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\n
1. Introduction
\n
The rural areas where coffee is cultivated are located mainly in the equatorial and sub‐equatorial zone in Africa, Asia and South America. The top ten producing countries are Guatemala (224,871 tonnes/year), Mexico (257,940), Uganda (314,489), Honduras (380,296), India (385,786), Ethiopia (423,287), Indonesia (814,629), Colombia (892,871), Vietnam (1,818,811) and Brazil (2,859,502) [1]. Coffee production and processing, the latter step often taking place in locations distant from the beans production sites, generate yearly over 20 million tonnes of liquid and solid waste to be disposed of by farmers and processing plants. Although the farms in these areas range in size from 0.5 to 6 hectares (ha), typically they are 1–2 ha and coffee is generally grown along with other cash and food crops, such as maize, as well as cattle. An example is provided by coffee farmers in Uganda [2] having larger‐than‐average farm plots, while farmers growing coffee and maize tend to have larger plots than coffee farmers without maize (2.69 ha compared to 1.86 ha, respectively). Thus, coffee and maize production is a key determinant for household incomes and poverty, and some land is dedicated to traditional staple food with low‐added value. Indeed coffee and maize producers have significantly lower poverty rates compared to coffee farmers that do not grow maize. In general, we can assume that coffee farm economics is dependent upon a wide variety of factors, including productivity, quality, costs of production and waste disposal, price premiums, the latter to achieve quality or sustainability standards. The options for the valorization of the coffee residues, not focusing on waste management in rural areas, have been recently reviewed [1, 3–6].
\n
The rural areas where olive trees are cultivated are located mainly in the Mediterranean basin, where in the northern side over 82.5% of the world production of olive oil (i.e. 2.34 out of 2.84 million tonnes) takes places (Spain, Italy, Greece, Portugal, France, Cyprus, Slovenia and Malta) [7]. This figure rises up to 94.1% of the world olive oil production, i.e. 2.63 million tonnes, if the countries of the southern side of the Mediterranean basin are included (Morocco, Algeria, Tunisia, Lybia, Egypt, Jordan, Israel, Lebanon, Syria and Turkey). Olive trees cultivation and olive oil processing, the latter step often taking place in locations distant from the olive production sites, generate every year in the northern side of the Mediterranean basin 6.01 million m3 of liquid waste (Figure 1) and 8.06 million tonnes of solid waste (Figure 2) as an average. This amount rises up to 30 million m3 of olive mill wastewater and 20 million tonnes of solid waste, called wet husks [6] if the southern side of the Mediterranean basin is included. The farming system in the Mediterranean area consists of a majority of small farms (e.g. in Italy 60% of olive farms are <2 ha, and less than 10% are >10 ha), and olive trees are generally grown along with other cash and food crops, infrequently with livestock. Overall farm economics is dependent upon a wide variety of factors, including productivity, quality, and costs of production and waste disposal. To achieve quality and sustainability standards, the costs are on the premises of the farmers, while premiums are limited to larger agro‐industrial installations transforming the waste into energy, i.e. electricity (Figure 3). The options for the valorization of the olive oil extraction solid residues, not focusing on waste management in rural areas, have been recently reviewed [8, 9].
\n
Figure 1.
Ponds for the confinement of the wastewater (left = before filling, right = after filling) from the extraction of olive oil at the facility of Coop. Sor Ángela de la Cruz, Estepa (Sevilla, Spain). Due to the environmental toxicity of the liquid phase, the large amounts produced from intensive olive tree cultivation in that area need to be stored separately before further processing, e.g. for biogas production (Source: Marco Nuti).
\n
Figure 2.
Olive pomace (wet husks) from the two‐phase decanter centrifugation olive oil extraction. The wet husks have an initial relative humidity of 65–70% (Source: Marco Nuti).
\n
Figure 3.
Power generation plant (1 Mw) fed with wet olive husks and wastewaters from the olive oil extraction. Biogas is generated in the digestor (right) and stored (left), then converted into electricity. Installation Friel Ionica Srl ‐ BTM Srl spinoff of the University of Pisa, located in Manduria (Taranto, Italy) (Source: Marco Nuti).
\n
There are many similarities between the chemical composition and end‐of‐use of the solid residues of the two production chains, besides their vast amounts available yearly. Both solid residues (i.e. coffee husks, defective coffee beans and spent coffee grounds on one side, and olive wet husks, olive stones on the other side) are problematic in terms of disposal, having similar environmental impacts, decontamination needs, similar possible re‐uses and similar chemical nature of the components, i.e. a high content in ligno‐cellulosic materials, low content of fat and protein, presence of (poly)phenols recalcitrant to degradation. The main end‐of‐uses in the poorer and less accessible rural areas are the production of heat and recycling into agriculture after modest composting. Production of heat for household heaters, electricity, recycling into agriculture after modest composting and minor uses for the production of commodities with high added‐value (e.g. cosmetics, mushrooms, fodder) characterize the end‐of‐use of the solid residues in areas with more intensive agriculture.
\n
In this chapter, the two types of solid wastes are critically reviewed separately and assessed for their valorization in the rural areas for production of coffee and olive oil, respectively.
\n
\n
\n
2. The management of residues of coffee production and transformation in rural areas
\n
Over 90% of the coffee production (Coffea arabica, Coffea canephora and the Ethiopia’s natural C. arabica cultivar Harrar) takes place in developing countries. In these countries, economy depends to a large extent on agriculture, coffee being one of the most important crops. In fact, countries like Vietnam, India, Kenya, Nicaragua, Ecuador and Mexico encouraged the cultivation of coffee in rural areas as a national economy strategy. About 70% of the world coffee production is cultivated in rural areas on small farms less than 6 ha [10]. The implemented policies, subsidies and incentive programs which promoted the conversion for land to intensive, technified mono‐crop coffee cultivation resulted in a catastrophic impact to the environment. Coffee farms are located indeed in some of the biologically most diverse, and most threatened, environments in the world [11].
\n
The isolated rural areas where the best coffee is grown are extreme poverty zones (Figure 4). They have limited or no basic services (Figure 5), access roads are in poor condition and farmers have little or any basic education. For coffee growers in many countries, coffee provides their sole source of cash income and it is a family activity. Farmers have relatively weak trade positions and, in spite of it, they have to hold the same high productions standards as the large‐scale producers who have additional resources to invest and access technological tools. To join the forces and improve the marketing of coffee, marginalized farmers created small communities called ‘cooperatives’ or ‘beneficios’ that are collection centres where they gather the crops and process the fruit until obtaining the coffee beans. The process of separation of the commercial product (beans) from coffee cherries generates enormous volumes of waste material in the form of pulp, residual water and parchment. Almost all these waste are disposed in the natural environment, causing bad odours, bad aspect, pathogenic insects’ attraction, and pollution of soils and water bodies. In fact, they represent the major source of river pollution in Ethiopia and northern Latin America [12, 13]. The appropriate use of coffee by‐products would help circumventing these problems, and valorization of the residues would represent a value addition from the point of view of environment protection [14]. The main chemical traits of the coffee processing residues at farm level, relevant for their valorization, are summarized in Table 1. The degradation process, occurring in natural conditions, is extremely slow and incomplete despite a favourable C/N mass ratio of 40, due to the recalcitrance of (poly‐)phenols and complex glucides, thus giving rise to toxicity problems.
\n
Figure 4.
The small ‘coffee farms’ in the Amazonas very often look like an orchard exhibiting great plant biodiversity (Source: Marco Nuti).
\n
Figure 5.
Coffee beans are air‐dried by small farmers in the western Amazonian forest at 1200 m of altitude (facility of the ‘Asociación de cultivadores y comercializadores de café organico Bosque Nublado Río Golondrinas ‘, Parroquia Jijon y Caamano, Carchi, Ecuador) (Source: Cristina Echeverria).
\n
\n
\n
\n
\n
\n\n
\n
Component
\n
Spent coffee grounds
\n
Coffee pulp
\n
Coffee husk
\n
\n
\n
g × 100 g−1 d.w.
\n
g × 100 g−1 d.w.
\n
g × 100 g−1 d.w.
\n
\n\n\n
\n
Proteins
\n
6.7–13.6
\n
10.1
\n
5.2–11
\n
\n
\n
Total lignin
\n
33.6
\n
–
\n
–
\n
\n
\n
Cellulose
\n
8.6–13.8
\n
–
\n
16.0–43.0
\n
\n
\n
Carbohydrates
\n
–
\n
63.2
\n
35.0–85.0
\n
\n
\n
Reduced sugars
\n
–
\n
12.4
\n
0.71
\n
\n
\n
Ash
\n
0.43–1.6
\n
8.3
\n
0.7–6.2
\n
\n
\n
Fat
\n
6.3–28.3
\n
–
\n
0.3–3.0
\n
\n
\n
Tannins
\n
1–9
\n
1.80–8.56
\n
\n
\n
\n
Caffeín
\n
1–2
\n
1.3
\n
1.0–1.3
\n
\n
\n
Organic carbon
\n
–
\n
–
\n
50.8
\n
\n
\n
N
\n
–
\n
–
\n
1.27
\n
\n
\n
Polyphenols
\n
–
\n
–
\n
1.22
\n
\n\n
Table 1.
Main chemical components of the solid coffee residues (spent coffee grounds, coffee pulp, and coffee husk) relevant for their valorization at small farm level.
Data collated from different authors ([65–67] and references cited therein), showing a fairly wide range of values, possibly due to the diversity of tested materials, i.e. Arabica or Robusta variety, not specified by Aa. The ligno‐cellulose component and tannins are the most recalcitrant components to degradation.
\n
Various attempts have been made to circumvent these environmental problems and minimize the toxicity levels, e.g. improving production systems, reducing the volume of wastewater or recycling wastes to obtain value‐added compounds such as enzymes and caffeine [1]. Out of the alternatives, only a few have been implemented in rural areas because of the costs and unavailability of the technology in these small communities. The valorization of coffee residues in agriculture, as animal feed and for energy production is still the most attractive application to solve in part the problems of people in these areas.
\n
During the years 2000–2004, many farmers started a transition to organic coffee production, encouraged by the growth of certified coffee markets and development projects. This transition involved the use of new forms of fertilization [11, 15]. From this point of view, large quantities of coffee pulp are available for those organic farmers. Approximately three‐quarters of the nutrients extracted to obtain the coffee beans are found in the pulp. Co‐composting the solid waste with animal manure is the most used alternative to minimize the environmental impact of the residue. However, in most cases the compost is not obtained under controlled conditions to ensure its stabilization and sanitization. Pulp is typically left to degrade in piles without any treatment, thus resulting in an organic material incorrectly named ‘compost’. Introducing a non‐stabilized organic matter into the soil has caused a negative effect on crops production [16]. Vermicomposting is an alternative widely used in Colombia and Ethiopia showing better results in terms of organic fertilization [17].
\n
Small projects to obtain bioethanol and biogas have been also implemented in some key areas of Africa and Central America [18–20]. The production of energy from coffee wastes partially meets the energy needs in rural areas. Furthermore, the technology needs further improvement in order to be applied in the most remote or marginalized places.
\n
The use of pulp as an animal feed has had limited use due to the high content of caffeine which affects ruminants. In Ethiopia, it has been used as a nutrient supplement to sheep feeding [21, 22].
\n
In conclusion, there is still a lot of pollution because of the lack of knowledge and government policies. There is a vital need to counterpart this production with an appropriate utilization of coffee by‐products. The valorization of the liquid and solid residues should be regarded as a value addition from an environmental point of view. However, it is essential that coffee production and processing take into account environmental needs to ensure sustainability, reasonable living standards for the populations involved with coffee, and ensure the maintenance of quality. Such an effort is one of the objectives of the International Coffee Agreement 2007, i.e. to encourage members to develop a sustainable coffee sector in economic, social and environmental terms [23].
\n
\n
\n
3. The management of residues of olive oil extraction process in rural areas
\n
The olive tree cultivation in the Mediterranean countries of EU (ca. 400 cultivars in Italy, 150 in Spain, 40 in Greece) takes place in 4.8 million ha, and the olive oil extraction process is carried out in about 12,000 olive‐mills, most of which are small and medium enterprises (SMEs), involving 800,000 jobs [6, 24]. Olive oil is obtained essentially via traditional pressing (TP), two‐phase decanter process (2‐PDP) and three‐phase decanter process (3‐PDP) [25], each of them generating different amounts of wastes (Table 2). There is an uneven distribution of the type of extraction process in southern Europe: in Spain 99% of the adopted technology is 2‐PDP, while in Italy 55% is 3‐PDP, 15% is 2‐PDP and 15% is TP. In Greece, 82% of the olive mills have adopted 3‐PDP and 18% 2‐PDP. However, there is an increasing interest in these last two countries for the two‐phase system, possibly coupled with the de‐pitting of the olive wet husks (synonyms: crude cake or pomace). In this way the stones can be separated and used for heating purposes, particularly at small community level and for household heaters.
\n
\n
\n
\n
\n
\n\n
\n
Extraction process
\n
Input
\n
Amount of input
\n
Output
\n
\n\n\n
\n
Traditional pressing
\n
Olives
\n
1 tonne
\n
Oil
\n
\n
\n
Washing water
\n
0.1–0.12 m3
\n
Solid waste (ca..25% water + 6% oil)
\n
\n
\n
Energy
\n
40–63 kWh
\n
Waste water (ca. 88% water)
\n
\n
\n
3‐Phase decanter (3‐PDP)
\n
Olives
\n
1 tonne
\n
Oil
\n
\n
\n
Washing water
\n
0.1–0.12 m3
\n
Solid waste (ca. 50% water + 4% oil)
\n
\n
\n
Fresh water
\n
0.5–1 m3
\n
\n
\n
Water to wash the impure oil
\n
10 kg
\n
Waste water (ca.94% water + 1% oil)
\n
\n
\n
Energy
\n
40–63 kWh
\n
\n
\n
2‐Phase decanter (2‐PDP)
\n
Olives
\n
1 tonne
\n
Oil
\n
\n
\n
Washing water
\n
0.1–0.12 m3
\n
Solid waste (ca. 60% water + 3% oil)
\n
\n
\n
Energy
\n
<90–117 kWh
\n
\n\n
Table 2.
Solid and liquid waste generated using different olive extraction technology. The solid waste contains olive pits [25].
\n
As far as the residues from the olive trees cultivation are concerned, in the rural areas of southern Europe, two main components of biomass burning are the incineration of wood as household fuel, and the combustion of crop residues (i.e. prunings and leaves of olive trees) in open fields. At the same time, as the population continues to rise in the African side of the Mediterranean basin, the contribution from these two types of biomass burning tends to increase. In the northern side of the Mediterranean basin burning olive branches and leaves in open fields is allowed (Figure 6) under an increasingly stringent legislation as they can contribute to greenhouse gas emissions (GHG). These burnings can be avoided once the agro‐residues are employed for sustainable, cost‐effective and environment‐friendly options such as composting and subsequent ploughing of the compost. A quantitative description of the spatial distribution of biofuel and open‐field burning has been attempted to assess the impact of this burning on the budgets of trace gases [26], but no real attempts to discourage burnings are currently made on the basis of continuous educational programs for small olive farmers. Therefore, open‐field burning of olive crop residues is still the most traditionally adopted end‐of‐use in rural areas. From a purely agronomic standpoint, the delivery of ashes in cropped agriculture would be meaningful for fertilization purposes only when the content of soil organic matter and organic nitrogen at plough depth is high, which seldom occurs in both northern and southern side of the Mediterranean basin [27–29].
\n
Figure 6.
Burning olive leaves and prunings in the open field in controlled (left) and uncontrolled (right) conditions. In the olive oil producing EU countries burning is submitted to stringent legislation (Source: https://i2.wp.com/www.quiantella.it/wp‐content/uploads/2016/06/a.jpg?fit=533%2C348&resize=350%2C200).
\n
The use of in‐house pressing (i.e. with large stone wheels or stone cones) of the olives in small farms has almost disappeared, and this type of extraction is often confined to demonstration farms for teaching or museum purposes. The traditional pressing is also decreasing in favour of the decanter‐centrifugation systems, either two‐ (olive oil and wet husks) or three‐phases (olive oil, husks and wastewater). The small olive mills in rural areas work preferably with 3‐PDP, but the availability on the market of 2‐PDP decanter extractors with reduced energy consumption is gradually offering new opportunities. On the contrary, in agriculture‐intensive areas, the preferred technology is 2‐PDP with large working capacity (Figure 7) or the last‐generation decanter extractors combining the modern extraction technology without the addition of water with batch processing, thanks to the bowl discharging device (Figure 8). Using the latter system, the waste is represented by a dehydrated husk similar to the one coming from the three‐phase decanter, along with the pulp from the husk, the so‐called ‘pâté’, i.e. wet husks without any trace of kernel directly inside the bowl. This pâté can be used for various purposes, including agronomic use, animal feeding, or can be mixed with other biomass for biogas production.
\n
Figure 7.
Two‐phase decanters in series in an olive mill for the extraction of olive oil (Picualia, Proyecto de traslado y perfeccionamento de almazaras por fusiòn de Cooperativas ‘Agricola de Bailén virgen de Zocueca’, Jaen, Spain) (Source: Marco Nuti).
\n
Figure 8.
Last generation decanter extractors of olive oil, which combines the two‐phase extraction technology without the addition of water with batch processing, thanks to the bowl discharging device. The installed power ranges from 7.5 Kw (more adapted to small quantities of olives to be extracted, i.e. process capacity of 0.5 tonnes/hour) to 45 Kw (for very large quantities of olives to be extracted, i.e. process capacity of 9 tonnes/hour) (Source: courtesy of Pieralisi SpA, Ancona, Italy).
\n
The biochemical and physical‐chemical traits of the solid waste ‘wet husks’ are reported in Table 3, where for convenience they are compared with the traits of the wet husks after microbially enhanced composting in mechanically turned static piles. The re‐uses at small farm level include (i) further oil extraction as the wet husk still contain 2–4% oil, (ii) delivery by soil treatment into the legally allowed soil acreage, (iii) sale to larger companies, (iv) re‐use as fodder for animals, which requires pre‐treatment with appropriate enzymes and process, (v) delivery into soil after composting, as a green (i.e. only plant materials) or mixed (i.e. plant material plus manure) fertilizer. None of the first three options is considered really profitable by small farmers, because pomace oil has a low price with very marginal profit, direct delivery into soil requires a lot of bureaucracy and intoxicates the soil and selling the husks as a fuel is poorly profitable and needs transportation of a material with 70% humidity. If air‐dried before transportation, the volatile phenolics can cause air pollution. The fourth option would be feasible, provided that the technology is available to the farmer. The last option is probably the most feasible in‐house, provided the farm has a tractor for the mechanical turning of the piles.
\n
\n
\n
\n
\n\n
\n
Parameter
\n
Time (days)
\n
\n
\n
\n
0
\n
60
\n
\n\n\n
\n
pH
\n
6.4aA
\n
8.1bB
\n
\n
\n
EC (dS m−1)
\n
1.28aA
\n
0.79bA
\n
\n
\n
TN (UoW)
\n
2.05aB
\n
1.88bB
\n
\n
\n
TOC (UoW)
\n
46.8aA
\n
31.9bA
\n
\n
\n
C/N
\n
22.8aB
\n
16.9bB
\n
\n
\n
HA (UoW)
\n
15.6aA
\n
41.6bB
\n
\n
\n
FA (UoW)
\n
14.3aA
\n
19.5bA
\n
\n
\n
HA/FA
\n
1.10aA
\n
2.14bB
\n
\n
\n
HI
\n
1.1aA
\n
0.1bB
\n
\n
\n
HD
\n
48aA
\n
94.5bB
\n
\n
\n
HR
\n
6.4aB
\n
19.2bB
\n
\n
\n
Ash (%)
\n
8.3aA
\n
11.6bB
\n
\n
\n
Fats (UoW)
\n
21.5aA
\n
2.9bB
\n
\n
\n
Lignin (UoW)
\n
47.7
\n
27.8
\n
\n
\n
Phenols (UoW)
\n
14.0bA
\n
1.6 bB
\n
\n
\n
Respiration (CO2–C)mg g‐1)
\n
1087.8aB
\n
678.3bA
\n
\n\n
Table 3.
Chemical‐physical properties of the initial olive wet husks (t = 0) and of the stabilized compost after 60 days of composting (t = 60) in controlled conditions.
UoW = units of weight. The microbially enhanced composting (static piles with mechanical turning) was carried out with the use of selected microbial starters [60]. Different letters indicate statistically significant differences (P < 0.05). Low case letters, comparison between sampling times within each treatment. Capital letters,comparison between treatments within each sampling time.
\n
\n
\n
4. Agronomic and legislative aspects
\n
Agricultural utilization of residues as organic amendments and fertilizers has been shown to be a sound alternative for both residue recycling and soil fertility improvement [16]. The latter goal can be achieved in the frame of a modern agronomic management such as the conservative and regenerative agricultural practices. Regenerative agriculture stands on the three pillars of the conservative agriculture (use of crop rotation, reduction in tillage, retention of adequate levels of crop residues and soil surface cover) plus the maintenance of soil carbon sink. All these management practices can lead to a significant increase of carbon content in soil [30]. In turn, the increase of organic matter and humic fractions in soil determine the increase of soil richness and diversity of microbiota [31]. Therefore the utilization of residues of both coffee and olive cultivation, along with the utilization of the residues of the first step of processing (i.e. those feasible at small farm level in rural areas) cannot be merely identified with their disposal. On the contrary, the utilization of these residues is advisable, particularly because advantages to crops and soil are expected, either in the short‐ or in medium‐term.
\n
More specifically, the good agronomic practices (GAP) adopted for coffee cultivation by both top and low‐producing countries, e.g. [32–34], define the criteria leading to a product conforming quality and safety criteria in regimes of both conventional and organic agriculture, and include the use of organic fertilizers and their quality. Though the aims are the same, the rules and recommendations can vary, reflecting the different pedo‐climatic characteristics of the cultivation area. The density and productivity of coffee plants per hectare for small holders coffee farms can range from 1332 plants of Arabica, with a very low productivity of about 400kg in the traditional organic coffee orchards of the Galapagos Islands (Ecuador) [35] to 1100 plants producing up to 3.5 tonnes per ha in Vietnam with Robusta variety grown with high farm inputs [36], or high yields in intensified monocultures with a density of 10,000 plants [37].
\n
Maximizing the small coffee farms seems to be linked nowadays more to the quality of the beans rather than to the yields per ha. In this sense, enhancing the bean quality by minimizing or avoiding chemical inputs and maximizing the re‐use of correctly composted residues could help in achieving the task. On the contrary, in intensive coffee cropping systems where the predominant criterion is the harvesting cost, the trend is to have much higher plantation density since it costs almost as much to harvest a low‐yield as a high‐yield field. But in this case, additional costs could emerge for shading management systems (arborization), for more irrigation inputs, and more plant protection products usage. For the legislative framework of organic fertilizers, biostimulants and microbial‐based amendements in coffee‐producing countries, most of them have installed recent rules for the safe use, production or import. As an example see the rules in Brazil [38], Vietnam [39] and Colombia [40] among the top producers, and Ecuador [41] among the smaller coffee‐producing countries.
\n
The olive tree is considered as one of the cultivated trees with the lowest demand for soil nutrients. This is the main reason why the tree can survive and be productive even in poor, rocky areas with soils mostly derived from hard limestone, e.g. in Greece, Italy and Spain, or in sandy soils in the southern side of the Mediterranean basin, e.g. Tunisia and Morocco. A significant portion of the olive groves can be found, in the small farms of the EU countries, on steep hill and mountain slopes which have been terraced with stone walls to hold the soil. For the olive chain residues, the amount of residues at farm level will be strongly dependent on the density of olive tree plantations. In the actual agronomic management of olive groves in the Mediterranean basin, the density of olive trees plantations ranges from 10 to 15 trees per ha of Tunisian or 40–50 trees per ha of Puglia’s (Italy) small farms (due to low water availability) and soil often maintained without cover, to more than 1500 trees per ha in the intensive new cultivation areas of Spain and Italy. The inter‐row space, in the intensive cultivation areas, is often left without cover in Andalusia, while many small farmers in Italy have continued to adopt the traditional intercropping of olive groves with vineyards and arable crops (Figure 9). In northern and central Greece, farmers have historically combined olive production with arable crops in the same plot. This practice is reputed to be appropriate to ensure a steady economic return year‐after‐year, irrespective of the weather conditions. The positive contribution of agroforestry mixed with olive groves include continued olive production along with benefits in terms of animal health, appropriate control of manure usage and the creation of wildlife habitats. In a recently started project in the province of Chalkidiki (Crete, Greece), the olive production that takes into consideration both biodiversity maintenance and wildlife habitats showed high performances, whereas the main negative effects included extra costs of management, administrative overburden, the complexity of the planning and field work and aspects related to mechanization [42]. Small farmers in Greece and Italy have identified that intercropping is probably only appropriate where the principal product is represented by the olives for olive oil production, rather than the edible olives which require a relevant use of pesticides. The presence of some understory species in the cropped area is thought to enhance both quality and flavour of the olive oil.
\n
Figure 9.
Extensive olive tree (var. Picual) cultivation (left) along the ‘Carretera de los olivares’ between Jaen and Sevilla (Spain). In the province of Jaen there are over 40 million olive trees. The olive cultivars (cv.) mostly grown in Andalucia are Hojablanca, Picual, Lechin, Picudo, Verdial, Cornicabra, Empeltre, Arbequina. In Tuscany (Italy) the small farms often grow olive trees (cv. Leccino, Moraiolo, Frantoio, Pendolino, Leccio del corno, Maurino) intercropped with vines (right) (Source: Marco Nuti).
\n
For the residues from olive cultivation and olive oil extraction, in the Mediterranean basin there is an increasing trend to frame the soil application with unprocessed residues into a more stringent legislation. At EU level the matter is regulated by the Waste Framework Directive 2008/98/EC [43], the Directive on Industrial Emission of 2010 [44] implemented by the European Commission in 2012 [45]. For landfill disposal during the whole life‐cycle of the landfill, the relevant rules to prevent or reduce the pollution of surface water, groundwater, soil and air, and the resulting risks to human health, are provided by the Landfill Directive 99/31/EC [46]. The EU legislation on this issue has been critically reviewed [47]. At national level, in Spain the disposal of olive chain wastes is regulated [48]. In Italy, the disposal of olive wastes is regulated by the national Law n. 574 of 1996 [49]. In Greece, the disposal of olive wastes is regulated by the national Laws n. 1650/86 and 3010/2002. The present legislative status in Greece does not allow the application of untreated olive mill wastes to soil surface [47]. Essentially, for the three major olive oil‐producing countries the disposal is prohibited or strongly restricted in quantity, land area and timing. Unfortunately, the small farms in marginalized rural areas sometimes tend to overcome the restrictions, mainly because of the small quantities produced, the transportation costs and road difficulties. Also the production and quality of amendments, including those derived from a composting process of the olive cultivation and olive oil extraction process, are regulated by national laws in the EU countries of the Mediterranean basin. In Spain, the matter is regulated by the Fertilizer Act n.7540 [50] and n.13094 [51]. In Italy, the matter is regulated by the Annex 2 to the Fertilizers Act n. 75 [52]. As an example, the requirements of the Italian law for green and mixed amendments are reported in Table 4. Emphasis has been given to the source of materials to be used and the transformation process, to the physical‐chemical traits of the amendments with particular attention for the level of humification, and to the hygienization and safety aspects. All the different types of amendments (non‐composted, green composted, mixed composted) must conform to the limits of heavy metals, namely (in mg per kg dry matter: Pb 140, Cd 1.5, Ni 100, Zn 500, Cu 230, Hg 1.5, Cr6+ 0.5). In Greece, the matter is regulated by the Fertilizer Act n. 30(I) of 2006, and n. P.I. 118 of 2006. At EU level, the legislation on fertilizers, i.e. the Regulation (EC) No. 2003/2003 of the European Parliament and of the Council of 13 October 2003 [53], which was cantered on chemical fertilizers only, is actually being repealed by a new legislation that includes the organic fertilizers, biofertilizers and amendments. The approval of the new Regulation is expected by the end of 2017. The agronomic benefits from the use of a correctly composted amendment include a positive effect on soil structure, an increase of phytostimulatory substances, and a direct effect on crop yield. The latter is obtained through an increase of nutrient availability. In addition, as secondary effect it has been often observed that these amendments act as biosimulants or bio‐effectors providing an increased biocontrol activity of soil‐borne phytopathogens and a substantial soil detoxification. These traits may lead to some difficulty in placing these borderline products into an appropriate legislative framework [54]. The agronomic advantages of delivering green compost from olive waste as a fertilizer for olive groves include the possibility to run organic agriculture, to maintain and increase the soil carbon stocks and to detoxify the cropped area.
\n
\n
\n
\n
\n
\n
\n\n
\n
\n
Process and essential components
\n
Minimum content/useful substances
\n
Obligatory to be declared
\n
Notes
\n
\n\n\n
\n
Green composted amendment
\n
Product obtained through a transformation and stabilization process, in controlled conditions, of organic residues. These can be prunings, olive husks, crop residues, other residues of plant origin.
\n
Max humidity: 50%
\n
Humidity
\n
The content of other forms of N, total P and total K can be declared.
\n
\n
\n
pH 6–8.5
\n
pH
\n
Plastics, glass and metals cannot be higher than 2%
\n
\n
\n
Minimum organic carbon: 20%
\n
Organic C
\n
Stony inerts (diameter ≥ 5 mm) cannot be higher than 5%.
\n
\n
\n
Humic and fulvic carbon: min 2.5%
\n
Humic and fulvic C
\n
Salmonella: absent in 25 g of the sample w.w. (where n = 5, c = 0, m = 0, M = 0)
\n
\n
\n
Organic N ≥ 80% of total N
\n
Organic N
\n
Escherichia coli lower than 1.000 cfu (where n = 5, c = 1, m = 1000 cfu/g, M = 5000 cfu/g)
\n
\n
\n
Max C/N: 50
\n
C/N
\n
Germination index (diluted 30%) ≥ 60%.
\n
\n
\n
Salinity
\n
Algae and aquatic plants are allowed, such as Posidonia left on the shores, after separation from sand of the organic fraction. Their content must be lower than 20% of the initial mix.
\n
\n
\n
Na content
\n
Thallium must be lower than 2 mg kg−1 (only in amendments containing algae).
\n
\n
\n
Mixed composted amendment
\n
Product obtained through a transformation and stabilization process, in controlled conditions, of organic residues. These can be by the organic fraction of USR from differentiated recycling of animal waste including liquid waste, residues of untreated wood processing and of the untreated textile industry, organic residues from effluents and muds, and all residues allowed for green composts.
\n
Max humidity: 50%
\n
Humidity
\n
The muds (defined according the Legislative Decree 27 January 1992 n.99, cannot represent more than 35% (w/w) of the initial mix. The content of other forms of N, total P and total K can be declared. Plastics, glass and metals cannot be higher than 2%
\n
\n
\n
pH 6–8.5
\n
pH
\n
Stony inerts (diameter ≥ 5 mm) cannot be higher than 5%.
\n
\n
\n
Minimum organic carbon: 20%
\n
Organic C
\n
Salmonella: absent in 25 g of the sample w.w. (where n = 5, c = 0, m = 0, M = 0)
\n
\n
\n
Humic and fulvic carbon: min 7%
\n
Humic and fulvic C
\n
E. coli lower than 1.000 cfu (where n = 5, c = 1, m = 1000 cfu/g, M = 5000 cfu/g).
\n
\n
\n
Organic N ≥ 80% of total N
\n
Organic N
\n
.Germination index (diluted 30%) ≥ 60%.
\n
\n
\n
Max C/N: 25
\n
C/N
\n
Algae and aquatic plants are allowed, such as Posidonia left on the shores, after separation from sand of the organic fraction. Their content must be lower than 20% of the initial mix.
\n
\n
\n
Salinity
\n
Thallium must be lower than 2 mg kg−1 (only in amendments containing algae).
\n
\n\n
Table 4.
Specifications and requirements of the Italian Legislative Decree n. 75 of 2010 (Annex 2) for green composted amendments and mixed composted amendments.
All requirements are expressed in dry weight. The category ‘Amendments’ includes also manure, artificial manure, green non‐composted amendment, composted turf, acid turf, neutral turf, humified turf, leonardite, vermicompost from manure, lignite. Cultivation substrates are in Annex 4, and the products with specific action on plants (e.g. mycorrhizal inoculants) are in Annex 6 of the same Legislative Decree [52].
\n
\n
\n
5. Perspectives of management practices
\n
Different approaches are clearly needed to upgrade the residues of coffee and olive tree cultivation, as well as the processing residues. The variety of approaches is a consequence of the diversity of (a) pedoclimatic areas that include altitude and latitude, soil texture and organic matter content, water regime and availability, (b) level of expertise of the small farmers, (c) social environment that includes training opportunities and availability to create associative forms among producers, (d) access to trade and communication networks, (e) easy access to community‐level processing installations.
\n
In the case of coffee, the valorization of residues (Figure 10) in agriculture, as animal feed and for energy production, apart from a few minor uses, is still the most attractive application to respond to the challenges of the rapidly evolving socio‐economic and poverty problems of the farmers in these areas. A minor use of plant leaves in organic coffee farms could be the production of herbal teas, whereas for the extraction of functional products for human food supplement, probably only more centralized processing installations can provide the appropriate machinery and food grade safety standards. Another minor use could be the production of edible mushrooms from (co)composted solid waste, i.e. mucilages and spent coffee grounds. This re‐use has long been studied by Cenicafé in Colombia and interesting results were obtained with shiitake [55] and Pleurotus [56] as simple technology among low‐income communities in the urban areas of the city of Manizales. However, sanitization and detoxification of the substrate remain the major problems and further development of substrate pre‐treatment would help to obtain a mushroom production meeting food‐grade safety standards.
\n
Figure 10.
Solid residues of coffee first step processing (i.e. up to the production of beans) in a small coffee farm in the Andean region (Ecuador). If not properly stored or quickly bio‐transformed, the residue can be easily re‐colonized by spoilage and pathogenic microorganisms (Source: Cristina Echeverria).
\n
The coffee prunings, actually mostly left in situ as a mulching agent or as an amendment, may retain their phytotoxity and presence of plant pathogens. Therefore their valorization in situ implies that they are processed via composting (or co‐composting in farms where cattle manure is available). (Co‐)composting will then be made by mixing prunings, leaves, coffee husk (i.e. the skin, pulps and parchment generated by pre‐ and post‐fermentation de‐hulling) and eventually manure. The residue amounts are relevant: for 1 tonne of coffee beans produced, ca. 1 tonne of husks are generated (dry coffee processing), while where wet processing is adopted, there will also be a relevant amount of wastewater from washings. The latter could be used to feed biodigesters for biogas production at community level since the process requires installations and machinery of capacity larger than the ones of a single small farm. In this case, transportation difficulties and costs should be taken into account.
\n
The transformation of coffee plantations residues at farm level, along with the residues up to the production of the coffee beans, for agricultural end‐of‐uses, requires a remarkable improvement of the process as it is actually adopted in most cases by small farmers. The composting process of cultivation residues (prunings, leaves) should lead to the production on‐farm of a detoxified, sanitized green composted amendment, suitable for use in organic agriculture, containing living microbial consortia. This goal can be properly achieved if these residues are bio‐transformed together with the coffee processing solid waste. The actual composting process, far from being a science‐based technology, needs the use of indigenous microbial starter cultures capable to degrade the recalcitrant substrates, to detoxify the phenolic toxic substances, transforming the intermediate and still toxic chemical compounds into useful phytostimulatory substances. In those farms where manure (preferably cow‐dung and horse manure) is available, the process of co‐composting should lead to a detoxified, sanitized mixed composted amendment. The two processes are different and require different expertises. In both cases, the use of selected starter cultures, bio‐compatible among them, allows to include those microbial cultures having relevant phytostimulatory activity to the plants and also bio‐control activity towards the most commonly encountered soil‐borne pathogens. The use of the mature, sanitized, humified compost obtained in this way as a fertilizer could substantially contribute to strengthen the natural plant defence traits and therefore minimize the density of the soil‐borne disease.
\n
The second alternative in small farms could be the re‐use of the solid residue as animal feed [57]. In different field trials, pigs and cows fed with up to 15% ensiled coffee pulp and 5% of bagasse showed no negative effects on weight compared to those fed with commercial concentrates, and the pulp used as a fodder in milking cows was shown to replace up to 20% of commercial concentrates. The advantages are that coffee husk and pulp are rich in glucides and minerals. However the presence of (poly)tannic complexes and of caffeine decreases the palatability of husk by animals. Furthermore, the caffeine has stimulatory and diuretic effects and tannins diminish the protein availability and inhibit digestive enzymes. By consequence, the removal of these two anti‐physiological components would require pre‐treatments consisting in repeated washings and the use of commercial inoculants to enhance the fermentation (i.e. silage) process. Therefore this alternative looks less feasible economically at single farm level, and would be probably feasible at more centralized facilities level.
\n
The third alternative of valorization could be the energy production. The use of biogas would fit for heating purposes at single farm level. Some case studies on the coffee processing factories indicate that the exploitation of the residues for the production of electricity is feasible. Studies carried out in Tanzania suggest that from coffee residues it is possible to obtain high methane yields: 650 m3 of methane per tonne of volatile solids for Robusta variety solid waste and 730 m3 methane per tonne of Arabica variety solid waste [58]. However, this alternative is probably more easily accomplished at a centralized facility level due to the engineering and expertise needed, rather than at single small farm level.
\n
It appears, in conclusion, that for the small coffee farms the valorization of solid wastes are in any case tightly linked to initiatives of socio‐economic nature, i.e. organize formal training and ‘hands‐on courses’ for farmers, improve the road system and accessibility of the single farms, and facilitate the formation of ‘cooperatives’ among farmers.
\n
In the case of olive tree cultivation waste, i.e. prunings and leaves, when they are still in the field can be finely cut and used as mulch (Figure 11) or ploughed into the soil. Another valorization would be to transform these residues into a humified compost. Recently a composting process of prunings and leaves enriched with phosphate rock has been described in Saudi Arabia [59]. This bio‐transformation process has a duration of 8 months, presumably because of the recalcitrance of the lignocellulosic substrate to degradation. In the case of olive oil extraction solid waste (wet olive husks), the most feasible option for small farmers is the re‐use in agriculture through composting. This process is a knowledge‐based technology, requiring some basic training for farmers. The process has been described by Echeverria et al. [60] at industrial level and can be applied also at farm level [61, 62]. Essentially it is a solid fermentation process carried out with the help of loaders for periodical turning the piles, and is different from static piles composting with/without forced ventilation. The biochemical transformation can be enhanced through the use of starters, prepared with virgin husks enriched with selected microbial cultures. The latter approach, with respect to composting without the use of the starter, allows to achieve deeper humification (i.e. higher content of humic substances), faster deodorization (disappearance of bad smells), shorter maturation time and better detoxification of the starting material. The process duration is, on average, 60– 90 days during which the initial material undergoes profound changes of its mechanical (e.g. particle size, texture), physical‐chemical (e.g. pH, humidity, phenol/lignocellulosic content, humification indexes), and biological traits (e.g. sanitization of all potential human pathogens, appearance of bioactive phytostimulatory substances, different microbiological profile). Microorganisms are the main drivers of the transformations occurring in the substrate, and their degradation activity leads to the production of carbon dioxide and minor amounts of other gases which evolve in the atmosphere, and to the production of heat (which, if let uncontrolled, can easily go to >70˚C leading to pasteurization of the matrix). From a biochemical point of view, the composting of wet husks must be viewed as a respiratory process which needs oxygen (the appropriate porosity and oxygen presence in the matrix is ensured by turnings and the presence of prunings) and gives rise to carbon dioxide. One of the consequences of the degradation of the substrate components with concurrent carbon dioxide formation is the loss of weight of the substrate, as an average 30–40% expressed in dry matter. Due to heat formation and periodical turnings, the water evaporates and as an average the humidity content decreases from the initial 65–70% to ca. 40% of the compost after 90 days. Complex biochemical reaction does occur too, which involves polycondensation and polymerization reactions leading to the formation of the humic substances useful for the soil fertilization purposes. The initial fresh matrix is toxic to plants, but after composting turns into a plant growth stimulator, due to the presence of auxins and other substances synthesized during the composting process and to the concurrent degradation of phenolic plant growth‐inhibitory substances, both processes being of microbial nature. The success of the composting process will ultimately depend on (a) the initial quality of the wet husks and starters and (b) the ability of the operator(s) to maintain the appropriate process conditions leading to the formation of mature compost in the time limits. The conditions will consist mainly in keeping under careful control the main process factors, i.e. oxygenation, heat and humidity. Appropriate oxygen presence and heat control will be achieved through periodical turning the piles when the temperature rises above 50˚C (indicated by long‐stem thermometers). The appropriate humidity will be ensured through the addition of wastewater, i.e. 60–70% (initial humidity, before composting) to obtain a compost with ca. 40 % (final humidity). The mature compost can be delivered to the farm soils as such for fertilization purposes [63]. In alternative, humidity can be further adjusted by air‐drying to the desired level. Humidity below 25% will allow longer storage of the product until use. The use of such a fertilizer on‐site is highly compatible with the principles of the regenerative agriculture, i.e. provides the opportunity to maintain and increase the carbon stocks in soil at farm level. This goal, if achieved until the threshold value of organic carbon reaches the minimum value of 3.5%, which allows to maintain the functional soil biodiversity [64]. If, on the contrary, the wet husks are not composted correctly, they will retain their bad odour and phytotoxicity, along with little or any humification of the initial material. In addition to the above described advantages using a correctly made compost as a fertilizer, the presence of microbial consortia, having phytostimulatory activity for the plants besides their fundamental role in the biotransformation of the initial matrix, would help substantially to strengthen the plant natural resources, minimize the attack by soil‐borne phytopathogens, and by consequence would allow the use of more eco‐friendly land management approaches.
\n
Figure 11.
A common agronomic practice in small farms for disposal of the olive tree prunings and leaves in situ: they are first placed inter‐rows, then finely cut and finally used as mulch or ploughed into the soil (facility ‘Azienda La Cerreta’, Castagneto Carducci, Livorno, Italy). This practice represents a step forward compared to the burning practice and is considered cost‐effective for small farms (Source: Marco Nuti).
\n
\n
Acknowledgments
\n
The authors wish to thank Prof. Laura Ercoli for critical reading of the manuscript. This work is part of a Research Grant (Proyecto Café) from UTN, Ibarra, Ecuador to MC Echeverria, PhD.
\n
\n',keywords:"rural areas, coffee solid waste, olive oil extraction solid waste, re‐use of agricultural waste, rural areas, regenerative agriculture, valorization of solid residues",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/55866.pdf",chapterXML:"https://mts.intechopen.com/source/xml/55866.xml",downloadPdfUrl:"/chapter/pdf-download/55866",previewPdfUrl:"/chapter/pdf-preview/55866",totalDownloads:2129,totalViews:465,totalCrossrefCites:3,totalDimensionsCites:4,totalAltmetricsMentions:1,impactScore:1,impactScorePercentile:61,impactScoreQuartile:3,hasAltmetrics:1,dateSubmitted:"November 15th 2016",dateReviewed:"April 25th 2017",datePrePublished:null,datePublished:"September 6th 2017",dateFinished:"June 6th 2017",readingETA:"0",abstract:"There are two problematic solid residues from agriculture and agro‐industry, produced in vast amounts in rural areas: those from coffee bean production and processing and those deriving from the extraction process of olive oil. Notwithstanding these residues originating in different geographical areas, they have striking similarities. They both derive from traditional, conventional and organic agriculture; they have a high content in lignins, celluloses and (poly)phenols; they are produced in million tonnes annually; they pose relevant environmental problems for disposal; they contain bioactive compounds; and the approach for their re‐use is often similar, sometimes overlapping. The most promising re‐uses in rural areas are for agriculture, as animal feed and for energy production. There are also minor uses, suitable for the production of added‐value commodities. The re‐use will be dependent on a variety of factors according to the diversity of (a) pedoclimatic areas that include altitude and latitude, soil texture and organic matter content, water regime and availability, (b) level of expertise of the small farmers, (c) social environment that includes training opportunities and availability to create associative forms among producers, (d) access to trade and communication networks and (e) easy access to community‐level processing installations. The perspectives of agronomic management and valorization are compatible with the objectives of a regenerative, sustainable agriculture.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/55866",risUrl:"/chapter/ris/55866",book:{id:"5979",slug:"solid-waste-management-in-rural-areas"},signatures:"Maria Cristina Echeverria, Elisa Pellegrino and Marco Nuti",authors:[{id:"201563",title:"Emeritus Prof.",name:"Marco",middleName:null,surname:"Nuti",fullName:"Marco Nuti",slug:"marco-nuti",email:"mn.marconuti@gmail.com",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:{name:"University of Pisa",institutionURL:null,country:{name:"Italy"}}},{id:"204216",title:"Dr.",name:"María",middleName:"Cristina",surname:"Echeverria",fullName:"María Echeverria",slug:"maria-echeverria",email:"mc.echeverria@hotmail.com",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:{name:"Universidad Técnica del Norte",institutionURL:null,country:{name:"Ecuador"}}},{id:"204217",title:"Dr.",name:"Elisa",middleName:null,surname:"Pellegrino",fullName:"Elisa Pellegrino",slug:"elisa-pellegrino",email:"elisa.pellegrino@sssup.it",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. The management of residues of coffee production and transformation in rural areas",level:"1"},{id:"sec_3",title:"3. The management of residues of olive oil extraction process in rural areas",level:"1"},{id:"sec_4",title:"4. Agronomic and legislative aspects",level:"1"},{id:"sec_5",title:"5. Perspectives of management practices",level:"1"},{id:"sec_6",title:"Acknowledgments",level:"1"}],chapterReferences:[{id:"B1",body:'Echeverria MC, Nuti M. Valorisation of the residues of coffee agro‐industry: Perspectives and limitations. Open Waste Management Journal. 2017;10:3-15\n'},{id:"B2",body:'Benin S, Thurlow J, Diao X, Kebba A, Ofwono N. Agricultural Growth and Investment Options for Poverty Reduction in Uganda. Washington D.C: International Food Policy Research Institute (IFPRI); 2008. Discussion Paper 790\n'},{id:"B3",body:'Hughes SR, López‐Núñez JC, Jones MA, Moser BR, Cox EJ, Lindquist M, et al. 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Universitad Tecnica del Norte, General José Maria Cordova, Ibarra, Ecuador
Institute of Life Sciences, Scuola Superiore Sant\'Anna, Piazza Martiri della Libertà, Pisa, Italy
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1. Introduction
The fast and uncontrolled growing population is a result of urbanization and industrialization. States economic growth is dependent on the number of working industries in it. Also, to fulfill the demands of growing population textile, food, petrochemical, plastic, leather, and metal factories are emerging day by day [1, 2, 3]. Each of these industries helps to the mankind for their betterment and responsible for creating several pollutants, destroying agricultural lands and natural habitats. On the other hand, all these industries are working on non-renewable energy sources like wood, coal, natural gas, and petroleum products [4, 5]. Non-renewable energy sources are of one-time use, once used one cannot utilize them again. Two main problems are associated with non-renewable energy sources firstly when they burnt the produces harmful pollutants which is not acceptable [6, 7]. From past couple of decades scientific community, is engaged to solve the pollutants removal/degradation problems which are not economical. When fossil fuel gets extensively used, they produce global warming. Global warming is mainly caused by carbon dioxide emission. Carbon dioxide is when produce it remains in the atmosphere and absorbs the harmful infrared radiations which are reflected from earth surface. Secondly, after consumption these energy sources are going to be extinct as their availability is limited [8]. Geographically, non-renewable energy stock is located only to certain territories hence, it might be the reason for clashes between energy enriched and energy deficient countries which may leads to the world war again. Because of all these problems like pollution, environmental and health hazards the use of non-renewable energy sources for long period are not viable [9, 10].
Use of renewable energy sources like solar energy, hydro energy, wind energy, geothermal energy and nuclear energy are the only alternatives for all above said problems. Major advantages of renewable energy sources are that they when used does not create any type of pollution as well as one can use them in cyclic manner. Only one thing that we must keep in mind that these can not be used directly as an energy, but one must convert in the form of energy [11]. Also, sometimes for the energy conversion process complex, huge and expensive machinery may require. The ultimate solution for all above discussed problems is the use of hydrogen energy. The sustainable and better future is the motivation for the production and use of hydrogen energy.
Hydrogen gas is also known as a green fuel, as it when used does not produced any harmful and toxic pollutants. Hydrogen is a very first element from the periodic table with symbol H and atomic number 1. It is present in a S block, first A (IA) group with electronic configuration 1S1. Because of only one electron present in its outermost shell, it can form only a single sigma bond with many other atoms. It is a nontoxic, colorless, odorless, and combustible element. Hydrogen is a nonmetal, present in a gaseous form under normal conditions. Hydrogen is at the top list in terms of abundance in the universe. Many studies shows that hydrogen is not only present on the planet earth but also it is present on and other planets too. Stars are producing helium from hydrogen under high temperature and pressure at their core. Being a smallest and lightest element hydrogen atom consist of one proton and one electron without any neutron.
Hydrogen has three isotopes adds proton (H), deuterium (D) and tritium (T) along with these chemists succeeded in the synthesis of 4H and 7H in a laboratory, which are not occurring naturally. Arrhenius theory of acids and bases is very useful in chemical science is depends on the hydrogen. Most of the chemical compounds which are synthesized in lab or naturally occurring are bonded to hydrogen because of its high reactivity. Water is a most important source for living organisms which is also known as a universal solvent is composed of two hydrogens and one oxygen. In the present chapter, different sources of hydrogen as an energy with photocatalytic hydrogen production methods mechanism from water and toxic hydrogen sulfide is depicted along with respective photocatalytic reaction setup for the generation of hydrogen. Both water and H2S splitting set ups are being reported in our latest work with the help of organic and inorganic semiconductor and composite photocatalyst materials.
2. Hydrogen production methods
After realizing the importance of hydrogen in clean energy and future fuel till date, many methods are well known for the generation of hydrogen.
Hydrogen can be produced mainly from biological, electrolytic, photocatalytic, steam reforming and thermochemical methods as shown in Figure 1. Microorganisms (algae and bacteria) can also be responsible for the generation of hydrogen using biological processes. Water can be spilt by using both electrolytic and sunlight (photo) into hydrogen and oxygen. Also, hydrogen sulfide can used as a rich source for hydrogen, which photocatalytically splits into hydrogen as a clean energy and sulfur for agriculture [12].
Figure 1.
Hydrogen production methods.
2.1 Biological method
Microorganisms such as algae and bacteria in absence of sunlight with organic matter can produce hydrogen using many biological reactions. In this method bacteria (microorganisms) break down the organic matter such as biomass, sugar, corn or waste and releases hydrogen gas. This method is also known as dark fermentation as no light is involved [13]. Biological method is under research and development stage as the efficiency of this process is not up to the mark.
2.2 Thermochemical method
Natural gas, coal, hydrocarbons and biomass is also rich with the hydrogen content. Thermal process like steam reforming is responsible for releasing hydrogen from these sources. Hydrogen when combines with carbon produces a hydrocarbon which are available naturally and are one of the main sources of hydrogen. Hydrocarbons like methane, ethane and propane (alkene and alkyne) are key compounds of hydrogen. More than 90% of hydrogen which we get nowadays is coming from hydrocarbons which has a fossil origin. These hydrocarbons are quite stable than the other sources of hydrogen and does not leave hydrogen easily unless catalysis process is used. Breaking of sigma bond present in carbon and hydrogen is most difficult but can be achieved by steam reforming in case of methane.
CH4+H2O→CO+3H2E1
Generally, in steam reforming process water (steam) and methane are mixed in presence of catalyst (noble metals) inside a tube in appropriate proportion. Main advantage of using this process to produce hydrogen is that many companies/industries are already with all the equipment’s setups are present. Perfect engineering and research and development in hydrogen generation from hydrocarbons field will fulfill the need of many upcoming generations [14].
2.3 Electrolytic method
This method uses electricity to get hydrogen and oxygen from decomposition of water. Now a days electrolytic water splitting is well developed and available in market commercially. This method is more efficient as compared to previous methods for production of hydrogen. Ultra-pure hydrogen can be produced by using electrolysis method. Also, bulk amount of hydrogen can be produced using this method but, the assembly required for this purpose is expensive [15]. Excess amount of energy is required in the form of overpotential to overcome activation barriers. If excess energy is not supplied the rate of hydrogen production is merely slow. Lately, hydrogen production using this method is not in demand as hydrogen can be generated in affordably amount from fossil fuels.
2.4 Photocatalytical method
In any chemical conversion reactants are converted into useful products either by photocatalytic or thermal reaction. The photocatalysis reaction method in which light/ photon is used to stimulate a photocatalyst substance (catalyst) which alters the rate of chemical reactions/process favorably without taking actual part in chemical process. Photocatalysis can also explained as a process in which light energy is used to activate the substance, which enhances the rate of a reaction without used in the chemical reaction [16]. Generally, electron-hole pairs are generated after absorption of light when the energy of the incident light/photons exact matches or exceeds the bandgap of that semiconductor photocatalyst material.
3. Mechanism of photocatalysis
In presence of light photocatalyst material shift the electron from valance band (VB) to the conduction band (CB). VB which has oxidative potential of +1.0 to +3.5 V versus the normal hydrogen electrode (NHE), and CB have a chemical potential of +0.5 to −1.5 V versus the NHE, hence they can act as reductants. Figure 2describes, photocatalysis method in three steps (1) migration of electrons (negative charge) from VB to CB, by leaving exact vacant holes (positive charge), (2) movement of excited holes and electrons to the surface and (3) excited electrons-holes they react with absorbed electron donors and electron acceptors for reduction and oxidation reactions. Along with proper band gap of semiconductor photocatalyst material its charge recombination rate, mobility and lifetime of electron and holes also plays a crucial role in overall hydrogen production [17].
Figure 2.
Mechanism of photocatalytic H2 production.
3.1 Semiconductor photocatalyst material
Recently, charge recombination is delayed using either use of co-catalyst (platinum) on the surface of semiconductor photocatalyst which boosts the overall efficiency of hydrogen. Sacrificial agents such as methanol, EDTA, sulfides, sulfates and benzyl alcohol are also act as an oxygen scavenger in the process by enhancing the total yield of hydrogen production. After first report on TiO2 for hydrogen production by Gratzelet al. the hydrogen generation field is considered as of immense importance [18]. Many researchers have published in the photocatalytic hydrogen generation field by changing catalysts, co-catalysts, combination of two catalysts (composites, coupled system). Till date, nano metal oxides, sulfides, niobates, tantalates and vanadates which contained the metal of d0 or d10 electronic configurations such as In, Ga, Sb, Bi and Ag. Further, binary and ternary nano sulfides (CdS, ZnS, SnS2, ZnI2S4, CdI2S4 and Sb2S3) nitrides oxynitrides, carbon based, and organic semiconductor materials has been reported as alternative photocatalysts for H2 generation. Nanomaterial based semiconductor photocatalyst systems (TiO2, SnO2, WO3, ZnO, Si2O7, ZrO2, SrTiO3, LaCrO3, BaTiO3) have many advantages as compared to their bulk counterparts and hence preferred in photocatalytic hydrogen generation [18, 19, 20]. These advantages are, high surface area, higher optical absorption, shorter charge migration length, higher solubility, tunable electronic structure, plasmonic resonance assisted charge injection and separation. All these plus points can be utilized to scale up photocatalytic hydrogen production using nanostructured semiconductor photocatalyst system. Following are the two photocatalytic hydrogen production setups are discussed with schematic representation using water and hydrogen sulfide as a source of hydrogen.
4. Photocatalytic hydrogen generation setups
4.1 Water splitting
Many attempts were taken place for the construction and engineering of setup for photocatalytic hydrogen generation [16]. Depending on the light source used (in sunlight or in a lab) reaction setup is modified, and the simplest form is described here with schematic representation Figure 3.
Figure 3.
Schematic representation of photocatalytic water splitting, (a) Light source fitted vertically in quartz tube having water circulation, (b) photoreactor, (c) a eudiometric tube.
Generally, photocatalytic hydrogen production experiments were carried out in a wooden cupboard box which is known as a photocatalytic water splitting setup. This box is having the dimensions around 30 × 30 × 30 inch with closed wooden/stainless steel chamber with observing window as shown in schematic. Figure 3 represents the schematic of setup and can be divided into three main parts as shown in figure. Firstly, the light source fitted vertically in quartz tube having water circulation (a) arrangement for cooling purpose. 400–600 W lamp with emission wavelength 200–800 nm can be used depending upon the photocatalyst. Secondly, inside this box a two neck 250 mL borosilicate round bottom flask (b) act as a photoreactor. In photoreactor water, co-catalyst, magnetic needle and scavenger are added. Lastly, produced H2 in a reactor is collected in a eudiometric tube (c) for characterization on gas chromatography (GC). The eudiometer tube is with a saturated solution of sodium chloride (NaCl) to avoid the dissolution of evolved gases [16].
4.2 H2S splitting
Irritating smell of H2S gas is the reason for less research and development in this area as compared to water splitting. Earlier, Claus process is used for H2S splitting which is mainly focused on sulfur and not on hydrogen. Photocatalytic H2S splitting experiments for the generation of H2 can be performed under light source or in sunlight depending upon the band gap of semiconductor photocatalyst [21, 22]. For light source (under lamp) an assembly is kept in a fuming hood to avoid bad smell and a schematic representation of a setup is shown in Figure 4. This setup can be divided in A to I parts as shown below.
Figure 4.
Photocatalytic H2S splitting reaction setup.
For avoiding over heating of the photoreactor (D) throughout the photo-reaction water circulation is added, Photoreactors are of various capacity (100 to 1000 mL) can be used, the quantity of photocatalyst (0.05 to 1 gram) was decided in every photoreaction. A source of light (F) of intensity 450–600 W can be used as discussed in above water splitting set up. Hydrogen sulfide generated in (A-B) and collected extra amount in (C) is bubbled through the solution in the photoreactor under continuous stirring (E). Bubble rate differs as the capacity of photoreactor changes. The excess H2S was trapped in NaOH solution (G-H). The amount of evolved H2 was measured using graduated gas burette (I).
Large scale production of hydrogen using toxic H2S is also possible like water splitting as discussed above in water splitting setup section.
5. Large scale hydrogen production and usage
Large scale production of hydrogen energy from water splitting is also possible by using this reaction setup. Appropriate photocatalyst with suitable band gap and light frequency source can leads to enhance hydrogen production. Quantity of photocatalyst and capacity of photoreactor promises the large-scale production of hydrogen energy. It can be achieved with proper engineering inside the lab as well as on roof of the lab under natural sunlight. Large scale production of hydrogen using toxic H2S is also possible like water splitting as discussed above. Hydrogen is a clean energy which have applications in soil refining, methanol generation, steel production and ammonia production. Nowadays, it is also used for all type of transportation (alternative for Compressed Natural Gas, CNG), power generation, homes and fuel in jets and ships. Recently, the worlds first hydrogen-powered train rolled in Germany. After this many countries tested hydrogen fuel-cell passenger trains. Also, a UK-based car manufacturer company produced a two-seater hydrogen vehicle. The US, Europe and China are the top consumers of hydrogen mainly in refineries sector. Alas, all these emerging hydrogen applications are not economical than the other energy resources as hydrogen costs around USD 12–16/Kg.
6. Transportation and storage of hydrogen gas
Nowadays, the production of H2 gas is not a new to a scientific community but the ways of transportation and storage of it is under continuous research. Transportation is mainly taking place either by road or by water routs in a cryogenic or compressed cylinders. As hydrogen is having low density the transportation is difficult and expensive so, for transporting H2 from industry to working sites is achieved using pipelines [23]. In many cases gas is compressed and then filled in appropriate cylinders as per the quantity and requirement. Laboratories and research centers require hydrogen in small quantities and transportation of such cylinders can be takes place using small trolleys. On the other hand, the amount of hydrogen required for industrial purpose is in large quantities which are once received by transported kept in a gas bank.
Storage of hydrogen gas as a future fuel is important because one cannot produce it efficiently and in large amount at the domestic or small industry level. For storage purpose research centers, industries and automobiles have well engineered tanks. The concept of adsorption is utilized for storage of gas, here a porous material with large surface areas like activated carbon are needed. In absorption metals are combined with hydrogen atoms to form a metal hydride. Palladium, zirconium and other transition metals are also reported for the large amount of gas absorption [24, 25].
Recently, photocatalytic solar hydrogen production from water splitting on a 100 m2 scale panel, carbon films, closed systems, plates and sheets is demonstrated by K. Domen research group. A 100 m2 array of panel reactors and other setup types effective for more than 90 days. Lately, chemical combination between hydrogen and boron or nitrogen is under investigation. During this combination hydrogen molecules are dissociated and forms hydrogen atoms which then goes in the empty spaces between the metals lattice structure [26].
7. Conclusions
Hydrogen produced from electrolytic, biological, steam reforming and photocatalytic methods can be utilized as a clean energy source. Still, plenty of research and development is needed to enhance the efficiency and to reduce the overall economy of the process. Though the various hydrogen production methods which are discussed here are better and less expensive, an effective method need to be developed for future energy crises. Photocatalytic hydrogen generation from water and hydrogen sulfide splitting using available setup is with opportunities to development for young researchers. Besides the transportation and storage of hydrogen gas it must be considered in a frame of the energy system globally.
\n',keywords:"energy, hydrogen, photocatalysis, storage",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/79642.pdf",chapterXML:"https://mts.intechopen.com/source/xml/79642.xml",downloadPdfUrl:"/chapter/pdf-download/79642",previewPdfUrl:"/chapter/pdf-preview/79642",totalDownloads:112,totalViews:0,totalCrossrefCites:0,dateSubmitted:"August 9th 2021",dateReviewed:"November 8th 2021",datePrePublished:"December 12th 2021",datePublished:null,dateFinished:"December 12th 2021",readingETA:"0",abstract:"Sustainable development of the world is mainly dependent on the use of present energy resources, which primarily includes water, wind, solar, geothermal, and nuclear power. Hydrogen as a clean and green energy source can be the resolution of the energy challenge and may satisfy the demands of several upcoming generations. Hydrogen when used it does not produce any type of pollutant and this makes it a best candidate as a clean energy. Hydrogen energy can be generated from natural gas, oil, biomass, and fossil fuels using thermochemical, photocatalytic, microbiological and electrolysis processes. Large scale hydrogen production is also testified up to some extent with proper engineering for multi applications. Alas, storage and transportation of hydrogen are the main challenge amongst scientific community. Photocatalytic hydrogen production with good efficiencies and amount is well discussed. Till date, using a variety of metal oxide-sulfide, carbon-based materials, metal organic frameworks are utilized by doping or with their composites for enhance the hydrogen production. Main intents of this chapter are to introduce all the possible areas of hydrogen applications and main difficulties of hydrogen transportation, storage and achievements in the hydrogen generation with its applications.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/79642",risUrl:"/chapter/ris/79642",signatures:"Vikram Rama Uttam Pandit",book:{id:"10687",type:"book",title:"Energy Efficiency",subtitle:null,fullTitle:"Energy Efficiency",slug:null,publishedDate:null,bookSignature:"Dr. Muhammad Wakil Shahzad, Prof. Muhammad Sultan, Dr. Laurent Dala, Prof. Ben Bin Xu and Dr. Yinzhu Jiang",coverURL:"https://cdn.intechopen.com/books/images_new/10687.jpg",licenceType:"CC BY 3.0",editedByType:null,isbn:"978-1-83969-828-6",printIsbn:"978-1-83969-827-9",pdfIsbn:"978-1-83969-829-3",isAvailableForWebshopOrdering:!0,editors:[{id:"174208",title:"Dr.",name:"Muhammad Wakil",middleName:null,surname:"Shahzad",slug:"muhammad-wakil-shahzad",fullName:"Muhammad Wakil Shahzad"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:null,sections:[{id:"sec_1",title:"1. 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DOI: 10.1016/j.enbuild.2013.06.018'},{id:"B12",body:'Saleska S, Harte J, Torn M. The effect of experimental ecosystem warming on CO2 fluxes in a montane meadow. Global Change Biology. 1999;5:125-141. DOI: 10.1046/j.1365-2486.1999.00216.x'},{id:"B13",body:'Hussein A. Applications of nanotechnology in renewable energies-A comprehensive overview and understanding. Renewable and Sustainable Energy Reviews. 2015;42:460-467. DOI: 10.1016/j.rser.2014.10.027'},{id:"B14",body:'Kalamaras C, Efstathiou A. Hydrogen production technologies: Current state and future developments. Power Options for the Eastern Mediterranean Region. 2013;2013:1-9. DOI: 10.1155/2013/690627'},{id:"B15",body:'Kumar S, Himabindu V. Hydrogen production by PEM water electrolysis—A review. Materials Science for Energy Technologies. 2019;2:442-454. DOI: 10.1016/j.mset.2019.03.002'},{id:"B16",body:'Pandit V, Arbuj S, Hawaldar R, Kshirsagar P, Ambekar J, Mulik U, et al. Hierarchical CdS nanostructure by Lawesson\'s reagent and its enhanced photocatalytic hydrogen production. RSC Advances. 2015;5:13715-13721. DOI: 10.1039/C4RA15138K'},{id:"B17",body:'Pandit V, Arbuj S, Pandit Y, Naik S, Rane S, Mulik U, et al. Solar light driven dye degradation using novel organo–inorganic (6,13-pentacenequinone/TiO2) nanocomposite. RSC Advances. 2015;5:10326-10331. DOI: 10.1039/C4RA11920G'},{id:"B18",body:'Kumbhar D, Pandit V, Deshmukh S, Ambekar J, Arbuj S, Rane S. Synthesis of hierarchical zno nanostructure and its photocatalytic performance study. Journal of Nanoengineering and Nanomanufacturing. 2015;5:227-231. DOI: 10.1166/jnan.2015.1250'},{id:"B19",body:'Nevase K, Arbuj S, Pandit V, Ambekar J, Rane S. Synthesis, characterization and photocatalytic activity of tungsten oxide nanostructures. Journal of Nanoengineering and Nanomanufacturing. 2015;5:221-226. DOI: 10.1166/jnan.2015.1249'},{id:"B20",body:'Jawale V, Gugale G, Chaskar M, Pandit S, Pawar R, Suryawanshi S, et al. Two-and three-dimensional zinc oxide nanostructures and its photocatalytic dye degradation performance study. Journal of Materials Research. 2021;36:1573-1583. DOI: 10.1557/s43578-021-00174-w'},{id:"B21",body:'Pandit V, Arbuj S, Hawaldar R, Kshirsagar P, Mulik U, Gosavi S, et al. In situ preparation of a novel organo-inorganic 6,13-pentacenequinone–TiO2 coupled semiconductor nanosystem: A new visible light active photocatalyst for hydrogen generation. Journal of Materials Chemistry A. 2015;5:4338-4344. DOI: 10.1039/C4TA06606E'},{id:"B22",body:'Pandit V, Arbuj S, Mulik U, Kale B. Novel functionality of organic 6,13-pentacenequinone as a photocatalyst for hydrogen production under solar light. Environmental Science & Technology. 2014;48:4178-4183. DOI: 10.1021/es405150p'},{id:"B23",body:'Mazloomi K, Gomes C. Hydrogen as an energy carrier: Prospects and challenges. Renewable and Sustainable Energy Reviews. 2012;16:3024-3033. DOI: 10.1016/j.rser.2012.02.028'},{id:"B24",body:'Schlapbach L, Züttel A. Hydrogen-storage materials for mobile applications. Nature. 2001;414:353-358. DOI: 10.1038/35104634'},{id:"B25",body:'Andersson J, Gronkvist S. Large-scale storage of hydrogen. International Journal of Hydrogen Energy. 2019;44:11901-11919. DOI: 10.1016/j.ijhydene.2019.03.063'},{id:"B26",body:'Nishiyama H, Yamada T, Nakabayashi M, Maehara Y, Yamaguchi M, Kuromiya Y, et al. Photocatalytic solar hydrogen production from water on a 100-m2 scale. Nature. 2021;598:304-307. DOI: 10.1038/s41586-021-03907-3'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Vikram Rama Uttam Pandit",address:"vikramupandit@gmail.com",affiliation:'
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\r\n\tTransforming our World: the 2030 Agenda for Sustainable Development endorsed by United Nations and 193 Member States, came into effect on Jan 1, 2016, to guide decision making and actions to the year 2030 and beyond. Central to this Agenda are 17 Goals, 169 associated targets and over 230 indicators that are reviewed annually. The vision envisaged in the implementation of the SDGs is centered on the five Ps: People, Planet, Prosperity, Peace and Partnership. This call for renewed focused efforts ensure we have a safe and healthy planet for current and future generations.
\r\n
\r\n\t
\r\n
\r\n\tThis Series focuses on covering research and applied research involving the five Ps through the following topics:
\r\n
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\r\n
\r\n\t1. Sustainable Economy and Fair Society that relates to SDG 1 on No Poverty, SDG 2 on Zero Hunger, SDG 8 on Decent Work and Economic Growth, SDG 10 on Reduced Inequalities, SDG 12 on Responsible Consumption and Production, and SDG 17 Partnership for the Goals
\r\n
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\r\n\t2. Health and Wellbeing focusing on SDG 3 on Good Health and Wellbeing and SDG 6 on Clean Water and Sanitation
\r\n
\r\n\t
\r\n
\r\n\t3. Inclusivity and Social Equality involving SDG 4 on Quality Education, SDG 5 on Gender Equality, and SDG 16 on Peace, Justice and Strong Institutions
\r\n
\r\n\t
\r\n
\r\n\t4. Climate Change and Environmental Sustainability comprising SDG 13 on Climate Action, SDG 14 on Life Below Water, and SDG 15 on Life on Land
\r\n
\r\n\t
\r\n
\r\n\t5. Urban Planning and Environmental Management embracing SDG 7 on Affordable Clean Energy, SDG 9 on Industry, Innovation and Infrastructure, and SDG 11 on Sustainable Cities and Communities.
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\r\n
\r\n\tThe series also seeks to support the use of cross cutting SDGs, as many of the goals listed above, targets and indicators are all interconnected to impact our lives and the decisions we make on a daily basis, making them impossible to tie to a single topic.
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Thus proteomics, an area of research that detects all protein forms expressed in an organism, including splice isoforms and post-translational modifications, is more suitable than genomics for a comprehensive understanding of the biochemical processes that govern life. The most common proteomics applications are currently in the clinical field for the identification, in a variety of biological matrices, of biomarkers for diagnosis and therapeutic intervention of disorders. From the comparison of proteomic profiles of control and disease or different physiological states, which may emerge, changes in protein expression can provide new insights into the roles played by some proteins in human pathologies. Understanding how proteins function and interact with each other is another goal of proteomics that makes this approach even more intriguing. Specialized technology and expertise are required to assess the proteome of any biological sample. Currently, proteomics relies mainly on mass spectrometry (MS) combined with electrophoretic (1 or 2-DE-MS) and/or chromatographic techniques (LC-MS/MS). MS is an excellent tool that has gained popularity in proteomics because of its ability to gather a complex body of information such as cataloging protein expression, identifying protein modification sites, and defining protein interactions. 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