Low Cost Wastewater Bioremediation Technology: Innovative Treatment of Sulfate and Metal-Rich Wastewater

India

Chapter 1

Microbial Treatment of Industrial Wastewater

Abstract

Industrial activities result in the production of a large quantity of polluted wastewater. The present chapter mainly focuses on the sulfate and metal-rich wastewater generated from industries such as mining, metal processing, electroplating, chemical processing, and pulp and paper processing. The contamination of water bodies with such wastewater results in aquatic ecological disability and causes various diseases, such as kidney failure, bone deformation, skin disease, and cardiovascular abnormalities, etc. The treatment of sulfate and metal-rich wastewater includes abiotic treatment and biological treatment. In biological treatment strategy the sulfate reducing bacteria (SRB) meditated removal of sulfate and dissolved metals is extensively used. The field application of SRB based treatment processes includes constructed wetlands, permeable reactive barriers, vertical flow systems, anaerobic bioreactors, etc. This chapter reviews the treatment processes that are influenced by factors such as pH, hydraulic retention time, temperature, pH, nutrient availability, and concentrations of sulfide, sulfate, and metals.

Keywords

Industrial wastewater; biological wastewater treatment; sulfate reducing bacteria; field application; anaerobic bioreactors; process parameters

1.1 Introduction

While industrial wastewater is a generic term involving a wide array of wastewater discharged out of various industries that could hardly be captured in a book, this book is about wastewater mostly produced by metalliferous industries and mining. The increasing trend of metal consumption has resulted in an increase in industrial activities such as mining, metal processing, smelting, alloy casting, and silver refineries, etc., resulting in the generation of metals containing wastewater with different anions, such as predominantly ions of sulfur, phosphorus, and carbon, etc. The discussions in this book will deal with sulfur, because of the criticality it poses.

) is the second most abundant anion in the sea, after chloride, and in rivers, after bicarbonate (Middelburg, 2000), and is a common pollutant in most industrial wastewater. The presence of sulfate and metal in natural or wastewater can be due to either natural emission, or anthropogenic activities (Lens et al., 1998). The current global estimate of sulfate flux is 430 Tg/y (teragrams per year), or 430 million tonnes per year, of which the annual anthropogenic sulfate flux range is from 138 to 178 Tg/y. Around 72 Tg/y is considered to be the maximum sulfate flux from non-fertilizers and nonfuel burning industries (Nordstrom, 2011). In the natural sulfur cycle, sulfate can be generated through geochemical or biological pathways. Oxidative weathering of sulfide-bearing rocks leads to the formation of sulfate and dissolved metals. This process can also be accelerated by microbial involvement (Bhattacharya et al., 2006). Sulfide-oxidizing bacteria may lead to the formation of elemental sulfur (S⁰) from sulfide (S²−), which is eventually further oxidized by other microbial species for their metabolic requirements (Bruser et al., 2000). Sulfide may be oxidized aerobically by chemolithotrophic sulfur-oxidizing bacteria (Thiobacillus or Beggiatoa spp.), or anaerobically by phototrophic sulfur bacteria (Chlorobium spp.) to elemental sulfur and sulfate (Muyzer and Stams, 2008). Elemental sulfur disproportionation by some microbial species (Desulfovibrio or Desulfobulbus spp.) also leads to the formation of sulphate in water (Muyzer and Stams, 2008; Hardisty et al., 2013). Rain water percolating through sulfate salt reservoirs dissolve sulfate and metal into groundwater. Atmospheric sulfate produced due to sea salt aerosols or by volcanic eruption can be bound with rain water and find its way into surface water as acid rain (Lens et al., 1998).

1.1.1 Sources of Sulfate and Metal-Rich Wastewater

Industrial wastewater containing dissolved metals and sulfate is produced from different industries such as electroplating, metal processing, textiles, tanneries, oil refineries, and mining (, Fe, Ni, Zn, Co, Mn, and Pb. A general list of the pollutants generated from different industrial activities is presented in Table 1.1. Among the industries mentioned, the major amount of sulfate and metal-rich wastewater is generated from the mining industries.

Table 1.1

Lists of the pollutants generated from different industrial activities

, Fe²+, and H+ (Eq. 1.1). Further oxidation of Fe²+ to Fe³+ leads to the generation of more acidity (Eq. 1.2 and 1.3). Similarly, the oxidation of trace elements associated with sulfide minerals results in the generation of acid mine drainage (AMD) containing toxic dissolved metals such as As, Cu, Mo, Ni, Cd, Zn, and Pb (Nordstrom et al., 2015).

(1.1)

(1.2)

(1.3)

In addition to the geochemical process, the microbial process also plays an important role in the generation of sulfate and metal-rich wastewater from sites including mines and excavations. Iron oxidizing bacteria such as Acidithiobacillus ferrooxidans, Acidianus brierleyi, Ferroplasma acidarmanus, etc., are reported to oxidize pyrite, arsenopyrite, chalcopyrite, marcasite, and sphalerite, resulting in the dissolution of the metals, acidification, and the production of AMD (Baker and Banfield, 2003; Akcil and Koldas, 2006).

1.1.2 Characteristics of Sulfate and Metal-Rich Wastewater

The nature of all sulfate and metal-rich industrial wastewaters is not the same as far as the presence of other pollutants are concerned. The important parameters for the presence of sulfate and dissolved metals are the pH, the abundance of chemical oxygen demand (COD), and the organic source of sulfate and metals in the wastewater. When sulfuric acid is used during the processing steps, most of the wastewater evolved is of low pH (tannery, textile or rubber, and the mineral processing industry). Still, it is fair to state that only in a few cases is the effluent water from these sources primarily acidic. More than 70% of mines throughout the world are facing the problem of acidic metal and sulfate-rich wastewater discharges (Lopez et al., 2009). The oxidation of pyritic minerals in active or abandoned coal or metal mines and earth work excavations results in the formation of acidic (pH as low as 2 to 4) metal and sulfate-rich wastewaters, often called acid mine drainage (AMD) or acid rock drainage (ARD). In contrast, the oxidation of common metallic sulfides may not release sufficient acid, and hence can result in sulfate and metal-rich circumneutral water. Even the buffering reaction due to the presence of carbonate rock (calcite or dolomite) or limestone may lead to alkaline water with sulfate and dissolved metals (Banks et al., 1997; Bigham and Nordstrom, 2000). Nevertheless, the presence of sulfate in higher amounts along with heavy metals is always found in low pH waters. Targeted metals are also found in mineral processing wastewater (Usinowicz et al., 2006). Chromium is reported to be present in chromium-tannery effluents (Genschow et al., 1996).

These industrial wastewaters can be categorized by the presence of high and low levels of COD. The production processes of food processing, pulp and paper, textile, tannery, petroleum, and rubber processing industries deal with organic substances that discharge high levels of COD with their effluents (Lens et al., 1998; Saritpongteerakaa and Chaiprapat, 2008; Dutta et al., 2010; Li et al., 2012). The COD in such wastewater is generally comprised of low chain volatile fatty acid (VFA), along with some ammonium nitrogen and phosphate. Low chain VFA is an oxidized substance of sulfate that can be reduced by sulfate reducing bacteria (SRB) which naturally treat such water, and can be used for treatment (Liamleam and Annachhatre, 2007; Neculita et al., 2007).

1.1.3 Effect of Sulfate and Metal-Rich Wastewater

The impact of the production and discharge of sulfate and metal-rich wastewater can be categorized into three classes of aspects: environmental impacts, impacts on health, and problems faced during industrial operations. Sulfate is a chemically inert, non-volatile, and non-toxic compound; therefore, the damage caused by sulfate emissions is not direct. Sulfate ions individually though are not so toxic, but the dissolved metals which are an obvious companion during sulfate discharge can have a serious impact on the environment, as well as on human health. Different oxidized forms of sulfur (sulfate, sulfite, or thiosulfate) can be present at the same time in the wastewater, and each can undergo several reduction paths with different available organic sources (Nikzad, 2007). These organic sources are intermediates of the natural mineralization process. Therefore, discharge of high sulfate concentrations into wastewater can cause various imbalances of the natural sulfur cycle (Lens et al., 1998). Problems caused by sulfates are most frequently related to their ability to form strong acids which change the pH of a water source. Acid, metal, and sulphate-rich wastewater from mines, textiles, rubber, or paper mill industries as a whole can have a severe impact on ecological balance. These waters have a major impact on rivers, lakes, estuaries, and coastal ecosystems. Major effects can be categorized into chemical, physical, biological, and ecological; however, the overall effect is the elimination of species, destroying the primary food chain and thereby reducing the ecological stability of any aquatic ecosystem (Gray, 1997; Jennings et al., 2008). Considering the volume and complexity of wastewater, the severity is practically immeasurable. The migration of sulfate from its source to nearby geological strata is another significant problem. Sulfate from earth works, excavations and mines, or landfill leachates can migrate and contaminate nearby aquifers (MacFarlane et al., 1983). Groundwater contamination from mining or agricultural originated sulfate can lead to an enormous increase in drinking water sulfate levels (Toran, 1987; Liu et al., 2013).

Sulfate is harmful to health compared to other pollutants, in different ways. Its concentration at more than 250 mg/L in drinking water gives an unpleasant medicinal taste. Water containing high levels of sulfates, particularly magnesium sulfate (Epsom salts) and sodium sulfate (Glauber’s salt), may have a laxative effect on persons unaccustomed to that water (Nikzad, 2007). People unaccustomed to drinking water with elevated levels of sulfate can experience catharsis, dehydration, diarrhea, and gastrointestinal irritation. Infants are often more sensitive to sulfate than adults. Animals are also sensitive to high levels of sulfate. In young animals, high levels may be associated with severe, chronic diarrhea, and in a few instances, death. Exposure of sulphate-rich wastewaters has been recently reported to have acute genotoxic effect on human leukocytes (Mihaljevic et al., 2011).

Mineral processing units and coal washeries are generally located near their respective mines. These processing plants depend on the mines for high amounts of water necessary for their operation. Also, rubber processing and textile industries need high water levels for processing, and they generally recycle parts of the effluent water. The effluents containing high sulfates effectively increase the total dissolved solid (TDS) and salinity that often limits the number of cycles for reuse of such water (Bowell, 2004). Scaling problems from sulfate salt produce a major drawback (Bader, 2007). This poses a great challenge where these industries are active in semi-arid to arid environments (Bowell, 2004). Mines are nowadays thought be a source of usable water. Some mining companies are also trying to reuse the wastewater for irrigation purposes, or as drinking water to recoup part of their expenses (Usinowicz et al., 2006). Sulfate, the common pollutant in mine waters, is therefore a target. Regulatory agencies are becoming increasingly concerned over elevated sulfate concentrations in effluent, owing largely to its impact on the salinity of receiving waters.

1.1.4 Treatment Technologies

Treatment of sulfate and metal-rich wastewater can be performed using different methods (Fig. 1.1) that are mainly divided into two different groups, such as abiotic treatment and biotic treatment. Abiotic treatments are divided into both active and passive systems (Taylor et al., 2005; USEPA, 2014).

Figure 1.1 Different treatment methods for sulfate and metal-rich wastewater.

1.1.4.1 Limestone Diversion Well (LDW)

The limestone diversion well (LDW) is a well containing crushed limestone aggregate. During treatment, acidic sulfate and metal-rich wastewater are diverted into the well through a pipeline. The hydraulic force of water flow causes grinding of the limestone gravel, and the contact with lime causes the removal of acidity and precipitation of dissolved metals (Taylor et al., 2005). Armoring of limestone particles over time, however, brings down the efficiency of operation.

1.1.4.2 Adsorption

Adsorption techniques use metal absorption sites, e.g., the surface of carbonized peanut shells, leaf litter, etc., for the removal of metals from wastewater.

Ferrihydrite adsorption is used for the removal of both Se and As from wastewater. In this method, ferric salt is added into the wastewater to generate ferric hydroxide and ferrihydrite precipitate which adsorbs the Se and As from the wastewater (USEPA, 2014). The process is still limited, due to the early saturation of adsorption sites and operational difficulty for site regeneration, in the face of high loads.

1.1.4.3 Ion Exchange

In this process, ion exchange resins are used to remove the metal contaminants from the wastewater. This process is useful for the removal of both hardness and metals (Dąbrowski et al., 2004). The presence of strong oxidizing agents can limit the process performance of their ability to degrade the resins. The process is economically expensive (USEPA, 2014). Significant new developments have taken place in the field in recent years (Fu and Wang, 2011). The typical ion exchange process is presented in Fig. 1.2.

Figure 1.2 Treatment of sulfate and metal-rich wastewater using the ion exchange method.

1.1.4.4 Evaporation

Evaporation techniques, such as solar and mechanical evaporation, are used to treat such industrial wastewater. In this process, the water is evaporated from the wastewater stream, and the contaminants are concentrated as a solid or in a brine stream (Jakob et al., 1996). This process is not always suitable for wastewater treatment in cold climatic areas, and also where large quantities of wastewater are produced and the space is limited. This treatment method has scope to create groundwater contamination. The requirement for additional storage ponds, regular clean ups, and revegetation make the processing economically ineffective over a long time (USEPA, 2014).

1.1.4.5 Electrodialysis Reversal (EDR)

This process applies electrode polarity reversal on an ion exchange membrane during the removal of the contaminants from the wastewater (, Ca, and nitrates from the wastewater (Chao and Liang, 2008; Montaña et al., 2013; USEPA, 2014).

Using the EDR system, sulfate was removed at 80% (Chao and Liang, 2008) and 90% (Roquebert et al., 2000; Karimi and Ghassemi, 2016) from industrial wastewater and contaminated water, respectively. The EDR system was reported to successfully treat the metal-rich wastewater generated from the battery manufacturing industry, and removed almost completely Pb, Fe, and Cu from the wastewater (Chen and Jiang, 2011). The treatment of electroplating industry wastewater using the EDR system remove 97% of the Ni from the wastewater (Lu et al., 2014).

1.1.4.6 Electrocoagulation

In this technique, graphite or stainless steel is used as a cathode in combination with a metal anode to remove the dissolved metals present in the wastewater. Upon applying a voltage, the anode generates charged ions which subsequently precipitate the dissolved metals present in the wastewater (Al-Shannag et al., 2015). In this process, the anode material depends on the pollutants being removed from the wastewater. Using this process, a lower amount of sludge is generated when compared to the chemical process, and little maintenance is required. Metals such as As, Cu, Zn, Pb, Cr, Ni, etc., are reported to be removed using this technique (Oncel et al., 2013). The electrocoagulation process removed 68.5% (Hossini et al., 2015) and 98.8% (Jo et al., 2016) of sulfate from synthetic and wet scrubber wastewater, respectively. The efficiency of the treatment process has been reported to be dependent on electrode materials, voltage, and reaction time (Jo et al., 2016). However, the method is still very expensive (USEPA, 2014; Al-Shannag et al., 2015).

1.1.4.7 Reverse Osmosis (RO)

This technique is based on the pressure driven separation process of the contaminants from the wastewater using semi-permeable membranes. The successful operation of the process requires high pressure. As scaling or fouling is the major problem in the membrane-based treatment process, there is a requirement for a pretreatment process (Fu and Wang, 2011). Different dissolved metals such as Fe, Cu, Zn, Ni, Mg, etc., and sulfate are removed from wastewater using this technique (USEPA, 2014).

The RO process was reported to remove almost all sulfate from the wastewater generated from the steel industry and metal finishing industry (Petrinic et al., 2015; Colla et al., 2016). The process was reported to remove Ni and Cu completely from wastewater (Qdais and Moussa, 2004; Silva et al., 2016). Similarly, all the metals (Cr, Cu, Fe, Ni, Sn, and Na) were reported to be removed completely from metal finishing wastewater (Benito and Ruíz, 2002).

1.1.4.8 Photoreduction

In this process, a photocatalyst (e.g., TiO2) is used to generate electron-hole pairs using ultraviolet light. The electrons and holes subsequently induce the redox reaction of contaminants absorbed on the surface of the photocatalyst (Chen and Ray, 2001). After the treatment is over, the photocatalyst is regenerated by desorption (USEPA, 2014).

The hollow, spherical-shaped TiO2 particles are reported to remove almost all Cr from water at pH 2.82 (Cai et al., 2017). Similarly, using H2O2 as a photocatalyst, Cr was reported to be removed completely at pH 2 (Chaudhary and Singh, 2014). The authors also reported complete removal of Cu and Zn, and 94.8% Ni removal under alkaline conditions.

1.1.4.9 Anoxic Limestone Drains (ALD)

In this treatment process, water to be treated is passed though the limestone drain under anoxic conditions. Near the source of the wastewater, a drainage line with coarse limestone aggregate covered with low permeable synthetic liner is constructed. When the wastewater comes in contact with the limestone, bicarbonate alkalinity is added to the water, and the pH is increased to 6−8 (Gazea et al., 1996). The main purpose of wastewater treatment using ALD is to remove acidity and increase alkalinity (Taylor et al., 2005; USEPA, 2014).

1.1.4.10 Oxic Limestone Drains (OLD)

This treatment system consists of open channels filled with coarse limestone aggregate. The exclusion of oxygen, like ALD, is not required in this system. The use of this system is important when acidic wastewater is transported long distances from the source. The length of the channels ensures a longer contact time between the limestone and wastewater, and increases the treatment efficiency (Johnson and Hallberg, 2005). This treatment system is generally used to remove acidity, Mg, Al, Fe, Cu, Zn, Pb, and Se from wastewater. Because of its low construction and operating costs, it is frequently used in several mining areas for the treatment of AMD (Taylor et al., 2005; USEPA, 2014).

1.1.4.11 Slag Leach Beds (SLB)

This system is similar to OLD, where slag is used as a neutralizing material instead of limestone. The slag materials generated from the steel manufacturing process are reported to be extensively used in this SLB-based treatment process, because of their high neutralizing capacity (Simmons et al., 2002). Although the process is cost-effective, there are certain disadvantages like the release of trace metals such as Al, Fe, Mg, Ti, Mn, and silica, if they are present in the slag (Taylor et al., 2005).

1.1.4.12 Alkalinity Producing Cover

Alkalinity producing cover is generally used at the mining site to prevent the formation of AMD. In this system, the alkaline materials are mixed with acid generating waste rock. The treatment process becomes ineffective, due to the deployment of carbonates in the limestone cover placed above the acidic materials. The low solubility and slow dissolution rate of carbonates in near neutral water makes the treatment process ineffective. Use of magnesium-based alkaline material instead of limestone often improves the acid neutralization capacity of this process (Taylor et al., 2005).

1.1.4.13 Pyrolusite Limestone Beds

Pyrolusite limestone beds are usually used for the treatment of AMD containing high Mn (Milavec, 1999). This system consists of limestone beds that are inoculated with aerobic microorganisms, such as algae. The respiration of aerobic microorganisms generates alkalinity which catalyzes the hydrolysis of Mn²+ to insoluble MnO2 (Eq. 1.4).

(1.4)

The acidity generated in the reaction is subsequently neutralized by the limestone. The treatment process is not suitable for the treatment of wastewater containing high concentrations of Fe. To make the treatment process effective, routine maintenance like regular dosing of the organic substrates for microorganisms and removal metal precipitates are important (Taylor et al., 2005).

1.1.4.14 Phytoremediation

In these techniques, plants are used to treat the metal contaminated wastewater. Several mechanisms for phytoremediation include sequestration of the contaminants in plant tissue, volatilization of volatile contaminants, degradation of the contaminants, and immobilization of the contaminants in plant roots (USEPA, 2014). This treatment process is beneficial because of its sustainability and eco-friendly nature. It requires no energy and generates much lower amounts of air, water discharge, and secondary wastes (Mendez and Maier, 2008). Phytoremediation is also helpful in land restoration and sequestration of greenhouse gases. However, the process is very slow and its efficiency can decrease over time (Zhang, 2010).

1.1.4.15 Aerobic Wetland

The anaerobic wetland in used for the precipitation of certain metals, such as As, Fe, Cr, and Mn, whose solubility is dependent on the pH of the water (Taylor et al., 2005). It consists of a shallow pond having some planted vegetation. The wetlands receive water diverted from other passive water treatment systems, and provide longer residence time for the precipitation to take place completely (Johnson and Hallberg, 2005). The precipitates are retained on the surfaces of the plants or flow downstream from the wetlands. This system is found effective in removing Fe (60−95 %) (Taylor et al., 2005).

1.1.4.16 Anaerobic Wetlands

Anaerobic wetland is a water retention pond containing organic matter as the substrate and limestone aggregate as the neutralizing agent. As the sulfate and metal-rich wastewater is passed through the organic matter, the oxygen is stripped out of the water, resulting in anaerobic conditions. Under anaerobic conditions, the sulfate-reducing bacteria (SRB) generate alkalinity by using the organic matter as a carbon source and sulfate as an electro acceptor (Johnson and Hallberg, 2005). The growth of SRB also generates hydrogen sulfide (Eq. 1.5).

(1.5)

The dissolved metal present in the wastewater can be precipitated by the sulfide generated due to SRB growth. Some metals can also be removed due to bicarbonate alkalinity provided by both the SRB growth and limestone aggregates (Taylor et al., 2005).

1.1.4.17 Alkalinity producing system (APS)

The alkalinity producing system (APS) is a combination of the ALD and anaerobic compost wetlands. In this system, the organic compost layer (18 inches) is placed on top of the limestone bed layer (18−24 inches). The sulfate-rich wastewater falls on the surface of the compost layer, and is subsequently passed through the layer to precipitate out the dissolved metal sulfide and consume the dissolved oxygen through organic matter decomposition (Watzlaf et al., 2000; Jarvis et al., 2002). The contaminants which are removed from the wastewater using this technique include Cu, Zn, Fe, Mn, and Pb (USEPA, 2014).

1.1.4.18 Successive Alkalinity Producing System (SAPS)

A successive alkalinity producing system (SAPS) is a pond which is a combination of ALD and organic substrates. The mixture of limestone and organic substrate is overlaid by the wastewater. When the wastewater is passed through the compost, limestone provides the initial alkalinity and the oxidation−reduction potential (ORP) of the water is decreased. This creates a favorable condition for the growth of SRB (Bhattacharya et al., 2008). The growth of SRB generates alkalinity and hydrogen sulfide, both resulting in the removal of dissolved metals. Using this method, acidity, Fe, Al, Cu, Mn, and Zn, etc., are removed from the wastewater (Cheong et al., 2010; USEPA, 2014).

1.1.4.19 Gas Redox and Displacement System (GaRDS)

This passive treatment technology is used to prevent sulfide oxidation by displacing oxygen from underground workings. To displace the air from mine voids, a mixture of anaerobic gases (CO2 and CH4) is used. Both the gases can be generated using an external bioreactor, and can be derived from coal bed methane (Taylor and Waring, 2001). In an anaerobic bioreactor, the biodegradation of organic compost materials generates the CO2 and CH4. When the pressure of the gases is increased, they migrate through the attached pipelines into the underground mine working. This treatment technology can be useful for underground mines where partial or complete flooding of the underground mines is not possible (Taylor et al., 2005). Long-term effectiveness of the technology is doubtful,