Asbjørn Haaning Nielsen

Corrosion of concrete sewers—The kinetics of hydrogen sulfide oxidation

Hydrogen sulfide absorption and oxidation by corroding concrete surfaces was quantified in a test rig consisting of 6 concrete pipes operated under sewer conditions. The test rig was placed in an underground sewer monitoring station with access to fresh wastewater. Hydrogen sulfide gas was injected into the pipe every 2nd hour to peak concentrations around 1000 ppm. After some months of operation, the hydrogen sulfide became rapidly oxidized by the corroding concrete surfaces. At hydrogen sulfide concentrations of 1000 ppm, oxidation rates as high as 1 mg S m(-2) s(-1) were observed. The oxidation process followed simple nth order kinetics with a process order of 0.45-0.75. Extrapolating the results to gravity sewer systems showed that hydrogen sulfide oxidation by corroding concrete is a fast process compared to the release of hydrogen sulfide from the bulk water, resulting in low gas concentrations compared with equilibrium. Balancing hydrogen sulfide release with hydrogen sulfide oxidation at steady state conditions demonstrated that significant corrosion rates--several millimeters of concrete per year--can potentially occur at hydrogen sulfide gas phase concentrations well below 5-10 ppm. The results obtained in the study advances the knowledge on prediction of sewer concrete corrosion and the extent of odor problems.

Influence of pipe material and surfaces on sulfide related odor and corrosion in sewers

Hydrogen sulfide oxidation on sewer pipe surfaces was investigated in a pilot scale experimental setup. The experiments were aimed at replicating conditions in a gravity sewer located immediately downstream of a force main where sulfide related concrete corrosion and odor is often observed. During the experiments, hydrogen sulfide gas was injected intermittently into the headspace of partially filled concrete and plastic (PVC and HDPE) sewer pipes in concentrations of approximately 1,000 ppm(v). Between each injection, the hydrogen sulfide concentration was monitored while it decreased because of adsorption and subsequent oxidation on the pipe surfaces. The experiments showed that the rate of hydrogen sulfide oxidation was approximately two orders of magnitude faster on the concrete pipe surfaces than on the plastic pipe surfaces. Removal of the layer of reaction (corrosion) products from the concrete pipes was found to reduce the rate of hydrogen sulfide oxidation significantly. However, the rate of sulfide oxidation was restored to its background level within 10-20 days. A similar treatment had no observable effect on hydrogen sulfide removal in the plastic pipe reactors. The experimental results were used to model hydrogen sulfide oxidation under field conditions. This showed that the gas-phase hydrogen sulfide concentration in concrete sewers would typically amount to a few percent of the equilibrium concentration calculated from Henrys law. In the plastic pipe sewers, significantly higher concentrations were predicted because of the slower adsorption and oxidation kinetics on such surfaces.

AEROBIC AND ANAEROBIC TRANSFORMATIONS OF SULFIDE IN A SEWER SYSTEM - FIELD STUDY AND MODEL SIMULATIONS

The formation and fate of sulfide in a force main and a downstream-located gravity sewer were investigated in an extensive field study. Sulfide formation in the force main was significant. However, during 14 minutes of transport in the gravity sewer, the sulfide concentration decreased 30%, on average. An application of a conceptual sewer process model for simulating the formation and fate of sulfide was demonstrated. Overall, the model predicted that approximately 90% of the decrease of the sulfide concentration in the gravity sewer was the result of sulfide oxidation and that only a small fraction entered the sewer atmosphere, causing odor and corrosion. Even so, the model predicted concrete corrosion rates of up to 1.2 mm/y in the gravity sewer section.

Modeling of hydrogen sulfide oxidation in concrete corrosion products from sewer pipes.

Abiotic and biotic oxidation of hydrogen sulfide related to concrete corrosion was studied in corrosion products originating from a sewer manhole. The concrete corrosion products were suspended in an acidic solution, mimicking the conditions in the pore water of corroded concrete. The removal of hydrogen sulfide and dissolved oxygen was measured in parallel in the suspension, upon which the suspension was sterilized and the measurement repeated. The results revealed the biotic oxidation to be fast compared with the abiotic oxidation. The stoichiometry of the hydrogen sulfide oxidation was evaluated using the ratio between oxygen and hydrogen sulfide uptake. The ratio for the biotic oxidation pointed in the direction of elemental sulfur being formed as an intermediate in the oxidation of hydrogen sulfide to sulfuric acid. The experimental results were applied to suggest a hypothesis and a mathematical model describing the hydrogen sulfide oxidation pathway in a matrix of corroded concrete.

Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers

Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria, were suspended in aqueous solution at pH similar to that of corroded concrete. Hydrogen sulfide was supplied to the reactor to provide the source of reduced sulfur. The removal of hydrogen sulfide and oxygen was monitored. The utilization rates of both hydrogen sulfide and oxygen suggested exponential bacterial growth with median growth rates of 1.25 d(-1) and 1.33 d(-1) as determined from the utilization rates of hydrogen sulfide and oxygen, respectively. Elemental sulfur was found to be the immediate product of the hydrogen sulfide oxidation. When exponential growth had been achieved, the addition of hydrogen sulfide was terminated leading to elemental sulfur oxidation. The ratio of consumed sulfur to consumed oxygen suggested that sulfuric acid was the ultimate oxidation product. To the knowledge of the authors, this is the first study to determine the growth rate of bacteria involved in concrete corrosion with hydrogen sulfide as source of reduced sulfur.

Improved urban stormwater treatment and pollutant removal pathways in amended wet detention ponds

Dissolved and colloidal bound pollutants are generally poorly removed from stormwater in wet detention ponds. These fractions are, however, the most bio-available, and therefore three wet detention ponds were amended with planted sand filters, sorption filters and addition of precipitation chemicals to enhance the removal of dissolved pollutants and pollutants associated with fine particles and colloids. The three systems treated runoff from industrial, residential and combined (residential and highway) catchments and had permanent volumes of 1,990, 6,900 and 2,680 m3, respectively. The treatment performance of the ponds for elimination of total suspended solids (TSS), total nitrogen (Tot-N), total phosphorous (Tot-P), PO4-P, Pb, Zn, Cd, Ni, Cr, Cu, Hg were within the range typically reported for wet detention ponds, but the concentrations of most of the pollutants were efficiently reduced by the planted sand filters at the outlets. The sorption filters contributed to further decrease the concentration of PO4-P from 0.04 ± 0.05 to 0.01 ± 0.01 mg L−1 and were also efficient in removing heavy metals. Dosing of iron sulphate to enrich the bottom sediment with iron and dosing of aluminium salts to the inlet water resulted in less growth of phytoplankton, but treatment performance was not significantly affected. Heavy metals (Pb, Zn, Cd, Ni, Cr and Cu) accumulated in the sediment of the ponds. The concentrations of Zn, Ni, Cu and Pb in the roots of the wetland plants were generally correlated to the concentrations in the sediments. Among 13 plant species investigated, Rumex hydrolapathum accumulated the highest concentrations of heavy metals in the roots (Concentration Factor (CF) of 4.5 and 5.9 for Zn and Ni, respectively) and Iris pseudacorus the lowest (CF < 1). The translocation of heavy metals from roots to the aboveground tissues of plants was low. Therefore the potential transfer of heavy metals from the metal-enriched sediment to the surrounding ecosystem via plant uptake and translocation is negligible.

Sorption media for stormwater treatment: A laboratory evaluation of five low-cost media for their ability to remove metals and phosphorous from artificial stormwater

Five sorption materials were studied with a focus on polishing pretreated stormwater: crushed limestone, shell-sand, zeolite, and two granulates of olivine. These materials are commercially available at comparatively low cost and have been subjected to a minimum of modification from their natural states. The sorbents were tested for phosphorus, arsenic, cadmium, chromium, copper, nickel, lead, and zinc at concentration and conditions relevant for typical stormwater. The materials were tested for sorption capacity and kinetics. Desorption was tested under neutral and alkaline conditions and in the presence of chloride. For most sorbent/sorbate combinations, significant sorption occurred within the first minutes of contact between sorbent and sorbate. Treatment to the low microgram per liter range could be achieved by contact times of less than 1 hour. The study indicated that sorption filters can be designed for long life expectancy at comparatively low cost by applying the materials tested.

Unified understanding of physico-chemical properties of activated sludge and fouling propensity

A range of parameters affecting floc characteristics, sludge composition and filtration properties was investigated by analyzing 29 sludge samples from municipal and industrial conventional activated sludge systems and municipal membrane bioreactors (MBR). Samples were characterized by physico-chemical parameters, composition of ions and EPS, degree of flocculation, settling properties, dewatering properties, and filtration properties. By analyzing the interplay between various metrics instead of single parameters, a unified understanding of the influence of sludge composition and characteristics was developed. From this, a conceptual model was proposed to describe the interplay between sludge composition, characteristics, and filtration properties. The article shows three major results contributing to describe the interplay between sludge characteristics and fouling propensity: First, the degree of flocculation could be quantified by the ratio between floc size and residual turbidity and was a key parameter to assess fouling propensity. Second, extracted EPS to polyvalent cations ratio was used as an indicator of the flocculation. A high ratio combined with a high concentration of EPS resulted in large, loosely bound, and weak flocs that were easily deformed, hence giving compressible fouling layers. Finally, high amounts of carbohydrates in both total and extracted EPS resulted in more pronounced fouling, which may be explained by carbohydrates forming poorer flocs than humic substances and proteins. Accordingly, samples with high humic content showed lower specific resistance to filtration due to better floc structure. The amount of carbohydrates in EPS correlated positively to the influent COD/N ratio, which may explain why systems with high influent COD/N ratio demonstrated higher fouling propensity.

Anaerobic Transformations of Organic Matter in Collection Systems

Anaerobic transformations of wastewater organic matter in the bulk water phase of collection system networks were investigated in laboratory-scale experiments. The wastewater was collected from three locations, which provided samples with different characteristics, ranging from young to mature. Hydrolysis, fermentation, and sulfate reduction were identified as the most important anaerobic processes. Significant quantities of readily biodegradable substrate were produced by hydrolysis of complex organic substrates. The readily biodegradable substrate was further fermented into volatile fatty acids (VFA). The rate of fermentation was found to be limited by the hydrolysis process. The readily biodegradable substrate generated was almost entirely composed of VFA, primarily acetic and propionic acids. A production of sulfide was observed in all experiments, demonstrating that part of the readily biodegradable substrate was consumed by sulfate respiration. The sulfide production was most pronounced in mature wastewater that had previously undergone extended anaerobic transport.

Effect of sewer headspace air-flow on hydrogen sulfide removal by corroding concrete surfaces.

Hydrogen sulfide adsorption and oxidation by corroding concrete surfaces at different air-flows were quantified using a pilot-scale sewer reactor. The setup was installed in an underground sewer research station with direct access to wastewater. Hydrogen sulfide gas was injected into the headspace of the sewer reactor once per hour in peak concentrations of approximately 500 ppmv. The investigated range of sewer air-flows was representative for natural ventilated sewer systems, and covered both laminar and turbulent conditions. The experiments demonstrated a significant effect of sewer air-flow on the kinetics of hydrogen sulfide removal from the sewer headspace. From the lowest to the highest air-flow investigated, the rate of adsorption and oxidation increased more than threefold. At all air-flows, the reaction kinetics followed a simple n-th order rate equation with a reaction order of 0.8. The effect of air-flow on hydrogen sulfide adsorption and oxidation kinetics was quantified by a simple empirical equation.