Hydrogen Sulphide in Agricultural Biogas Systems
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Hazardous gases are found in many locations on farms where organic material is present. These areas may contain dangerous levels of gases, such as hydrogen sulphide (H2S), if the gases are not handled properly. This Factsheet focuses on H2S found around agricultural biogas systems and recommends safety precautions for protecting farm workers.
When biogas is produced for renewable energy production, 50%70% of the gas volume is made up of methane (CH4). Biogas also contains a lot of carbon dioxide (CO2), 30%50% by volume, and traces of gases such as ammonia (NH3), hydrogen (H2) and nitrogen (N2) along with (H2S). Input feedstocks and output digestate materials (including manure) can produce these gases when stored, mixed or handled in biogas systems. These gases are considered dangerous and can create a hazardous atmosphere if ventilated improperly. H2S is most commonly found and is considered the most dangerous of the gases.
Exposure to elevated concentrations of H2S is extremely harmful. H2S interacts immediately with the blood's hemoglobin to block oxygen from being carried to the body's vital organs and tissues. Table 1 describes the effects of H2S on human health.
A major concern with the detection of H2S is that the human nose loses its ability to detect the gas when exposed to dangerous levels or for prolonged periods of time. This results in a false sense of security. Never rely on the sense of smell to detect H2S, instead use a personal gas monitor to monitor levels.
Source: American Society of Agricultural and Biological Engineering Standards, 2003
H2S is heavier than air, so it is found just above the surface of the organic material undergoing decomposition. Presently, there are no standards for H2S exposure limits in the farm workplace, but employers must take all reasonable precautions to protect the health and safety of workers. A current best management practice in Ontario is to set the minimum alarm level at 10 parts per million (ppm) for H2S on gas monitoring devices in areas where H2S is present.
Locations where H2S is found around agricultural biogas systems are divided into three categories:
The following sections describe the potential sources of H2S gas in these areas and the best management practices for reducing associated risks.
Agricultural Source Input Materials
The most common agricultural source input material is manure, either in a liquid or solid form. Liquid manure is usually stored in below-ground concrete/earthen storages where H2S and other hazardous gases can develop. In contrast, solid manure is stored outside in the open where the potential to accumulate hydrogen sulphide is minimal. Other solid materials, such as feeds for livestock, are stored in a sealed environment or in structures where air circulates.
Dangerous levels of H2S, methane or nitrogen dioxide (NO2, commonly known as silo gas) are present in these structures and can cause serious health problems. See OMAFRA Factsheet, Hazardous Gases on Agricultural Operations, Order No. 13-025, for information on how to recognize and manage these common hazards associated with agricultural operations.
Liquid Nutrient Transfer Systems
Liquid nutrient transfer systems are used to transfer liquid manure from the livestock operation to the anaerobic digester. Sump-like pits are located inside (floor transfer system, Figure 1) or outside the livestock barn to collect liquid manure from the livestock operation. Both of these systems have the potential to generate and accumulate dangerous levels of H2S.
An agricultural biogas system may use nutrient transfer systems located in a partially enclosed facility to pump liquid manure from the barn and to mix in drier agricultural source materials. This practice represents a higher risk of producing and releasing H2S in enclosed areas, where it can get trapped, and increases the risk of exposure to unsafe levels of H2S.
Figure 1. A liquid nutrient transfer system where liquid manure from the livestock facility is transferred to the anaerobic digester.
Past research demonstrates that mixing liquid hog manure stored in sub-floor slurry storage pits immediately releases a rapid surge of H2S (Patni and Clarke, 2003). The following management suggestions are provided to reduce the risk of exposure to H2S around nutrient transfer systems:
Off-farm Input Materials: Co-substrate Input Tank
Using off-farm materials to boost biogas production is a popular practice for agricultural biogas systems. Materials such as grease from restaurants and residues from agri-food processing are co-digested with livestock manure generated on the farm. If the dry matter content (DM) of these off-farm materials is less than 18% or is easily pumped, they must be stored in a sealed tank called a co-substrate input tank (Figure 2). Gas production by active bacteria can accumulate inside the sealed co-substrate tank.
Figure 2. An in-ground co-substrate input tank where liquid off-farm materials such as fats, oils and grease are stored temporarily.
The following management practices and design features are recommended to minimize the risk of exposure to generated gases:
Off-farm Input Materials: Dry Off-farm Materials
Dry off-farm materials, typically greater than 30% dry matter, are commonly ensiled on the farm in partially enclosed horizontal silos (Figure 3). Hydrogen sulphide and nitrogen dioxide can be trapped inside the materials and released when handled or mixed. Also, the pile can heat up if left unattended for an extended period of time.
Figure 3. A horizontal concrete silo use to store drier off-farm materials such as corn husks and grape pumice.
Best management practices to safely store these materials and reduce risk of exposure to H2S include the following:
Anaerobic Digester with Over-Under Pressure Relief Valve
The vessel where biogas production occurs is called the anaerobic digester. It is equipped with a safety valve called the over-under pressure relief valve to avoid unsafe gas pressure levels (negative or positive) in the tank. During normal operating conditions, consider the following best practices and design features to minimize risk of exposure to H2S gas:
Figure 4. A freeze-proof over-under pressure relief valve installed on an anaerobic digester in Ontario.
Operators may have to remove the inflatable gas storage membrane or cover to repair equipment inside the anaerobic digester, during certain maintenance procedures. It is essential that operators follow the safety procedures learned in their training due to the hazards encountered.
The anaerobic digester contents continue to produce biogas and H2S even when the cover or gas storage membrane is removed. It is dangerous to enter an anaerobic digester that has recently been emptied. H2S and other dangerous gases will linger at the bottom of the tank and inside the tank's sediments.
To minimize exposure to H2S and hazardous gases during maintenance procedures:
Condensation Trap (Condensate collection or drip trap)
In most agricultural biogas systems, moisture in the biogas is removed by passing it through an underground network of cooling pipes. The moisture cools and condenses, and is collected at the lowest point in a structure, called a condensation trap (Figure 5). The trap has a high probability of containing H2S, other hazardous gases and low levels of oxygen. Access to this structure must be restricted, as the condensation trap is considered a confined space.
Figure 5. Access point to the condensation trap where the moisture removed from the biogas is collected.
Storage of Output (Digested) Materials After Digestion
Liquid Digestate Storage
Handling liquid digestate for land application is as dangerous as handling undigested manure. Fresh digestate from the anaerobic digestion tank contains active bacteria and will release H2S and other hazardous gases for a short time. Although a high fraction of the organic matter is converted to biogas, other organic materials (such as straw and sawdust) decompose slowly during long-term storage and trap H2S in the liquid digestate. Hire an engineer to design the liquid digestate storage (Figure 6) and ensure that H2S and other hazardous gases are:
Storing digestate in an under-barn storage, unless it is designed by a professional engineer, is not a recommended practice for several reasons:
Figure 6. An earthen permanent digestate storage that resembles common permanent liquid manure storages used on dairy farms.
Separated Manure Solids
Some biogas operators process output digestate materials using a solid manure separator. The materials are used for bedding, compost or even as a surface cover over feedstock materials. They typically do not sit in the same location for long and are kept away from precipitation; otherwise, the solids may start to ferment. H2S can be trapped in the solids, and exposure must be managed.
To minimize this hazard:
Figure 7. A manure separator connected to the anaerobic digester used to separate the solid fraction of digestate.
Certain activities can generate an increased risk of exposure to H2S. These activities include:
To reduce these risks:
Hazardous gases are measured with commercial handheld monitors available from safety and scientific supply stores (Figure 8). Gas monitors monitor environmental gases constantly, are compact in size, and sound an alarm when a dangerous gas level is detected. When purchasing a gas monitor for H2S, verify whether the unit can be calibrated at the farm or has to be serviced. Certain units will stop working if the calibration has expired. Operating the calibrating equipment can be done with minimal training. The cost for the monitors ranges from $250 to $400.
Figure 8. A personal hazardous gas monitor, which triggers an audible and visual alarm when acceptable concentration of a gas goes beyond the safe threshold.
There are many confined spaces on the farm where hazardous gases are a risk. See Section 7 of the Occupational Health and Safety Guidelines for Farming Operations by the Ontario Ministry of Labour or from a regional Ministry of Labour office at 1-877-202-0008. Section 7 lists requirements for confined spaces in agricultural operations and offers sample procedures to minimize exposure.
H2S is considered a very dangerous gas in agricultural biogas systems and other manure storage systems such as storage under fully slatted barns. Keep the following tips in mind when approaching a situation where H2S is found:
This Factsheet provides basic awareness information on hydrogen sulphide (H2S) found on agricultural operations with biogas systems. This document does not intend to provide assurance of compliance with occupational health and safety regulations in Ontario. Contact a biogas system's engineer for specific technical questions.
Ontario Ministry of Labour, 2009. Occupational Health and Safety Guidelines for Farming Operations in Ontario, "Section 7: Hazardous Atmospheres and Confined Spaces."
N.K. Patni and S.P. Clarke. 2003. Gaseous Emissions in Swine Barns and During Slurry Mixing in Sub-Floor Pits. ASAE Meeting Paper Number #034081. St Joseph, Mich.
American Society of Agricultural and Biological Engineers. 2005. Manure Storage Safety. ASAE Standard EP470 JAN1992, R2005.
Enform Canada. 2007. H2S Alive Hydrogen Sulphide Safety Training. Sixth Edition.
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