Encyclopedia of Wildfires and Wildland-Urban Interface (WUI) Fires

Living Edition
| Editors: Samuel L. Manzello

Emissions Measurements

  • Eric GuillaumeEmail author
Living reference work entry
DOI: https://doi.org/10.1007/978-3-319-51727-8_117-1

Synonyms

Definition

Emissions from a fire include both airborne and waterborne products of combustion. Airborne products are most commonly thought of and include both gases and particulate emissions.

Introduction

Wildland fires impact their environment by different pathways and at different contamination levels. At the wildland-urban interface, fires are potentially modified by the presence of other fuels from construction products and human landscaping. These pathways, levels, and fuels influence species to be analyzed and matrixes for the analytes. As generic environmental impact of fires is an increasing topic nowadays (ISO 2011b, 2017), ISO is developing a guide dedicated to the impact of wildland fires (ISO 2018a). There are a lot of variables to be considered when evaluating the environmental impact of wildland fires. Some of these variables have an impact on combustion efficiency and environmental impact (ISO 2011b). Depending on the particular fire conditions, there can be other variables that need to be considered (Sandberg et al. 2002):
  • Fire size influences the quantities of airborne pollutants that are produced.

  • Fire duration influences the quantities of airborne pollutants that are produced and its impact on soils.

  • Fuels type and form, moisture content, and fuel density affect the fire intensity and rate of spread. In a particular wildland fire, the predominant fuel can be grass, scrub or trees, or the fire can progress from an area with one predominant form of fuel to an area with a different predominant form of fuel.

  • Topography: upslope conditions result in a fire that produces different emissions from those produced by a fire occurring under no slope or downslope conditions: the former case results in more efficient combustion. Slopes are also more prone to erosion following a fire (Myronidis and Arabatzis 2009). Postfire turbidity levels in watercourses are affected by the steepness of the burned slopes (Neary et al. 2005).

  • Weather conditions:
    • Weather preceding a fire includes rainfall, air temperature, and humidity. High temperature, no rainfall, and low humidity from a fire produce emissions that are different from those produced by a fire occurring after a period of low temperatures, rainfall, and high humidity: the former case results in more efficient combustion (GAO 2004b). Prolonged drying is not necessary. Surface fuels can dry out sufficiently to support a fire in 1 week without rain (Brotak 2011).

    • Weather during a fire includes wind speed, air temperature, and humidity. High winds, high temperatures, and low humidity results in a fire that produces different emissions from those produced by a fire occurring when there is little or no wind, low temperatures, and high humidity: the former case results in more efficient combustion.

    • Weather following a fire includes rainfall and humidity. Rainfall immediately after a fire can lead to soil loss and contamination of water supplies. Humidity has an influence on the nature and persistence of aerosols and particulates in smoke plumes.

  • Location of sampling: depending on this location, concentration of effluents may vary from several orders of magnitude.

Contamination Overview and Selection of Analytes

Background

The measurement of fire effluents (including soil, water, gases, and aerosols) from wildland fires and at wildland-urban interface remain a great challenge to the analyst (Le Tallec and Guillaume 2008; Fardell and Guillaume 2010). For example, the mobile atmosphere close to the fire may typically be at temperatures of over 1000 °C, highly turbulent, contain a very wide range of compounds (possibly several hundred of direct interest to the toxicologist and environmentalist) and with concentrations varying over several orders of magnitude. The atmosphere will typically contain acidic or corrosive species, labile or unstable species, condensable vapors (including water), and a range of liquid and solid aerosols covering a very wide range of particle size fractions and physical properties. In addition such aerosols may also contain a wide range of adsorbed and/or absorbed chemical species that can contribute to the overall toxicity and environmental effects.

Close to the fire, temperatures are likely to be high enough to promote a range of chemical reactions resulting in a very time-variable content in the effluent. Chemical content of the emission here is likely to be mainly governed by thermodynamic equilibrium considerations. As the distance from the fire increases, the chemical nature of the atmosphere will change due to an increase of kinetically “frozen” chemical reactions as the gases cool. Agglomeration of aerosol particles can occur and any changes in concentrations of species will mainly be the result of dilution rather than further chemical reaction, although some components (e.g., nitrogen oxides, aldehydes) will continue to be modified at cooler temperatures and under other influencers such ultraviolets (UVs). Chemical species may also be partially absorbed and/or condensed onto surroundings. At positions relatively distant from the fire source, other phenomenon such as sedimentation of particulates may occur and affect measurements.

The choice of analytes and analytical techniques depends in a large proportion on the phase of the analysis (air, soil, water), the matrix effects (interactions between analytes and their phase), and the level of concentration. As a consequence, choice of the species to be analyzed and related techniques first starts with study of the contamination pathways as detailed in this section. The effect of these various emissions depends on the transfer mechanism and on the specific species, and these species could present chemical changes after emission. A common example is the evolution of nitrogen oxides (NOx) in the atmosphere due to ultraviolet (UV). A wide variety of toxic effluents are emitted in fires. These effluents can follow a number of pathways to impact on human, animal, or plants targets.

Initial decomposition is generally through pyrolysis, by which combustibles are broken down by heat to yield a range of organic by-products that provide the volatile fuel for combustion. The elemental composition of combustibles provides guidance when predicting the combustion or decomposition products that can be generated during a fire. However, wildland fires consist of a complex mixture of fuels from biomass, largely dependent on land, climate, and the local ecosystem. This can affect combustion efficiency and the mix of combustion products generated in such wildland fires. Fires at wildland-urban interface add other natures of fuels such human-made ones through construction products, furnishing, and finishes. The relative yields of the various combustion and pyrolysis compounds depend mainly upon the combustion conditions. In the evaluation of potential impacts to the environment, ventilation-controlled flaming fires are probably the most environmentally harmful. Recent investigations of emissions from large fires indicate that whereas gases such as CO, CO2, HCN, NOx, and other irritants are most important from an acute toxicological point of view, organic species of high molecular weight and aerosols, polycyclic aromatic hydrocarbons (PAHs) and dioxins, are most significant from an environmental point of view (Blomqvist et al. 2007). Carbon dioxide is the highest airborne combustion product by mass, followed by carbon monoxide (Clinton et al. 2006). Particulate matter (PM10) is probably the third highest airborne combustion product by mass. Fine particulate matter (PM2.5) is produced in particularly large portions during prescribed burning (Lee et al. 2005). Species of interest also include dioxins (Meyer et al. 2004; Tame et al. 2005), hydrocarbons in substantial quantities (Clinton et al. 2006) and aldehydes, mainly formaldehyde (Reisen and Brown 2009).

Contamination Pathways

Air

Airborne emissions from wildland fires comprise particulates, aerosols and gases. Wildland fires are a significant source of airborne particulates and aerosols on a global scale. Their effects could be local and acute near the fire (Lighty et al. 2000), or have an action at long distances, for example, on climate (Sandberg et al. 2002) and/or regional visibility (Bravo et al. 2002). The production of aerosols plays an important role in the regional radiative balance and can produce regional cooling (Christopher et al. 1998). Forest fires, when compared to all fires, are a significant source of PAHs (polyaromatic hydrocarbons) and VOCs (volatile organic compounds) (Blomqvist et al. 2007). Prescribed burns can also have a significant impact on air quality, due to the production of airborne particulates, such as fine particles (PM2.5) (Reisen et al. 2013). Prescribed burning can produce smaller smoke plumes than wildfires (Williamson et al. 2013). Agricultural fires can cause long-term air quality issues (BBC 2013). Gases, especially the lighter ones, are often characterized by their acute effect near the fire. As well as the primary combustion products, secondary combustion products can result from photochemical reactions in the smoke plume (Dokas et al. 2007).

An estimate of the total quantities of pollutants produced in a wildland fire can be modeled by the USDA (US department of Agriculture) First Order Fire Effects Model (FOFEM) (Ryan and Elliott 2005). However, this approach is often oversimplified: Fuel consumption is used to determine the emissions of effluents by multiplying by pre-tabulated emissions factor. During prescribed burns, land-based measuring stations may be used to record both gases and particulates (Lee et al. 2005). Aircrafts have been be used to carry out comprehensive analyses of smoke plumes (Fiedler et al. 2011) and more recently drones. In areas remote from the fire, the impact on air quality should be measured by a 3-hour Pollutant Standards Index (PSI) developed by the US Environmental Protection Agency (Wong 2013). While real-scale fire tests provide important information concerning airborne emissions, some measurements, such as emission factors for CO and CO2, can be conducted at laboratory scale with several limitations: in one hand, laboratory experiments allow to collect all effluents and provide global values more readily. In the other hand, there are some difficulties understanding if the behavior at laboratory scale represents what would occur at larger scales, and phenomenon such smoldering/flaming transition would be different. In that way, laboratory data can overestimate the quantity of emissions of some species (Meyer et al. 2005).

The dispersion of the fire plume within the atmosphere causes elevated concentrations of airborne pollutants, increased risk from exposure to airborne pollutants, and reduced visibility. Particulate atmospheric emission results from reducing visibility and obstructing fire-fighting operations, as well as pervasive reduction in the environmental quality and in potential long-term toxicity. PM10 airborne particles present an important potential environmental problem due to their direct effect on the respiratory system and to their transport of carcinogenic organic species such as PAHs, dioxins, and furans. Both local topography and meteorological conditions, such as wind speed and air stability characteristics, have an influence on the characteristics of dispersion and the extent of the fire plume zone. Furthermore, the fire-fighting strategy also impacts the levels of pollutants in the plume. Short-term environmental impacts are most significant in this zone. Valleys, hills, basins, and canyons, adjacent to or surrounding the fire, constrain dispersion of the plume. Low wind speed, temperature inversions, and other conditions that promote rapid plume deposition also hinder plume dispersion. The combined effects of local topographical features and local meteorological conditions that lead to restricted dispersion are generally additive and result in higher air pollutant concentrations within the fire plume. Visual impairment occurs during fires as a result of atmospheric particles, reducing visibility by scattering and absorbing light. This issue tends to receive lower priority than other environmental aspects because there is no associated biological toxicity or clearly definable cost; nevertheless, it results in a pervasive reduction in environmental quality.

The plume deposition zone encompasses the area under the fire plume zone. The plume deposition zone is influenced by topographical features and meteorological conditions. Air temperature normally decreases with increasing altitude. Reversal of this gradation in which a layer of warmer air lies above a cooler layer is known as temperature inversion. As the cooler layer of air is denser than the warmer layer, it cannot rise, and this results in any pollutants emitted below the “warm” inversion layer becoming trapped. Most particulate deposition occurs close to the fire source. Atmospheric releases also affect terrestrial and aquatic environments through deposition of pollutants. Many thermal degradation products can be adsorbed by the soot particles and be transported with the smoke.

Health and ecological damage can arise from exposure to deposited pollutants though a variety of pathways, such as aerial deposition to water and land, and accumulation in the food-chain and subsequent consumption, either directly or indirectly by contaminated food. Important species in this zone include high-molecular-weight organic compounds, such as PAHs and dioxins. In order to obtain an accurate measure of the environmental impact of a particular fire, full knowledge of weather conditions is essential for the determination of deposition patterns.

Emission to the Terrestrial Environment

Contamination of the terrestrial environment occurs both from direct emissions from the fire and emissions prompted either by fire-fighting activities, or through interaction with weather, especially wind and rain. Atmospheric releases also affect the terrestrial environment through deposition of pollutants, which can be exacerbated through the effect of weather. Pollutants can be solid or liquid, both being soluble or not in water. Adverse impacts include breakdown of surface structure, deposition of ash and impact on soil microbiota (GAO 2004a). Nutrient losses can be enhanced by soil leaching and erosion (Welch 2011). Vegetation removal can lead to erosion and soil loss by wind and by rain. A major short-term impact is an increase in pH as ashes are generally basic. There are also nonadverse effects such as recycling of nutrients (Couto-Vázquez and González-Prieto 2006). The application of fire-fighting chemicals can also have an impact on soil microbiota (GAO 2004a).

Soils could be sampled prior to and following prescribed burning in order to study changes in soil nutrients (Niemeyer et al. 2005). Techniques for the prevention of erosion and soil loss are dependent on the local ecology and climate. Mitigation solutions comprise in the short term mulching and planting of seeds to encourage the rapid regrowth of grasses (Welch 2011). Long term mitigation should include reforestation where appropriate, with potentially less combustible vegetation, depending on land management goals.

Emission to Water Environment

Water fluxes potentially affected include streams, rivers, lakes, water storages, aquifers, and coastal waters (Fowles et al. 2001; Noiton et al. 2001; Fowles 2001). Pollutants can come from water run-off from firefighting activities or rain following fires. Contamination can be caused by combustion products of vegetation, combustion products of manufactured items or structures also involved during fires, soils loosened by vegetation loss and firefighting activities. Pollutants can be solid or liquid both being soluble or not in water. Soluble materials can be toxic to riverine wildlife. Insoluble materials can cause trouble which can interfere with the ecology of a water flux (Adams and Simmons 1999). Vegetation removal can lead to erosion and soil loss by wind and by rain for an extended period after the fire. These sediments run-off into nearby watercourse could be a source of pollution. Water temperatures can also increase due to both radiation and run-off (Neary et al. 2005) and biotopes may be very sensitive to rapid changes in water temperature. Run-off from fires in coastal areas can have a negative impact on the ecology and biota of coastal regions and coral reefs, especially massive release of sediments and water temperature.

The major threat to the water environment posed by fires arises from the direct run-off of contaminated fire-fighting water, foam, and chemical agents into rivers, streams, lakes, coastal water, groundwater, or sewage treatment works, although some threat to water fluxes is caused by the deposition of airborne pollutants into the water environment. Existing water monitoring stations shall are used to provide data on the impact of wildland fires on water quality (Crouch et al. 2006). The impact that any discharge of fire run-off has on the water environment is dependent on a wide variety of factors, including:
  • The volume of run-off produced, the time of travel from the site of the fire to the target, the dilution afforded in the receiving water body, the temperature, chemistry, and type of the receiving water

  • The chemical composition of the run-off, influenced to a great extent by the chemistry of the wildland fire, which involves a complex mix that includes soot, ash, and other suspended solids, the decomposition products of combustion washed off by the run-off, and the fire-fighting agent

  • The sensitivity and the distance time of travel from the fire to the receiving targets, such as public drinking-water abstraction points, fisheries, or valuable aquatic ecosystems

The effects of a water run-off from fires or fire suppression activities to surface water are mainly short term and can include the contamination of public drinking-water supplies during or immediately following the fire. The effects are usually greatest within the immediate vicinity of the fire, where the levels of pollutants are at their highest. As well as short-term impacts, one can observe long-term impacts arising from direct ingestion of some organic compounds in watercourses contaminated by fire-water run-off and/or plume deposition, as well as chronic effects on ecosystems. It is important that run-off water does not reach water treatment plants as these can be rendered nonfunctional by the inclusion of large volumes of pollutants or surfactants such fire-fighting foams. In the case of the pollution of groundwater, the effects can sometimes last for decades as renewal times may be very long, and lead to long-term or permanent closure of some water supplies. The pollution of groundwater can also involve the pollution of groundwater-dependent surface water. The polluting effects of fire-water run-off, related to both surface water and groundwater, are due to direct toxicity of firefighting agent, oxygen depletion, or physical aspects such suspended solids covering the river bed or effecting the gills of fish. Both land and aerial application of fire-fighting media shall be considered. US Forest Service produced guidelines (USDA 2007) to minimize the likelihood of firefighting chemicals entering a stream or other body of water. The Australian authority supplemented guidelines to mitigate impacts on runoff, erosion, and water quality (Smith et al. 2010). For aerial application, US Forest Service recommends to avoid the application of retardant or foam within 100 m of waterways. Where such an application occurs, an immediate assessment of the adverse effects on threatened and endangered species shall be performed (USDA FS/FAM 2007).

Contamination Targets

Impact of Wildland Fire on Wildlife

Remnant populations of endangered species can be extremely vulnerable to wildland fires. Studies shall cover the most endangered species, in particular the quantification of habitat destruction. For some animal species, habitat loss can lead to nonviable populations of species; however, it is difficult to relate that to any specific emissions. Hunt (2015) details the effect of habitat loss for a possum species after Australian fires. It has been proven that amphibian diversity can be affected with increased frequency of prescribed burns (Schurbon and Fauth 2003). Fire retardant chemicals can be toxic to aquatic wildlife and mammals (Smith et al. 2010). Only fire-fighting chemicals that have been tested and met specific requirements with regard to mammalian toxicity shall be used (USDA 2007).

Impact of Wildland Fire on Vegetation

Endangered species of vegetation can be extremely vulnerable to wildland fires. Plant communities can be very complex, and the loss, temporary or permanent, of one species can have an impact on other species. Some species respond more rapidly than others after a fire. Fire can lead to a change in the dominant species in an area (Karpachevskiy 2004). Short-term fire-fighting chemicals can have an impact on the health of plants (Adams and Simmons 1999). They can increase the effects of fire on cations in the soil (Welch 2011). Long-term firefighting chemicals can act as nutrients, having both positive and negative impacts on vegetation (Adams and Simmons 1999). The presence of fire-fighting chemicals can produce greater increases in soil pH than that produced by the fire itself (Welch 2011). Mitigation includes protecting vegetation from further damage caused by run-off, re-seeding as rapidly as possible, and restricting access to critical areas after fires.

Impact of Wildland Fire on Exposed Human Populations

The predominant impact on exposed human populations is from airborne combustion products. The main pollutants are persistent gases and fine particulate matter. While most emissions are from the biomass consumed in the fire, the emissions from man-made articles, including buildings, building contents, and structures, are also to be considered (Reisen 2011). As well as the short-term effects of smoke and gas exposure, prolonged exposure can lead to long-term effects. Smoke haze from wildland fires can have deleterious effects on the health of distant human populations (Sastry 2002). It can significantly increase the mortality burden for effected human populations and has large effects for vulnerable groups, such as seniors (Anon. 2002). If the fire spreads to buildings or infrastructure either in farmland or at the Wildland Urban Interface (WUI), hazardous household materials can be present after the fire (Anon. 2009). The respiratory health impacts identified include chronic respiratory illness people that can experience a worsening in their respiratory symptoms, increase of incidence of mild respiratory symptoms among previously healthy individuals, and increased doses of anti-inflammatory and bronchodilator medication. While airborne combustion products provide the major impact on health, exposures to contaminated soil and water are also health threats (Finlay et al. 2012).

Contamination Duration

Short-Term Impacts

Short-term environmental impacts from exposure to fires pertain mostly to the local environment, within the fire plume zone and water run-off zone. Short-term environmental impacts from exposure arising from atmospheric releases are principally associated with asphyxiant gases and irritant gases/aerosols as detailed in ISO 13571 (ISO 2012b). Species of interest are listed in Table 1. Most toxic releases are unlikely to be generated in sufficiently high concentrations apart from in the local environment so as to result in immediate incapacitation. High concentrations of substances of acute toxicity in run-off water, draining within a local catchment area, represent worst-case impacts on natural water courses and associated aquatic habitats and species. Impacts on land, through deposition, from large fires are unlikely to result in short-term impacts. Environmental impact to surface water is typically short term.
Table 1

Pollutants associated with short-term effects in wildland fires

Species

Analytical environmental phase

Halogenated acids Nitrogen oxides Sulfur dioxide Volatile organic compounds (VOCs)

Air

Metals

Air, water, soil

Particulates

Air, water, soil

Long-Term Impacts

Long-term environmental impacts are those occurring after the fire over a period of years. They are experienced largely within the local environment, within the fire deposition zone and along impacted surface and groundwater. Long-term environmental impacts from emissions within the local environment and within the fire deposition zone are principally associated with persistent organic pollutants and other long-lived toxicants. Pollutants associated with long-term adverse effects of the fire on the environment are listed in Table 2. Long-term environmental impacts on surface waters are rare if sediments are not impacted, as there is a rapid exchange of water. Long-term environmental impacts on groundwater can be due to persistent organic pollutants and metals that are able to percolate into the groundwater system. Effects of endocrine disruptors have also to be considered as they could massively impact reproduction of animal species.
Table 2

Pollutants associated with long-term effects in wildland fires

Species

Analytical environmental phase

Metals

Air, water, soil, sediment

Particulates

Air, water, soil

Perfluorinated compounds (PFCs)

Polychlorinated biphenyls (PCBs)

Water, sediment, soil

Polychlorinated dibenzodioxins and furans (PCDD/PCDF)

(air), water, sediment, soil

Polycyclic aromatic hydrocarbons (PAHs)

Air, water, soil

Volatile organic compounds (VOCs)

Air, water, sediment, soil

Endocrine disruptors

Water, sediment, soil

Sampling

Sampling Requirements

The size of the fire and the distribution or spread of fire effluents into the environment determine the need for, and location of, sampling and analysis in the postfire assessment of the environmental impact. The flow chart shown in Fig. 1 facilitates the determination of which samples should be made and which analysis of the samples is to be preferred. Sampling of the atmosphere may be performed according to ISO 11771 (ISO 2010). Samples from water (surface and groundwater) as well as firefighting water run-off can be collected according to ISO 5667-1 (ISO 2006d) and ISO 5667-20 (ISO 2008e). Sampling of soils can be performed downwind of the fire according to ISO 10381-1 (ISO 2002a).
Fig. 1

Sampling choices

Apparatus and Techniques

The equipment and techniques needed to analyze contaminant samples are dependent on the environmental phase (air, surface water, groundwater, sediment, or soil) and on whether the analysis takes place in situ or in a laboratory. They are also dependent on the nature of the chemical compound or specie of interest. Many compounds and species are emitted into multiple phases as fire effluent or are transported across phase boundaries over time.

Emissions to the Air

Sampling of emissions to the air can mainly be made when the fire is on-going. Sampling from the fire plume is extremely difficult. While attempted at times through airborne sampling from a variety of aircraft or drones, it is unclear how such point samples can be related to deposition. Ground-based sampling below the plume can provide more direct input concerning potential deposition. Grab sampling and postanalysis in the laboratory could also provide data on the emissions of toxic and ecotoxic species, including inorganic gases, PAHs, and dioxins. These data would not, however, be time-resolved and some losses or concentration changes may occur during transportation.

In general, chemical analysis techniques for gases and vapors require a relatively “clean”, stable, cool, sample, free from solid contaminants-conditions rarely arising in fire gases. In presenting such a sample to the analyzer from its source in the fire atmosphere, various losses and physical and chemical changes can be anticipated due to the need to cool and filter the sampled gases and to remove condensable species (e.g., water). It is therefore necessary to take all these factors into account when sampling and analyzing a fire atmosphere. However, for some species it must be accepted that accurate analysis will be very difficult – e.g., where sampling times may not be long enough for a representative sample, or where the species may be highly volatile and subject to change over a short period (e.g., Dioxins). The requirement for any fire atmosphere sampling system is to obtain a realistic and representative sample for presentation to the analysis equipment. How far this ideal is achieved depends on a number of factors including the chemical and physical nature of the species for analysis, the temperature, length, and material used for the sampling probe and extract tubing (sampling line), sample flow rate, the type and position of particulate filters, and type and position of condensate (e.g., water) traps. Fardell and Guillaume (2010) give a lot of recommendations on sampling and analysis of fire effluents.

Sampling can be either “extractive” where the samples are removed from the fire for analysis either immediately or at a later stage, or “in situ” where the measurements of chemical species are made directly at their point of generation, e.g., the space within or immediately surrounding the fire. The choice is often limited by the methodology available for analysis or the risk associated with the sampling. The more commonly used extractive methods usually utilize a sampling probe positioned at the required sampling point, connected to an inert (often heated) tube connected to a pump to conduct samples continuously to the collection or analysis point. Particulate filters and condensate traps are also commonly used in such a sampling line. The samples may be analyzed immediately or stored for analysis at a later stage. Typical extractive methods include:
  • Direct continuous analysis from the sampling line using nondispersive infrared spectroscopy (NDIR) for CO, CO2, paramagnetism for O2, quasi-continuous analysis by Fourier transform infra-red spectroscopy (FTIR) for a variety of inorganic and organic species.

  • Indirect analysis from the sampling line (Gas valve, gas syringe or auto-sampler followed by gas chromatography (GC) or GC/mass spectrometry (GC/MS)) for many inorganic and organic species.

  • Trapping with a solid adsorbent/absorbant, with chemical reaction e.g., silica with a 2,4-dinitro phenyl hydrazine (DNPH) coating for aldehydes and ketones.

  • Trapping by solid, inert, adsorbent, e.g., “zeolites” or activated charcoal for polycyclic aromatic compounds (PAH), benzene, and other volatile organic compounds (VOC) followed by GC/MS or GC/flame ionization detector (FID).

  • Trapping by solution in the liquid phase, e.g., sodium hydroxide (NaOH) solution for HCN, HF, water for HCl, HBr, hydrogen peroxide (H2O2) for SO2, and HCl + DNPH for aldehydes.

  • Collection in an inert bag (e.g., chemiluminescence for analysis of oxides of nitrogen).

As a general rule the sampling probe and sampling line should both be inert to the species of interest and other compounds present in the effluent, be heated to a temperature sufficient to avoid condensation of any component of the sample, be as short as possible to minimize losses, and have a high extract velocity to limit the time delay between sampling point and analyzing or trapping system. Fire plume sampling or sample collection procedures shall be as possible conducted in accordance with standardized methods as included in ISO 19701 for sampling for in-situ and laboratory analysis for general fire gases (ISO 2013c), ISO 19702 for sampling for in-situ FTIR analysis (ISO 2015), ISO 29904 for aerosols (ISO 2013d), ISO 12884 (ISO 2000), and ISO 16362 (ISO 2005c) for PAH.

Consideration must also be given to the storage of samples not analyzed in real time directly from the sampling line. This will arise where samples such as those from a bubbler train, solid sorbant sampling tube, or inert gas bag are to be analyzed at some period after collection. Clearly, to reduce losses it is important to store such samples for the minimum possible time and under refrigerated conditions where possible. In some cases, the adsorbing and/or absorbing medium where used can react with the required species over time and produce a lowering of the measured concentration.

Recently, qualitative and semi-quantitative methods have been used to obtain gas-phase data from external fires, without sampling. These are detailed in section “Long-Distance Atmospheric Measurements.”

Emissions to the Water Environment

Emissions to the aquatic environment can affect both surface and ground water. Transport of fire effluents to the aquatic environment can occur through deposition of airborne contaminants onto soil or water surfaces or from fire water run-off that carries extinguishing media and/or residue from the fire ground. The location and nature of sampling should be based on the knowledge of the pathway by which fire water run-off spreads into the environment. A detailed postincident analysis of pathways should be conducted to reveal all potential or actual routes to receptors.

The exact analysis of the samples should be determined on the basis of the fuel involvement from the fire and their likely breakdown products, as well as on the fire-fighting agent used. Examples of the determinants that can be analyzed include PAHs, volatile organic compounds (VOCs), hydrocarbons, ammonia (NH3), pH, biochemical oxygen demand (BOD), chemical oxygen demand (COD), and suspended solids (SSs). In some cases, toxicity tests and biological monitoring can also be useful. Dioxins or metals are rarer in such natural fires as chlorine/bromine or lead are not necessary supposed to be massively present in the original fuel, but depending on the scenario, wildland fire could also affect specific areas such human occupation sites that could generate such effluents.

Liquid samples should be collected in accordance with standardized methods; such methods are detailed in Table 3 and include ISO 5667-1 (ISO 2006d) for waster waters, sludge, effluents, and bottom deposits. ISO 5667-6 (ISO 2005d) for rivers and streams, ISO 5667-10 (ISO 1992) for waste water, and ISO 5667-11 (ISO 2009b) for groundwater. ISO 5667-15 (ISO 2009c) provides guidance on procedures for the preservation, handling and storage of samples of sewage and waterworks sludge, suspended matter, saltwater sediments and freshwater sediments, until chemical, physical radiochemical and/or biological examination can take place. It only applies to wet samples. Liquid phase samples should be stored and handled in accordance with standardized methods; such methods include the USEPA Method 1669 for metals (USEPA n.d.).
Table 3

Guidance available for water environment sampling

References

Details

ISO 5667-1 (ISO 2005d)

Provides guidance on the design of sampling programs and sampling techniques for all aspects of sampling of water (including waste waters, sludge, effluents, and bottom deposits)

ISO 5667-6 (ISO 2005d)

Provides guidance on the design of sampling programs, sampling techniques and the handling of water samples from rivers and streams for physical and chemical assessment

Not applicable to estuaries, coastal waters, sediment, suspended solids, or biota and has limited applicability to microbiological sampling

ISO 5667-10 (ISO 1992)

Contains details on the sampling of domestic and industrial waste water, including the design of sampling programs and techniques for collection of samples

Covers all kinds of waste water, but not accidental spillage

ISO 5667-11 (ISO 2009b)

Guidance on necessary considerations when planning groundwater sampling for assessing quality

Includes saturated and unsaturated zones

Not applicable for potability measurements

ISO 5667-12 (ISO 1995)

Provides guidance on the sampling of sediments from rivers, streams, lakes, and similar standing waters and estuaries. Sampling of industrial and sewage plant sludge and ocean sediments are excluded

Consideration must be given to the storage of samples not analyzed in situ but at some period after collection. Clearly, to reduce losses it is important to store such samples for the minimum possible time and under refrigerated conditions where possible. In some cases the adsorbing and/or absorbing medium where used can react with the required species over time and produce a lowering of the measured concentration.

Emissions to the Terrestrial Environment

Samples of soil in the downwind direction from the fire and in the path of the fire plume should be taken, downwind being used as reference. The exact analysis of the samples should be determined on the basis of the fuel involved as well as on the basis of the fire-fighting agent used. Examples of the determinants that can be analyzed for include PAHs, and pH. In some cases, toxicity tests, dioxins, and metals analysis can also be useful.

Emissions may occur to the terrestrial environment. Samples of soil and sediment should be taken of soil at least in the downwind direction from the fire in the path of the fire plume. Solid phase sample collection procedures should be conducted in accordance with standardized methods; such methods include ISO 5667-12 (ISO 1995) for sediments, ISO 10381-1 (ISO 2002a) and ISO 10381-5 (ISO 2005a) for soils, ISO 5667-1 (ISO 2006d) for sludge and effluents and bottom deposits. ISO 10381-1 (ISO 2002a) describes general principles for designing sampling programs for characterizing and controlling soil quality and identifying sources and effects of contamination. It emphasizes sampling locations, instrumentation, sample size, combination of samples, collection methods, and containment, storing, and transport of samples. ISO 10381-5 (ISO 2005a) provides guidance on the procedure for investigating urban and industrial sites where soil contamination is suspected. This is useful when there is a need to establish the environmental quality of a site. It includes guidance on the collection of information for risk assessments and remediation action plans.

Solid samples should be stored and handled using standardized procedures to preserve the sample quality; such methods include ISO 5667-15 (ISO 2009c) and ISO 10381-2 (ISO 2002b). This last standard gives guidance on techniques for taking and storing soil samples. It includes information on equipment and references to groundwater and soil gas sampling. It is not applicable to hard strata. As for air and water samples, consideration must be given to the storage of samples should at some period after collection. Losses of volatile compounds is one of these issues. Soil samples shall be preserve in inert and tight containers such glass flacons and kept in relatively fresh conditions where possible. In all cases, samples may evolve from sampling to analysis and corrections may occur.

Analysis

Pollution Indicators

Every major change in physical or chemical compositions of water or soils (and in a lesser extend air) should be considered as an indicator of pollution. Pollutants indicators that either typically occur as a result of a large outdoor fire (including wildland fires and WUI fires) are listed ISO 26367-2 (ISO 2017) and are also given here. The properties listed in Table 4 represent general indicators of environmental pollution, the relevant environmental phase, and examples of available techniques in each case. Specific pollutants can be associated with short-term adverse effects and/or long-term adverse effects on the environment.
Table 4

Guidance available for pollution indicators analysis

Indicator

Phase

References of the method

Biological oxygen demand (BOD)

Water (surface and groundwater), sediment

ISO 10707 (ISO 1994a) ISO 10708 (ISO 1997)

Chemical oxygen demand (COD)

Water (surface and groundwater), sediment

ISO 15705 (ISO 2002d)

Alkalinity

Water (surface and groundwater), sediment, soil

ISO 9963-1 (ISO 1994c) ISO 22719 (ISO 2008d)

Acidity – pH

Water (surface and groundwater), sediment, soil

ISO 10523 (ISO 2008a) ISO 10390 (ISO 2005b)

Electrical conductivity

Water (surface and groundwater), sediment, soil

ISO 7888 (ISO 1985)

Soil

ISO 11265 (ISO 1994b)

Turbidity

Water (surface and groundwater)

ASTM D 4189 (ASTM 2007a)

Hydrocarbon and oil

Water (surface and groundwater), sediment, soil

ASTM D 5412 (ASTM 2011)

Toxicity assessment (direct)

Water (surface and groundwater)

ISO 6341 (Daphnia test) (ISO 1996a)

Soil

ISO 15952 (Snail test) (ISO 2006a)ISO 17155 (ISO 2002e)

Fire effluents could affect global parameters of waters and soils such biological oxygen demand (BOD) or chemical oxygen demand (COD). These two parameters are essential characteristics of media and used for potability measurements. Other global parameters of interest include alkalinity, acidity and conductivity of water, all possible indicators of modifications to the phase. Alkalinity is covered by ISO 9963-1 (ISO 1994c), which specifies a method for the determination of alkalinity of water, applicable for the analysis of natural and treated water, and waste water. For sea water, ISO 22719 (ISO 2008d) is recommended. Acidity of water is covered in ISO 10523 (ISO 2008a), describing a method for determining the pH value in rain, drinking and mineral waters, bathing waters, surface and ground waters, as well as municipal and industrial waste waters, and liquid sludge, within the range pH 2 to pH 12. Soils are covered in ISO 10390 (ISO 2005b). Conductivity is covered in ISO 7888 (ISO 1985).

Turbidity is also a parameter of first importance to describe how fire plume deposition and fire water run off could affect the surface water. ASTM D 4189 (ASTM 2007a) may be used for the determination of the silt density index (SDI) of water. This test method can be used to indicate the quantity of particulate matter in water and is applicable to relatively low turbidity waters (1.0 NTU) such as well water, filtered water, or clarified effluent samples. Since the size, shape, and nature of particulate matter in water may vary, this test method is not an absolute measurement of the quantity of particulate matter.

PAH and oil residues in water are covered by methods such as ASTM D 5412 (ASTM 2011). This test method covers a mean for quantifying or characterizing total polycyclic aromatic hydrocarbons (PAHs) by fluorescence spectroscopy (Fl) for waterborne samples. The characterization step is for the purpose of finding an appropriate calibration standard with similar emission and synchronous fluorescence spectra.

There are also toxicity test methods (direct methods), which evaluate the global impact on target species, whatever the pollutant is. These methods are powerful as they do not request identification of the origins of contamination. However, it is sometimes difficult to relate the observed effect to the suspected cause. For example, significant mortality in the target species may be related to factors other than those thought to be due to fire effluents, making interpretation difficult. Some analysis techniques address eco-toxicity in a general sense, such as ISO 17155 (ISO 2002e) for soils. These techniques measure the effects of the contamination on the environment rather than concentrations of specific chemicals. Daphnia tests are used for water; trout and Salmonidae are also good indicators of water pollution, supposing a preexisting sufficient population. Juvenile snails or earthworms are commonly used to characterize soil pollution.

Analytical Techniques Suitable for Air

Ground and Laboratory Analysis

Analysis of air contamination should be made using standardized in-situ measurement methods or by laboratory analysis of collected air samples. Table 5 gives an overview of main test methods. Fardell and Guillaume (2010) ISO 19701 (ISO 2015) and ISO 19702 (ISO 2013c) provide more details on several analytical techniques.
Table 5

Guidance available for atmospheric analyses of pollutants from fires

Species

Reference method

General atmospheric pollutants

ISO 19701 (ISO 2013c)

ISO 19702 (ISO 2015)

Volatile organic compounds (VOC)

ISO 19701 (ISO 2013c)

ISO 19702 (ISO 2015)

Polycyclic aromatic hydrocarbons (PAH)

ISO 12884 (ISO 2000)

ISO 16362 (ISO 2005c)

Polychlorinated dibenzodioxins and furans (PCDD/PCDF)

EN 1948-3 (CEN 2006)

ISO 16000-14 (ISO 2009a)

Metals

ISO 19701 (ISO 2013c)

General atmospheric pollutants of interest include CO, CO2, hydrogen halides, sulfur dioxide, nitric oxides. Ozone could be interesting too at large distances, as a secondary generated pollutant following atmospheric reactions. These species can be all measured with a large number of techniques, including the appropriate methods given in ISO 19701 (ISO 2013c), ISO 19702 (ISO 2015), and ASTM E 800 (ASTM 2007b). ASTM E 800 is a tool for the selection of a suitable technique from alternatives to quantify gaseous fire effluent, but it does not provide enough information for the setup and use of a specific procedure. Several other methods are available from airborne analysis standards from ISO TC 146, but they have not necessary being evaluated on matrixes such fire effluents.

ISO 12884 (ISO 2000) specifies sampling, cleanup, and analysis procedures for the determination of polycyclic aromatic hydrocarbons (PAH) in ambient air. It is designed to collect both gas-phase and particulate-phase PAH and to determine them collectively. Samples are collected on sorbent-backed filters followed by gas chromatographic/mass spectrometric analyses. ISO 16362 (ISO 2005c) specifies a sampling and analysis procedure for PAH that involves collection from air onto a filter followed by analysis using high performance liquid chromatography usually with fluorescence detector (FLD).

Standardized methods available for dioxins and furans have been developed for constant emission sources and then are difficult to apply in fire-related environment. The most important methods for air phase are those developed for constant emission according to EN 1948 – 3 (CEN 2006) or for interior air according to ISO 16000 -12 to -14 (ISO 2008b, c, 2009a), generally using gas chromatography coupled with isotopic dilution. However, although dioxin concentrations in the atmosphere are often not able to generate dangerous conditions for populations, contamination of soil, water, and ultimately food is more critical, which is why these other phases of analysis are more important for such species than atmosphere.

Particulates and aerosols are of first importance in fire plume and sometimes far from fire. Parameters of interest are their total concentration, their optical properties (often represented by their extinction coefficient), their size distribution (often represented by their aerodynamic diameter distribution), the morphology of the particles, and their chemical composition. Depending on the objective and sampling possibilities, there are many different techniques applicable. These analytical methods are described in ISO 29904 (ISO 2013d). Some methods are also used to monitor air quality and air pollution stations may be a good tool to assess ground concentration of aerosols, often through PM10 and PM2.5 values. In air quality measurements, the reference method used for the sampling and measurement of PM10 and PM2.5 is that described in EN 12341 (CEN 2014).

Long-Distance Atmospheric Measurements

LIDAR and infrared spectroscopy (open field) have been used for the analysis of fire gases and provide valuable semi-quantitative data (Ward and Radke 1993). LIDAR consists of emitting laser pulses into the atmosphere and analyzing the backscattered radiation at the same wavelength using a telescope, using the absorption and scattering properties of the laser light by particles and molecules. Differential absorption LIDAR (differential absorption Lidar, DIAL) is the most widely used. The laser source emits simultaneously in the atmosphere at two wavelengths, one is strongly absorbed by the gas considered and the other is weakly absorbed. By applying the Beer-Lambert law, the concentration of the desired gas as a function of distance is determined by difference. LIDAR is able to provide quantitative data on particles through long-distance light-scattering coefficients along the fire plume. In addition to airborne particles, LIDAR can also detect, for example, the following gases: benzene, toluene, xylene, styrene, ozone, sulfur dioxide, carbon monoxide, nitric oxides.

More recently, terahertz analysis has been performed on fire plumes and has been shown as valuable for gases such HCN (Song and Nagatsuma 2015). Validation has been made compared to sampling methods. The results shown the feasibility of portable systems used as gas sensors in fire disasters.

In addition to being devastating for local ecosystems and economies, wildfires significantly alter air quality, sometimes on regional to hemispheric scales, and are an important component of the climate system. Satellite analysis is suitable for such purpose. Instruments such as Infrared Atmospheric Sounding Interferometer (IASI) on board METOP-A satellite have demonstrated the possibility to assess carbon monoxide (CO) during extreme fire events several hundred kilometers far from the fire, giving quantitative results of the concentration of atmosphere columns (Turquety et al. 2009).

Analytical Techniques Suitable for Water Run-Off

Analytical methods used for water run-off are listed in Table 6. Currently, the most sensitive and practical means for measuring low concentrations of trace elements are by graphite furnace atomic absorption spectrophotometry as proposed in ASTM D3919 (ASTM 2015e), by direct current plasma atomic emission spectroscopy (DCP) as covered by ASTM D4190 (ASTM 2015f), or by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) according to ASTM D5673 (ASTM 2016).
Table 6

Guidance available for water analyses of pollutants from fires

Species

Reference method

Cyanides (free and metal-complexed)

ASTM D6888 (ASTM 2009a)

ASTM D7284 (ASTM 2008)

Metals and elements

ISO 11885 (ISO 2007a)

Polycyclic aromatic hydrocarbons (PAH)

ASTM D5412 (ASTM 2011)

Volatile organic compounds (VOC)

ISO 15680 (ISO 2003)

ISO 20595 (ISO 2018b)

Polychlorinated biphenyls (PCB)

Perfluorinated compounds (PFC)

ISO 6468 (ISO 1996b)

Polychlorinated dibenzodioxins and furans (PCDD/PCDF)

ISO 18073 (ISO 2004b)

Cyanides in water environment are often a consequence of water run-off. Sampling, preservation, and mitigation of interferences for water samples intended to be analyzed for cyanides is covered in ASTM D7365 (ASTM 2009b). As speciation is of first importance with cyanides, analysis of free cyanide (HCN and CN) in natural water, saline waters, and wastewater effluent is covered by ASTM D6888 (ASTM 2009a) by gas diffusion separation and amperometric detection. ASTM D7284 (ASTM 2008) is used for free cyanides that are free and strong-metal-cyanide complexes that dissociate and release free cyanide when refluxed under strongly acidic conditions.

Metals are frequent contaminants to water from massive outdoor fires, as released from soils, mines, or vegetation, which can concentrate specific metals. ISO 11885 (ISO 2007a) specifies a method for the determination of dissolved elements, elements bound to particles (“particulate”), and total content of elements in different types of water (e.g., ground, surface, raw, potable, and waste water) for the following elements: aluminum, antimony, arsenic, barium, beryllium, bismuth, boron, cadmium, calcium, chromium, cobalt, copper, gallium, indium, iron, lead, lithium, magnesium, manganese, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silver, sodium, strontium, sulfur, tin, titanium, tungsten, vanadium, zinc, and zirconium. Methods specific of several metals are also described, such ASTM D2972 (ASTM 2015a) for arsenic in water through the photometric and atomic absorption method. ASTM D3558 (ASTM 2015b) covers dissolved and total recoverable cobalt in water by atomic absorption spectrophotometry. ASTM D3559 (ASTM 2015c) concerns dissolved and total recoverable lead in water by atomic-absorption spectrophotometry and differential pulse anodic stripping voltammetry. ASTM D3859 (ASTM 2015d) covers the dominant species of selenium reportedly found in most natural and wastewaters, including selenities, selenates, and organo-selenium compounds.

ASTM D5412 (ASTM 2011) covers a means for quantifying or characterizing total polycyclic aromatic hydrocarbons (PAHs) by fluorescence spectroscopy (Fl) for waterborne samples. The characterization step is for the purpose of finding an appropriate calibration standard with similar emission and synchronous fluorescence spectra.

Volatile organic compounds in water may be analyzed by gas-chromatography using purge-and-trap and thermal desorption according to ISO 15680 (ISO 2003). The most highly volatile species could be analyzed using gas chromatography and mass spectrometry using a static headspace technique (HS-GC-MS) according to ISO 20595 (ISO 2018b).

Polychlorinated biphenyls (PCB) or perfluorinated compounds (PFC) in water can be analyzed using gas chromatography after liquid-liquid extraction according to ISO 6468 (ISO 1996b). This method is adapted to water containing suspended solids. For dioxins and furans, as quantities may be very low, method using isotope dilution from ISO 18073 (ISO 2004b) is recommended.

Analytical Techniques Suitable for Soils

Contamination of soils from fire effluents is probably the most important pathway in terms of long-term contamination. Analytical techniques listed in Table 7 are applicable for soils include sediment, soil, and fire debris. ISO 22892 (ISO 2006c) may be used as a guidance for the identification of target compounds that could be extracted and analyzed through mass spectrometry. A large part of compounds of interest, including metals, are analyzed through ISO 11047 (ISO 1998) using atomic absorption or by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS).
Table 7

Guidance available for soil analyses of pollutants from fires

Species

Reference method

Metals and elements

ISO 11047 (ISO 1998)

Polycyclic aromatic hydrocarbons (PAH)

ISO 18287 (ISO 2006b)

ISO 13859 (ISO 2014a)

Hydrocarbons

ISO 16703 (ISO 2004a)

Volatile organic compounds (VOC)

ISO 15009 (ISO 2016b)

Polychlorinated biphenyls (PCB)

ISO 10382 (ISO 2002c)

ISO 13876 (ISO 2013a)

Perfluorinated compounds (PFC)

ISO 22155 (ISO 2016c)

Polychlorinated dibenzodioxins and furans (PCDD/PCDF)

ISO 13914 (ISO 2013b)

Endocrine disruptors

ISO/TS 13907 (ISO 2012c)

ISO 13913 (ISO 2014b)

Polycyclic aromatic hydrocarbons (PAH) are analyzed through ISO 18287 (ISO 2006b) and ISO 13859 (ISO 2014a), respectively, through GC-MS and HPLC techniques. Hydrocarbons in the range C10–C40 are covered by ISO 16703 (ISO 2004a). Volatile aromatic hydrocarbons, naphthalene, and volatile halogenated hydrocarbons are covered in ISO 15009 (ISO 2016b) through purge-and-trap method with thermal desorption.

Polychlorinated biphenyls (PCB) analysis in soils is covered in ISO 10382 (ISO 2002c) and ISO 13876 (ISO 2013a). Perfluorinated compounds (PFC) are analyzed through ISO 22155 (ISO 2016c). ISO 13914 (ISO 2013b) specifies a method for quantitative determination of 17 2,3,7,8-chlorine substituted dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls in sludge, treated biowaste, and soil using liquid column chromatographic cleanup methods and GC/HRMS.

Endocrine disruptors in soils are of first interest. ISO/TS 13907 (ISO 2012c) describes the gas chromatography with mass selective detection (GC-MS) method to analyze nonylphenols (NP) and nonylphenol-mono- and diethoxylates in soils. ISO 13913 (ISO 2014b) covers phthalates using capillary gas chromatography with mass spectrometric detection.

Metrology of Measurement

Range of Analysis: Limits of Detection and Quantification

Data on the environmental impact of fire effluents may be required from a variety of sources by the environmentalist and for a variety of end uses (e.g., calculations to estimate health hazards to local populations). It is important to ensure that the sampling and analysis procedures and methodologies employed should reflect the required limits of concentration, quantification, accuracy, and precision of the end use of the results. Thus, there is probably little value in employing a range of highly sophisticated (and possibly expensive) instrumentation to determine the concentrations of a large number of species to a high degree of accuracy and precision when the data will be used for estimations of hazard using far less sophisticated calculations with relatively wide “error bands.” In presenting chemical analysis results therefore, it is clearly of importance to be able to state for a particular sampling and analysis regime, the limits of detection (LoD), and limits of quantification (LoQ) for specific compounds. ISO 12828-1 (ISO 2011a) covers these two aspects within fire effluents and is especially adapted to airborne effluents in fire plume. The range of the method is also of first importance. It is defined as the values between where a quantitative analysis is feasible and can be achieved in practice. Its lower limit is mainly characterized by the limits of detection and quantification for the particular species with the chosen method.

Accuracy, Repeatability, and Reproducibility

It is necessary to choose a methodology, which has been proven to be repeatable and reproducible and not overly sophisticated and/or expensive for the required particular end use. This includes uncertainties estimates.

Accuracy is defined as the difference between the real value and the true value, where this last quantity is never really known in the field of fire emissions. Trueness, although a key parameter, is difficult to measure in fire effluent analysis. Repeatability is the coherence between results obtained on a given measurement in one laboratory, by one operator and one piece of equipment. Reproducibility is the coherence between results obtained in various laboratories for the same published method. For both repeatability and reproducibility, it is also essential to separate the processes involved in the chemical analysis with the processes involved in the fire event itself. As wildland fires are by nature unique, only the first cited component from the method may be evaluated. So, these notions are generally verified on small scale experiments. A proper analytical method shall have been evaluated in the range and matrix similar to those for the expected analysis. Effects of sampling are difficult to assess in such conditions.

ISO 12828-2 (ISO 2016a) presents examples of complete method validation for fire effluents. ISO 20988 (ISO 2007b) provides more general guidelines for estimating measurement uncertainty and may be used for generic airborne pollutants. Water analyses uncertainties are described in ISO 11352 (ISO 2012a).

Cross-References

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Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Efectis FranceSaint AubinFrance

Section editors and affiliations

  • Michael Gollner
    • 1
  1. 1.Department of Fire Protection EngineeringUniversity of MarylandCollege ParkUSA