19.3 Emissions Evaluation, Mitigation, and Remediation
Key Takeaways
- Emissions are classified as **point sources** (stacks and vents), **fugitive sources** (valve stems, flanges, pump seals, sampling points), and **area sources** (tank farms, wastewater basins), and each is quantified by a different method.
- Electrostatic precipitator efficiency follows the **Deutsch-Anderson** relation \(\eta = 1 - \exp(-wA/Q)\), so each additional "nine" of collection efficiency requires a fixed **additive** increment of \(\ln(10) = 2.303\) in the group \(wA/Q\).
- 40 CFR 60.18 sets flare operating criteria — a continuous pilot, exit velocity limits, and a net heating value of at least \(300\text{ Btu/scf}\) steam- or air-assisted (\(200\text{ Btu/scf}\) unassisted) — and EPA credits a flare meeting them with **98% destruction efficiency**.
- The pollution prevention hierarchy ranks **source reduction first**, then reuse and recycling, then treatment, and disposal last; an end-of-pipe control device is the least preferred answer when a process change can eliminate the stream.
- Groundwater and soil remediation technologies are selected by contaminant volatility and biodegradability: **soil vapor extraction and air sparging** for volatile organics, **bioremediation** for biodegradable hydrocarbons, and **pump-and-treat** where the plume must simply be contained.
19.3 Emissions Evaluation, Mitigation, and Remediation
The NCEES specification lists Environment (e.g., emissions evaluation, mitigation, remediation) as the third subtopic under Safety, Health, and Environment. It is the subtopic most often absent from PE Chemical preparation, and it is examined the same way as any other unit operation — quantify the stream, select a technology, size it.
1. Classifying and Quantifying Emissions
| Source type | Examples | Usual quantification method |
|---|---|---|
| Point | Stacks, process vents, flares, incinerator outlets | Direct stack testing (EPA reference methods) or continuous emission monitoring (CEMS) |
| Fugitive | Valve stems, flanges, pump and compressor seals, connectors, sampling points | EPA Method 21 screening with correlation equations, under an LDAR program |
| Area | Storage tank vents, wastewater basins, cooling towers, landfarms | Emission factors (EPA AP-42) or model calculation |
Three quantification approaches recur:
- Material balance. The most defensible method when the inventory is well measured: what enters minus what leaves in product, waste, and recycle is what was emitted. If a tank farm receives (500{,}000\text{ kg/yr}) of toluene and (499{,}200\text{ kg/yr}) is accounted for in product and shipped waste, the (800\text{ kg/yr}) difference is the emission estimate. The weakness is precision: the emission is a small difference between two large numbers, so a (0.5%) metering error swamps the answer.
- Emission factors. Published mass of pollutant per unit of activity (per (\text{m}^3) processed, per tonne produced, per tank turnover). EPA's AP-42 compilation is the standard source. Fast, but factors carry wide uncertainty ratings.
- Direct measurement. Most accurate, most expensive, and the basis of compliance demonstration for major point sources.
Storage tank emissions split into working losses (vapor expelled as liquid is pumped in) and breathing losses (vapor expelled as the vapor space heats and expands diurnally). Both are attacked structurally: a floating roof eliminates most of the vapor space and is the standard control for volatile liquids in large fixed-roof service; a nitrogen blanket with a vapor recovery unit handles smaller or higher-value streams.
2. Air Emission Control Technologies
| Pollutant | Technology | Governing relation / typical performance |
|---|---|---|
| Particulate, coarse | Cyclone (Section 12.4) | Lapple cut diameter; ineffective below (\sim 5\ \mu\text{m}) |
| Particulate, fine | Baghouse | (> 99%); sized by air-to-cloth ratio |
| Particulate, fine, high volume | Electrostatic precipitator | Deutsch-Anderson, below |
| VOC, dilute high volume | Carbon adsorption (Section 12.3) | Breakthrough curve, regeneration by steam |
| VOC, concentrated | Thermal or catalytic oxidizer | (\ge 99%) destruction typical; RCRA incinerators require (99.99%) DRE on principal organic hazardous constituents |
| VOC, intermittent / emergency | Flare | (98%) destruction credited when operated within 40 CFR 60.18 criteria |
| Acid gas, (\text{SO}_2), (\text{HCl}) | Wet scrubber (Section 12.1) | Absorption with caustic or limestone slurry |
| (\text{NO}_x) | SCR (ammonia + catalyst), low-(\text{NO}_x) burners | (80-90%) reduction |
The Deutsch-Anderson equation for an electrostatic precipitator:
where (w) is the particle migration velocity, (A) the collecting plate area, and (Q) the gas volumetric flow.
Worked example. (w = 0.10\text{ m/s}), (A = 3{,}000\text{ m}^2), (Q = 50\text{ m}^3\text{/s}):
Now tighten the permit to (99.9%). Required (wA/Q = \ln(1/0.001) = 6.908), so (A) must rise by (6.908/6.00 = 1.15), a (15%) area increase. But going from (99%) to (99.9%) requires (wA/Q) to rise from (4.605) to (6.908) — an additive increment of (\ln(10) = 2.303). Every additional nine costs the same absolute increment of (wA/Q), so the marginal cost of capture is constant in "nines" and explosive in absolute terms. That structure is why permit limits expressed as (99.99%) are enormously more expensive than (99.9%), and it appears identically in adsorption bed depth and in scrubber transfer units.
Flares. 40 CFR 60.18 does not itself state a destruction efficiency; it sets the operating criteria a flare must meet — a continuously present pilot flame, exit velocity below the specified limit, and a net heating value of at least (300\text{ Btu/scf}) for steam- or air-assisted flares ((200\text{ Btu/scf}) for unassisted). EPA then credits a flare operated within those criteria with (98%) destruction efficiency for emission inventory and compliance purposes. Over-steaming a flare quenches the flame and destroys the destruction efficiency, which is why steam ratio is controlled rather than maximized.
3. Water and Waste
Wastewater treatment is staged by contaminant class:
- Primary (physical): equalization, oil-water separation (API separator), dissolved air flotation, sedimentation.
- Secondary (biological): activated sludge, trickling filter, anaerobic digestion — for biodegradable organic load measured as BOD/COD.
- Tertiary (polishing): filtration, carbon adsorption, air stripping (Section 12.1), membranes (Section 12.3), advanced oxidation.
Stream segregation is the highest-leverage decision: mixing a small, concentrated, toxic stream into a large dilute one creates a large toxic stream and forfeits the option of treating the concentrate at its source.
The pollution prevention hierarchy, established by the Pollution Prevention Act of 1990, ranks responses:
1. SOURCE REDUCTION <- eliminate the stream (solvent substitution, leak-free seals,
improved conversion/selectivity, closed sampling)
2. REUSE / RECYCLE <- return it to the process or recover the material
3. TREATMENT <- destroy or convert what remains (oxidizer, biotreatment)
4. DISPOSAL <- landfill, deep well, incineration without recovery
Exam questions frequently offer a control device where a process change is available. If one option eliminates the stream and another captures it, the hierarchy says eliminate it.
4. The Regulatory Framework
A licensed PE is expected to recognize which statute governs which stream.
| Statute | Governs | Key mechanisms |
|---|---|---|
| Clean Air Act (CAA) | Air emissions | NAAQS, NSPS, NESHAP/MACT standards, Title V operating permits, PSD review for new major sources |
| Clean Water Act (CWA) | Discharges to surface water | NPDES permits with numeric effluent limits; pretreatment standards for discharge to POTWs |
| RCRA | Hazardous waste | Cradle-to-grave manifest tracking; generator, transporter, and TSDF standards |
| CERCLA (Superfund) | Remediation of contaminated sites | Strict, joint and several liability for cleanup of historical releases |
| EPCRA | Community right-to-know | Toxics Release Inventory reporting; release notification thresholds |
| OSHA PSM (29 CFR 1910.119) | Process safety (Section 20.1) | Fourteen elements including PHA and mechanical integrity |
5. Remediation
Once a release has reached soil or groundwater, technology selection is driven by contaminant volatility, solubility, and biodegradability.
| Technology | Best for | Principle |
|---|---|---|
| Soil vapor extraction (SVE) | Volatile organics in the unsaturated (vadose) zone | Vacuum draws vapor from soil pores to a treatment unit |
| Air sparging | Volatile organics below the water table | Air injected into the saturated zone strips volatiles into the vadose zone, usually paired with SVE |
| Pump and treat | Plume containment; soluble, non-volatile contaminants | Extraction wells create a capture zone; water is treated above ground |
| Bioremediation | Biodegradable hydrocarbons | Stimulate indigenous microbes with oxygen and nutrients; in situ or in a landfarm |
| Permeable reactive barrier | Chlorinated solvents, metals | Passive trench of reactive medium (e.g., zero-valent iron) intercepts the plume |
| Thermal desorption / excavation | Hot spots, high concentrations | Physical removal; fastest, most expensive |
Two practical facts shape almost every remediation question. First, pump and treat is very good at containing a plume and very poor at cleaning one up: once the mobile dissolved mass is removed, contaminant desorbs slowly from soil and the effluent concentration plateaus, a phenomenon called tailing, so cleanup asymptotes rather than finishing. Second, dense non-aqueous phase liquids (DNAPLs) such as chlorinated solvents sink below the water table and pool on low-permeability layers, where they act as a long-term source that no groundwater extraction system can reach. Locating and removing the source zone matters more than pumping the plume.
An electrostatic precipitator currently achieves 98.0% particulate collection. A revised permit requires 99.8%. Migration velocity and gas flow are unchanged. By what factor must the collecting plate area increase?
A plant emits a chlorinated solvent from an open sampling station. Four options are proposed: install a carbon adsorption unit on a new local exhaust hood; route the vent to the existing thermal oxidizer; replace the open station with a closed-loop sampling system; or collect the vapor and landfill the spent carbon. Which option does the pollution prevention hierarchy rank highest?
A site investigation finds trichloroethylene, a dense non-aqueous phase liquid, pooled on a clay layer beneath the water table, with a dissolved plume extending downgradient. A pump-and-treat system has operated for eight years; effluent concentrations dropped rapidly for two years and have since plateaued well above the cleanup standard. What best explains this, and what is the appropriate response?