L, respectively. Fecundity and onset to reproduction was impaired at 10 and 100 mg/L. Kinematic viscosity ranged from 0.98 cSt at 1 mg/L to 2.9 at 100 mg/L. At these levels, mechanical and physiological impairments due to the viscous properties of LA-PAM are the proposed mechanisms of reduction in the life history traits of D. magna.

Nitrification is a process in which ammonia is oxidized to nitrite (NO ₂ ⁻ ) that is further oxidized to nitrate (NO ₃ ⁻ ). The relations between these two steps and ambient ammonia concentrations were studied in surface water of Chinese shallow lakes with different trophic status. For the oxidations of both ammonia and NO ₂ ⁻ , more eutrophic lakes generally showed significantly higher potential and actual rates, which was linked with excessive ammonia concentrations. Additionally, both potential and actual rates for ammonia oxidation were higher than those for NO ₂ ⁻ oxidation in the more eutrophic lakes, while in the lakes with lower trophic status, both potential and actual rates for ammonia oxidation were almost equivalent to those for NO ₂ ⁻ oxidation. This can be explained by the excessive unionized ammonia (NH₃) concentration that inhibits nitrite-oxidizing bacteria in the more eutrophic lakes. The laboratory experiment with different ammonia concentrations, using the surface water in a eutrophic lake, showed that ammonia oxidation rates were proportional to the ammonia concentrations, but NO ₂ ⁻ oxidation rates did not increase in parallel. Furthermore, NO ₂ ⁻ oxidation was less associated with particles in natural water of the studied lakes. Without effective protection, it would be selectively inhibited by the excessive ammonia in hypereutrophic lakes, resulting in NO ₂ ⁻ accumulation. Shortly, the increased concentrations of ammonia cause a misbalance between the NO ₂ ⁻ -producing and the NO ₂ ⁻ -consuming processes, thereby exacerbating the lake eutrophication.

Levels and chemical forms of heavy metals in forest, paddy, and upland field soils from the Red River Delta, Vietnam were examined. Forest soils contained high Cr and Cu levels that were higher in subsurface than in surface layers. Levels of Cu, Pb, and Zn that exceeded the limits allowed for Vietnamese agricultural soils were found in the surface layer of a paddy field near the wastewater channel of a copper casting village. High amounts of Zn accumulated in the surface soil of paddy fields close to a fertilizer factory and an industrial zone. In these cases, larger proportions of Cu, Pb, and Zn were found in the exchangeable and acid-soluble fractions compared to the low-metal soils. We conclude that no serious, large-scale heavy metal pollution exists in the Red River Delta. However, there are point pollutions caused by industrial activities and natural sources.

The evolution of microbial communities with increasing carbon tetrachloride concentrations was studied in two anaerobic columns containing sand and two different clay soils, one of which contained high levels of iron. Microbial communities were characterized through analysis of column effluents with denaturing gradient gel electrophoresis and quantitative polymerase chain reaction for archaea and eubacteria as inlet carbon tetrachloride concentrations were increased from 0.8 to 29 μM. Inhibition of microbial activity was observed in both columns, and was associated with the accumulation of chloroform at concentrations of 0.2 to 0.4 μM as inlet CT concentrations were increased to 2.4-3.0 μM in the low-iron clay column and approximately 16 μM in the iron rich clay column. Inhibition was indicated by decreasing rates of methanol and carbon tetrachloride degradation, decreases in effluent levels of DNA, and shifts in microbial communities of the columns. Even with the inhibition observed, in the iron-rich clay column CT degradation continued to the end of the study with inlet CT concentrations of 29 μM, in contrast to the low-iron clay column in which minimal CT degradation occurred once CT inlet concentrations exceeded 3 μM. The greater capacity for CT degradation in the column containing the iron-rich clay was hypothesized to be the result of reaction with biogenic ferrous iron produced by biological dissimilatory iron reduction.

The impact of plants (Phalaris arundinacea L.) on the leakage of ammonium, cadmium, copper, nitrate, phosphate, and zinc from sulfidic mine tailings covered with wood fly ash and sewage sludge was investigated. Either ash or sludge was placed in contact with the tailings, and ash layers of either low or high compactness were used. It was revealed that an ash/sludge cover effectively decreased the metal leaching from the tailings regardless of the order in which the materials were applied. Plants decreased the amount of leachate and the concentrations of ammonium and phosphate. The presence of ash below the sludge decreased the plant uptake of copper and zinc and nitrate leakage. However, when the ash was added as a thin (1.5 cm) porous layer, roots and air reached the tailings and caused high metal leakage. The results support the use of a vegetated ash/sludge cover in the treatment of mine tailings, provided that the sealing layer is firm enough to prevent root penetration.

For more than a decade, Lakeland, FL, has invested in restoring its urban Lake Hollingsworth from a hypereutrophic state to its natural eutrophic state. The lake bottom was dredged of nearly 2 million m3 of accumulated organic sediments, and treatment wetlands, storm water curb inlet strainers, and a storm water baffle box were installed within the lake’s catchment area to reduce the loading of dirt, leaves, and trash to the lake. After dredging ceased, the lake was dosed one time with alum to improve water clarity and reduce phosphorus recycling from its sediments. Water quality surrogates for algal biomass— Secchi disk transparency and water column total nitrogen, total phosphorus, and chlorophyll-α concentrations— were reviewed to assess Lakeland’s progress towards its goal. In the years since dredging has stopped, algal biomass concentration in Lake Hollingsworth has significantly declined. Even with these improvements, however, the lake still remains hypereutrophic.