No / This is the third in a series of papers from a pilot project that has attempted to answer the question ‘does the application of agrochemicals accelerate the corrosion of archaeological metals in the top 50cm of the soil?’. We have approached it by a combination of field-based experiments, by establishing laboratory microcosms and by using geochemical modeling techniques to understand the processes involved. This paper reports on the geochemical modelling simulations that trace the potential corrosion pathways followed in two sets of laboratory microcosm experiments (‘Lab Beakers’ and ‘Lab Bins’) and one field experiment (at Palace Leas). This approach uses soil solution as the fluid mediating corrosion in the soil vadose zone. Soil solution was displaced following controlled exposure to fertilizers. Modelling using The Geochemists Workbench was carried out to mimic the experimental conditions, and predictions were compared with image analysis results, limited XRD analysis and published corrosion observations. We focus here on a sub-set of the data relating to the behaviour of the thinnest samples of copper in each case. As with the field and laboratory data previously reported, the results are sometimes contradictory, but on balance this project has demonstrated that applied agricultural chemicals are likely to accelerate the rate of corrosion of metal objects within 50cm of the surface. In particular, it is likely that any fertilizers containing KCI (‘potash’) will be particularly aggressive. Geochemical modeling generates plausible corrosion predictions based on post-depositional interaction between archaeological copper and soil solution, and appears to be useful in helping to simplify and understand corrosion pathways in naturally complex systems.

No / Part of a project that has attempted to answer the question ‘does the application of agrochemicals accelerate the corrosion of metals in the top 50cm of the soil? ’ is reported. We have approached the question by a combination of field-based experiments (on two sites), establishing laboratory microcosms (one involving simple aqueous systems and the other a series of simulated burial experiments) and by using geochemical modelling techniques to understand the processes involved. Two different experimental approaches in the field are documented — one using in situ monitoring of corrosion potentials and the other assessing the degree of induced corrosion using image analysis on recovered samples. The first was carried out on arable land close to the University of Bradford to which we applied different fertilizer regimes. The second was established on land owned by the University of Newcastle at Palace Leas, Morpeth, Northumberland, which has a documented field management regime extending back over one hundred years. We focus here on a sub-set of the data relating to the behaviour of the thinnest samples of copper in each case. There does seem to be some evidence of an effect resulting from the applied fertilizer, but the data are sometimes contradictory. We suggest a number of improvements for future field experiments that monitor in situ corrosion in the vadose zone.

No

Master of Science

The research presented in this report is in two sections. Section I involved the performance of a moving bed biofilm reactor (MBBR) versus a biological aerated filtration (BAF) and Section II involved study on causes of deposition in anaerobic digester gas piping. The first section evaluated and compared the performance of a laboratory-scale MBBR and BAF for organic carbon and suspended solids removal. A kinetic study was also performed on the MBBR to evaluate the system performance. The purpose was to recommend one of the systems for the Force Provider project, which provides a containerized "city" for the U.S. Army. The effluent criteria against which the systems were evaluated were total 5-day biochemical oxygen demand (TBOD5) and total suspended solids (TSS) of 30 mg/L each. The report is based on a 5-month laboratory -scale study of the two reactors. The MBBR performance depended on the percent of media provided in the reactor and the organic loading. At a media volume, which displaced the reactor volume by 40 % (heretofore called 40 % media volume), and surface area loading rate (SALR) of 20 g BOD5/m2-d, the system performance deteriorated with time. At 40 % media volume and SALR below 15 g BOD5/m2-d, the system performance improved but still did not meet effluent criteria or average. TBOD5 reduction was generally poor (approximately 50 %). Soluble BOD5 (SBOD5) concentrations were frequently below 30 mg/L and TSS concentrations were often higher than influent TSS. Overall, TSS wastage from the system (both effluent TSS and intentional wastage) averaged 0.032 kg/d. BAF system performance was excellent for TBOD5, CBOD5, SBOD5 and TSS removal, and were consistently less that 30 mg/L. Overall TSS wastage from the BAF (both via effluent and backwash) average 0.027 kg/d and was 16 % less than for the MBBR. Based on demonstrated performance, the BAF was the only viable reactor for the project. Section II of the report focused on possible causes of deposition in an anaerobic digester gas piping at a local wastewater treatment facility (Peppers ferry regional wastewater treatment facility). Industrial waste input to the treatment facility has increased lately and accounts for 40 % of the plant's wastewater inflow. An industry in Pulaski, VA, Magnox Inc. generates and disposes highly concentrated sodium sulfate, (70,000 mg/L) which is a by-product of its activities, to PFRWTF wastewater influent stream. As a result of Magnox industrial waste input, a pilot study was carried out to determine the effect of its waste on the activated sludge treatment units. Results indicated that Magnox industrial waste input would not have adverse effect on the aeration basins. However production of H2S, which can have effect on the anaerobic digester was reported (Olver Inc., 1995). Field analysis of data reported by Olver Inc. (2000) showed that H2S concentration in PFRWTF anaerobic digester gas was rising. X-ray photoelectron spectroscopy analysis of deposits found in the digester pipe together with results obtained from the laboratory-scale study revealed that iron and sulfur played a role in the deposition in the digester gas pipe. The laboratory scale study revealed that ferrous ion in the digester feed possibly precipitated over 90 % of the hydrogen sulfide gas produced in the digester, thus protecting the digester from adverse effects caused by hydrogen sulfide. / Master of Science

Interactions between copper and chlorine disinfectants were examined from the perspective of disinfectant decay and copper pitting corrosion. Sparingly soluble cupric hydroxide catalyzed the rapid decay of free chlorine, which in turn, led to production of less soluble and more crystalline phases of cupric hydroxide. The catalytic activity of the cupric hydroxide was retained over multiple cycles of chlorine dosing. Experiments with chloramine revealed that copper species could also trigger rapid loss of chloramine disinfectant. In copper pipes, loss of free chlorine and chloramine were both rapid during stagnation. Reactivity of the copper to the disinfectants was retained for weeks. Phosphate tended to decrease the reactivity between the copper pipe and chlorine disinfectants. A novel, inexpensive and real-time test to monitor copper pitting corrosion was developed. In a normal pipe, it is not possible to measure the electron flow or pitting current from the pit anode to the cathode. But a new method was developed that can form an active pit on the tip of a copper wire, which in turn, allows the pitting current to be measured. Preliminary experiments presented herein have proven that this technique has promise in at least one water condition known to cause pitting. The method also quickly predicted that high levels of orthophosphate could stop pitting attack in this water, whereas low levels would tend to worsen pitting. Future research should be conducted to examine this technique in greater detail. / Master of Science

In 1989, the specific ion electrode was identified as the best field method available to assess the chloride content of powdered concrete samples. Since the initial investigation, the manufacturer of the packaged device has altered the product. The alterations presented a equipment difference, as well as an increase in cost. To eliminate the problem of random manufacturer alternations, a generic method was developed for evaluating the chloride contents of concrete with the specification electrode. The method outlined the required equipment, the proportioning of the calibration solutions, the proportioning of the concrete digestion solution, and the measuring procedure. The developed method eliminated the problems of the digestion reaction temperature and the measurement inaccuracies of the higher chloride contents by diluting the measured concentrations. The testing procedure was validated for field application by measuring the chloride contents of concrete samples from four state bridge structures. The analysis of operator variance proved the method was applicable to any operator capable of following the procedure. / Master of Science

Gaseous cavitation is examined from a practical and theoretical standpoint. Classical cavitation experiments which disregard dissolved gas are not directly relevant to natural water systems and require a redefined cavitation inception number which considers dissolved gases. In a pressurized water distribution system, classical cavitation is only expected to occur at extreme negative pressure caused by water hammer or at certain valves. Classical theory does not describe some practical phenomena including noisy pipes, necessity of air release valves, faulty instrument readings due to bubbles, and reports of premature pipe failure; inclusion of gaseous cavitation phenomena can better explain these events. Gaseous cavitation can be expected to influence corrosion in water distribution pipes. Bubbles can form within the water distribution system by a mechanism known as gaseous cavitation. A small scale apparatus was constructed to track gaseous cavitation as it could occur in buildings. Four independent measurements including visual observation of bubbles, an inline turbidimeter, an ultrasonic flow meter, and an inline total dissolved gas probe were used to track the phenomenon. All four measurements confirmed that gaseous cavitation was occurring within the experimental distribution system, even at pressures up to 40 psi. Gaseous cavitation was more likely at higher initial dissolved gas content, higher temperature, higher velocity and lower pressure. Certain changes in pH, conductivity, and surfactant concentration also tended to increase the likelihood of cavitation. For example, compared to the control at pH 5.0 and 30 psig, the turbidity increased 295% at pH 9.9. The formation of bubbles reduced the pump's operating efficiency, and in the above example, the velocity was decreased by 17% at pH 9.9 versus pH 5.0. / Master of Science

Concrete provides a nearly perfect environment for corrosion protection of steel; However, the use of de-icing salts on the highway system has accelerated the deterioration rate of bridge decks in the snow belt. In 1981, over 100,000 bridges were reported to be structurally deficient, and the estimated cost of repair was placed at $93 billion. Concrete specimens, 1 ft. x 1 ft. x 4 in., containing four pieces of steel reinforcing bars, were prepared. In a first time, five specimens with different rebar networks were cast in order to study the effects of the rebar network on corrosion. Half-cell potential measurements were used to monitor the corrosion behavior of each specimen. In a second time, calcium nitrite, monofluorophosphate and sodium borate were evaluated for their capacity to control corrosion. The various corrosion inhibitors were tested either externally (in the test solution), internally (as a concrete admixture). The specimens were exposed to alternate complete immersion in a 6 wt% sodium chloride solution, plus eventual addition of corrosion inhibitor, for 3 days and 12 hours of drying at 110°F. The effects of corrosion inhibitors were evaluated using half-cell potential measurements and Electrochemical Impedance Spectroscopy (EIS) measurements. The EIS data were analyzed through a computer assisted EIS data analysis system. This allowed for circuit modeling of the corrosion mechanisms and evaluation of polarization resistance values for the different specimens. In both phases of this work, chloride concentration profiles as function of depth were determined. The half-cell potential measurements in complete immersion were found to give an average over the length of bar or electrically connected bars. The corrosion inhibitors applied internally were found to reduce corrosion better than corrosion inhibitors applied externally. It was shown that chloride concentration is not the only parameter controlling corrosion initiation. / Master of Science

Corrosion is an unstoppable process that occurs spontaneously in many areas of industry, specially, oil and gas industries. Therefore, the need of developing protective coating to lower the cost of corrosion is very consistent. Among different methods, electrodeposition has been a popular method since it offer many advantages such as low cost, ability to control the surface and thickness of the coating, ability to perform at low temperature and pressure, and very convenience. Ceramic nanoparticles have been widely incorporated into metal coating and used as a protective layer to improve both corrosion and hardness properties. Diazonium synthesis was used to modify cerium oxide nanoparticles by grafting with ferrocene for use in nickel nanocomposite coating. Citric acid and citrate salt were used as stabilizing ligands for yttrium oxide and praseodymium oxide nanoparticles in nickel plating solution to prevent the formation of hydroxide, thus, higher amount of nanoparticles was able to incorporate into nanocomposite coatings. These fabricated coatings were evaluate for the corrosion and mechanical properties using many different instruments and electrochemical techniques. As modified cerium oxide, stabilized yttrium oxide or praseodymium oxide added into nickel coatings. The results showed an increase in hardness and corrosion resistance leading to the overall improvement compare to pure nickel coating.