BOX MODELS - The category of simple urban air quality models has been called box models.

The figure above is a schematic diagram of a box model including source emissions near the lower boundary (surface), advective inflow and outflow to and from the sides, entrainment of pollutant from aloft due to increasing mixing height, and chemical transformations. Since uniform mixing is assumed to occur within the box whose horizontal boundaries enclose the urban area of interest, the model can predict only the volume-averaged concentration as a function of time. Diffusion from individual sources is not considered, but all sources are considered in estimating source emissions into the box. With the simplified treatment of meteorology in terms of the effective transport winds and mixing height, one can use a sophisticated chemical and photochemical module. For the simplest box model without chemical transformations, one can derive a simple differential equation for the average concentration within the box from the consideration of mass conservation within the box or a slice of the box with a unit width normal to the wind flow, length L in the direction of flow, and height h equal to the mixing depth. The rate of change of mass within the box must be equal to the sum of the rates at which the pollutant mass is added by all the emission sources in the box, the change due to horizontal advection, and the change due to entrainment from the top resulting from the growth in mixing height. This can be expressed mathematically. (e.g., Hanna et al., 1982) TYPES OF REACTORS IN WATER QUALITY MODELING There are three main basic models used to estimate the most important process variables of different chemical reactors:

batch reactor model (batch), continuous stirred-tank reactor model (CSTR), and plug flow reactor model (PFR).

A semi-batch reactor is operated with both continuous and batch inputs and outputs. A fermenter, for example, is loaded with a batch, which constantly produces carbon dioxide, which has to be removed continuously. Analogously, driving a reaction of gas with a liquid is usually difficult, since the gas bubbles off. Therefore, a continuous feed of gas is injected into the batch of a liquid.One chemical reactant is charged to the vessel and a second chemical is added slowly. In a CSTR, one or more fluid reagents are introduced into a tank reactor equipped with an impeller while the reactor effluent is removed. The impeller stirs the reagents to ensure proper mixing. Simply dividing the volume of the tank by the average volumetric flow rate through the tank gives the residence time, or the average amount of time a discrete quantity of reagent spends

inside the tank. Using chemical kinetics, the reaction's expected percent completion can be calculated. Some important aspects of the CSTR:

At steady-state, the flow rate in must equal the mass flow rate out, otherwise the tank will overflow or go empty (transient state). While the reactor is in a transient state the model equation must be derived from the differential mass and energy balances. The reaction proceeds at the reaction rate associated with the final (output) concentration.

In a PFR, one or more fluid reagents are pumped through a pipe or tube. The chemical reaction proceeds as the reagents travel through the PFR. In this type of reactor, the changing reaction rate creates a gradient with respect to distance traversed; at the inlet to the PFR the rate is very high, but as the concentrations of the reagents decrease and the concentration of the product(s) increases the reaction rate slows. Some important aspects of the PFR:

All calculations performed with PFRs assume no upstream or downstream mixing, as implied by the term "plug flow". Reagents may be introduced into the PFR at locations in the reactor other than the inlet. In this way, a higher efficiency may be obtained, or the size and cost of the PFR may be reduced. A PFR typically has a higher efficiency than a CSTR of the same volume. That is, given the same space-time, a reaction will proceed to a higher percentage completion in a PFR than in a CSTR.

Steady vs unsteady flow system When all the time derivatives of a flow field vanish, the flow is considered to be a steady flow. Steady-state flow refers to the condition where the fluid properties at a point in the system do not change over time. Otherwise, flow is called unsteady (also called transient[5]). Whether a particular flow is steady or unsteady, can depend on the chosen frame of reference. For instance, laminar flow over a sphere is steady in the frame of reference that is stationary with respect to the sphere. In a frame of reference that is stationary with respect to a background flow, the flow is unsteady. Turbulent flows are unsteady by definition. A turbulent flow can, however, be statistically stationary. According to Pope: The random field U(x,t) is statistically stationary if all statistics are invariant under a shift in time. This roughly means that all statistical properties are constant in time. Often, the mean field is the object of interest, and this is constant too in a statistically stationary flow. Steady flows are often more tractable than otherwise similar unsteady flows. The governing equations of a steady problem have one dimension fewer (time) than the governing equations of the same problem without taking advantage of the steadiness of the flow field. Mass balance for water quality A mass balance, also called a material balance, is an application of conservation of mass to the analysis of physical systems. By accounting for material entering and leaving a system, mass flows can be identified which might have been unknown, or difficult to measure without this technique. The exact conservation law used in the analysis of the system depends on the context of the problem, but all revolve around mass conservation, i.e. that matter cannot disappear or be created spontaneously.

Therefore, mass balances are used widely in engineering and environmental analyses. For example, mass balance theory is used to design chemical reactors, to analyse alternative processes to produce chemicals, as well as to model pollution dispersion and other processes of physical systems. The general form quoted for a mass balance is The mass that enters a system must, by conservation of mass, either leave the system or accumulate within the system . Mathematically the mass balance for a system without a chemical reaction is as follows:

Strictly speaking the above equation holds also for systems with chemical reactions if the terms in the balance equation are taken to refer to total mass, i.e. the sum of all the chemical species of the system.. The equation is given below simplifies to the earlier equation in the case that the generation term is zero.

In the absence of a nuclear reaction the number of atoms flowing in and out must remain the same, even in the presence of a chemical reaction. For a balance to be formed, the boundaries of the system must be clearly defined. Mass balances can be taken over physical systems at multiple scales. Mass balances can be simplified with the assumption of steady state, in which the accumulation term is zero.

Biochemical oxygen demand model Biochemical oxygen demand or B.O.D is the amount of dissolved oxygen needed by aerobic biological organisms in a body of water to break down organic material present in a given water sample at certain temperature over a specific time period. The simple model is based on the assumptions that a single BOD input is distributed evenly at the cross section of a stream or river and that it moves as plug flow with no mixing in the river. Furthermore only one DO sink (carbonaceous BOD) and one DO source (reaeration) is considered in the classical Streeter-Phelps model. These simplifications will give rise to errors in the model. For example the model does not include BOD removal by sedimentation, that suspended BOD is converted to a dissolved state, that sediment has an oxygen demand and that photosynthesis and respiration will impact the oxygen balance. Expanded model-In addition to the oxidation of organic matter and the reaeration process, there are many other processes in a stream which affect the DO. In order to make a more accurate model it is possible to include these factors using an expanded model. The expanded model is a modification of the traditional model and includes internal sources (reaeration and photosynthesis) and sinks (BOD, background BOD, SOD and respiration) of DO. It is not always necessary to include all of these parameters. Instead relevant sources and sinks can be summed to yield the overall solution for the particular model.[2] Parameters in the expanded model can be either measured in the field or estimated theoretically.

Figure: Streeter-Phelps DO sag curve and BOD development.

Hazardous and trace metal modeling Transport of hazardous materials (HAZMAT) and trace metal is a worldwide problem of growing interest, mainly because of the increasing transported volumes of materials that can be classified as hazardous. When dealing with these issues, many problems are still open, such as: i) technological problems linked to the safety of hazmat shipment, delivery and storage; ii) monitoring and control of vehicles transporting hazmat on the road infrastructures; iii) definition of tools and standardized procedures for emergency management; iv) characterization of the risk induced over the territory by hazmat transport for planning and prevention purposes. Hazardous substances released into the environment during floods are transported and dispersed in complex environmental systems that include air, plants, soil, water and sediment. Effective environmental models demand holistic modeling of the transport and transformation of the materials in the multimedia arena. Among these models, fugacity-based models are distribution based models incorporating all environmental compartments and are based on steadystate fluxes of pollutants across compartment interfaces (Mackay Multimedia Environmental Models 2001). The applications range from contaminant leaching to groundwater, runoff to surface water, partitioning in lakes and streams, distribution at regional and even global scale. Many potential sources of toxics releases during floods exist in cities or rural area: hydrocarbons fuel storage system, distribution facilities, commercial chemical storage, sewerage system are only few examples. When inundated, homes and vehicles can also be source of toxics contaminants such as gasoline/diesel, detergents and sewage. The research focus is on developing fugacity based model for fate and transport of chemicals during floods. A first two dimensional, depth averaged model has been developed. The model has a first module that estimates toxins sources during floods; a second module that simulates the hydrodynamic of the flood and a module that simulates the dynamic distribution of chemicals in the domain during and after the flood.