3.1 Sludge characterization and multiple valorization alternatives
The quality of the EBPR sludge was addressed with the objective of determining the potential downstream valorization pathways. Table
2 summarizes the global parameters of the raw, dried sludge, and sludge’s ashes in terms of macronutrients (NPK), PHA content, and calorific value (HHV).
Table 2
Main characteristics of the raw EBPR sludge sampled at the end of the aerobic phase and before dewatering, after drying (105 °C), and after combustion (850 °C)
TS | g Kg-1 | 7.47 ± 0.05 | - | - |
VS | g Kg-1 | 5.78 ± 0.10 | - | - |
PHA | % CDW | 42.21 ± 0.01 | - | - |
TP | g 100 g TS-1 | 4.22 ± 0.13 | 4.14 ± 0.61 | 17.41 ± 0.66 |
Loosely bound P | % of TP | 5.45 | 7.97 | - |
Biological P (poly-P) | % of TP | 85.13 | 80.27 | - |
Chemically bound P | % of TP | 9.42 | 11.76 | - |
TKN | g 100 g TS-1 | 7.68 ± 0.65 | 7.38 ± 0.97 | 0.45 ± 0.03 |
K+ | g 100 g TS-1 | 0.37 ± 0.06 | 0.47 ± 0.02 | 1.38 ± 0.07 |
HHV | MJ Kg-1 TS | - | 22.53 ± 2.42 | - |
COrg/N | g C g N-1 | 10.04 | | |
In terms of nutrient (NP) content in sludge, our results show interesting valorization opportunities as raw material for biofertilizer manufacturing after a biologic post-treatment resulting in these high nutrient concentrations. As such, they are consistent or even higher than reference concentrations in studies addressing resources recovery. Regarding N, [
49] reported 1–2.7 (g 100 g TS
-1) in anaerobically digested biowaste and in urban and agro-industrial sludges after a composting process which were then successfully tested in ryegrass pot trials. Moreover, [
50] informs 3.87 (g 100 g TS
-1) in composted urban sewage sludge aimed for field application as a source of nutrients and soil conditioner which was accepted after a complete decision support framework application. Finally, [
51] showed results ranging between 4.9 and 6.7 (g 100 g TS
-1) for air-dried, heat-dried, and composted sludge also in line with [
52,
53] who concluded that the quality of their obtained products were as efficient as commercially available phosphate fertilizers. Hence, the 7.38 g P 100 g TS
-1 found in the dried sludge in our trials shows a very interesting concentration of this nutrient. Regarding P, reference values are around 1–2.3 (g 100 g TS
-1) after anaerobic digestion, and several thermal, crystallization, and processes combination of sewage sludge aiming to resource and energy recovery [
53‐
55]. Our results, in line with typical P content reported for full-scale EBPR (4–5 g 100 g TS
-1) [
52,
56,
57], roughly represent two times the P content in conventional activated sludge. As such, considering N and P contents, this nutrient-rich material is a suitable candidate for valorization via BBFs manufacturing for both N and P recoveries.
Available inorganic fertilizers, particularly diammonium phosphate [(NH
4)
2HPO
4], one of the most applied fertilizers, is recognized for its excellent source of P and N for plant nutrition [
58]. This mineral fertilizer has a standard grade of 18-46-0 (18% N, 46% P
2O
5 (~ 20% TP), and 0% K by weight). Our recovered products show approximately half of these nutrient concentrations which shows a great opportunity for nutrient rich recovered materials that would otherwise have been wasted. Moreover, the fertilizing value of any given product is not only related to its NP content, but also organic matter and carbon, microelements, microorganism population, growth-regulating substances, and metabolites which are present in the sludge and can potentially act as a biostimulant enhancing plant growth as demonstrated in several studies [
52,
55,
59] and improve the overall health of soils.
Interestingly, the P fractionation analysis showed that around 80% of the TP included in the sludges (raw and dried materials) are mainly poly-P, a polymer of orthophosphate (PO
43-). Poly-P serves as a reservoir for inorganic PO
43- and an energy source for fueling cellular metabolism [
20]. According to the length of the polymer chain, the rate at which the PO
43 - is mobilized depends on the activity of phosphorus-solubilizing organisms existing in the soil. Hence, the obtained percentage of poly-p in our material shows an interesting potential to act as a slow/moderate release fertilizer favoring sustained plant growth with reduced PO
43- runoff, thus reducing potential environmental impact [
60].
In order to address the suitability of the analyzed sludge for fitting in a specific product function category (PFC) within the European regulation (EU) 2019/1009, physicochemical characteristics in terms of nutrient (NPK) and total solids (TS) were established. Regarding nutritional characteristics, considering the produced sludge, the obtained fertilizing product after a stabilization/sanitization process would most likely meet the requirements on nutrient content of PFC 1(A)(I): SOLID ORGANIC FERTILISER and PFC 3(A): ORGANIC SOIL IMPROVER. Moreover, heavy metal content was analyzed against the legal threshold established for those categories and against Spanish law regarding the use of sludge as fertilizer. As it can be observed in Table
3, heavy metal content complies with the EU fertilizer regulation and also with the Spanish regulation which legally authorizes sludge as raw material for fertilizer products, provided it complies with heavy metal maximum concentration values (Spain RD 506/2013 on Fertilizer Products (BOE, 2017).
Table 3
Heavy metal content in one sample of raw sludge and relevant European regulatory limits for different product function categories (PFCs) within the EU fertilizing products and Spanish regulation establishing quality of raw materials for fertilizers
Average concentration in this study | < 0.50 | 47.8 ± 0.9 | 295 ± 3 | 64 ± 4 | 0.57 ± 0.01 | 16.1 ± 0.4 | < 0.50 | 3.81 ± 0.12 |
REGULATION (EU) 2019/1009 | PFC 1(A)(I): SOLID ORGANIC FERTILISER | 2 | 50 | 800 | 300 | 1.5 | 120 | 1 | 40 |
PFC 3(A): ORGANIC SOIL IMPROVER | 2 | 50 | 800 | 300 | 2 | 120 | 1 | 40 |
Spain - RD 503/2013 on fertilizers products (BOE, 2017) | Compost Class A | 70 | 25 | 200 | 70 | 0.7 | 45 | 0.4 | nd |
Compost Class B | 250 | 90 | 500 | 300 | 2 | 150 | 1.5 | nd |
Compost Class C | 300 | 100 | 1000 | 400 | 3 | 200 | 2.5 | nd |
As it can be observed, it is remarkable to state that metal contents of the studied EBPR sludge (mg Kg
-1 dw) were always below the limits established in the analyzed regulations. Therefore, its characteristics make it suitable for its use directly in agricultural field since it complies with the Directive (86/278/EEC), and also with some of the most stringent worldwide regulatory limits for agricultural application of sludge, such as the national regulations from Austria, the Netherlands, Denmark, Canada, or Japan [
61,
62]. Regarding other compounds of concern such as PAHs of the sludge, every PAH family component analyzed was below detection limit of 0.010 mg kg
-1 TS, except for naphthalene (0.014 ± 0.002) and phenanthrene (0.020 ± 0.003). And the overall PAH content of raw sludge was in the low range of what was found in literature for conventional sludges used to formulate organo-mineral fertilizers [
63]. Moreover, our material complies with the EU legislation (EC, 2000 and EU 2019/1009) which propose that the “sum of PAHs,” should not exceed 6 mg kg
-1 TS
-1 in sludge for land application. In addition, by the application of a downstream biological process such as biodrying or composting exhibiting a thermophilic phase, these compounds along with other micropollutants will be likely degraded resulting in even lower concentrations in the final product as reported in [
64].
Finally, regarding safety assessment, EU regulation establishes a limit of Absence of CFU in 25 g for Salmonella spp., and < 1.000 CFU in 1 g of sample for Escherichia coli or Enterococcaceae. In this regard, the proposed methods for drying the material before its field application or use as feedstock in fertilizing products manufacturing (thermal drying or biodrying by the action of thermophilic micro-organisms) will most likely grant the maintenance of the solid matrix at a temperature of at least 70 °C for 1 h (such is the process condition stablished in the EU Regulation 142/2011 for animal by products and End of waste Criteria EUR 23990). Within this high temperature, pathogenic micro-organisms are killed, and the material could be considered hygienically safe.
This work exhibits that wastewater-derived sludges can be considered to be equal to other authorized feedstocks for fertilizing products manufacturing in terms of quality and safety [
65‐
69]. Nevertheless, sewage sludge is currently not considered within the allowed 2019/1009 feedstocks to produce component material categories (CMCs). Consequently, we identify the necessity of deepening the discussion regarding the inclusion of valuable raw materials such as the sludge in this study in future versions of the regulation. Considering the inclusion of this type of materials into the regulation would help boosting the impacts of the current circular economy and zero waste policies.
Another interesting characteristic of the produced EBPR sludge is its high PHA content. It is noteworthy that the EBPR reactor was fed with a short-chain VFA-rich solution produced on-site in a pre-fermenter (See 2.1 EBPR WWTP). As stated by [
70], the PHA production is strongly related to the short-chain VFA concentration being high when VFA availability is elevated. As an energy-rich compound, PHA can be derived for biofuel production and to be used as a raw material for bioproducts such as bioplastics or other biopolymers. Our results show a PHA accumulation of 42.21% ± 1.29 (dw) close to some of the highest reported values. For instance, [
71] obtained PHA concentration of 57% (dw) treating domestic wastewater, [
72] reached 62% (dw) using activated sludge acclimatized in a microaerophilic-aerobic process, and [
73] reported about 50% (dw) using activated sludge as a feed for EBPR process.
Recently, [
74] obtained 41% (dw) in a side-stream system fed with fermented VFA liquors and remarked that a minimum value of 40% (g PHA g
−1 VS) is necessary for an economical down-stream recovery of the PHA polymer. Hence, our produced sludge strikes as being potentially promising for bioplastics production. Moreover, being PHAs an energy-rich material, results also show that EBPR sludge can be derived to biofuel manufacturing since it exhibits a HHV comparable with wood bark, olive husk, and walnut shell [
75] after drying it. These previous drying steps will be accomplished by submitting the produced sludge to a biodrying process which enables to reach a moisture content below 40% which is the reported value for an effective and sustained combustion process [
76].
All in all, the sludge characteristics open a wide range of potential valorization pathways to be used either as a raw material for direct fertilizing, as an input material for BBFs manufacturing, as biofuels, and alternatively for biopolymer production.
3.3 Product benchmarking
Several value-added products have been obtained from sludge at lab scale in this study such as nutrient-rich, PHA-rich, energy-rich sludge, and nutrient- and protein-rich biomass. However, to address the feasibility and the economic potential of these products for reaching full-scale applications, a comparative analysis using commercially available products, which our products intend to replace, must be performed. Hence, a benchmark of alternative products in terms of costs and values is presented hereby. Noteworthy that this preliminary analysis will not consider potential variations of the sludge nutrient composition, transport and spreading costs which are crucial to provide real-time assessment [
114]. Also, the saved costs of sludge management and treatment, which WWTP must currently take care of, are not included. Hence, the values presented here could certainly be more attractive when overall economic and environmental saved costs are included.
Regarding the potential use as a BBF, the nutrient fertilizer value of sludge and of the produced MA and PPB biomass depends on the total major plant nutrient (NPK) composition [
115] and the economic valuation of these materials which is the total value of available nutrients (TVANS) calculated using Eq. (
3) [
114]:
$$TVANS= TVAN+ TVAP+ TVAK$$
(3)
where TVAN is the total value available nitrogen per ton (€); TVAP is the total value of phosphorus available per ton (€); and TVAK is the total value of available potassium per ton (€). Net TVANS is calculated by subtracting the production costs or the market price to the TVAN so to get the real value of nutrient normalized by the cost of obtaining it. Net TVANS of our products are compared with net TVANS of commercially available fertilizer products in Table
6.
Table 6
Nutrient availability and nutrient value of this study’s products compared against commercially available products
Raw sludge | Organic fertilizer | 7.68% | 4.22% | 0.37% | 0.18 | 0.18 | Transport/application/safety | This study | |
Dry sludge | Organic fertilizer | 7.38% | 4.14% | 0.47% | 0.17 | 0.01 | Available drying facilities | | |
Sludge ashes | Fertilizer | 0.45% | 17.41% | 1.38% | 0.24 | -0.08 | Available incineration facilities | | |
MA biomass | Organic fertilizer | 15.19% | 8.10% | 0.40% | 0.35 | -0.38 | Scaling up production costs | | |
PPB biomass | Organic fertilizer | 26.07% | 1.50% | 2.50% | 0.45 | -0.85 | Scaling up production costs | | |
Urea | Inorganic fertilizer | 46.00% | 0.00% | 0.00% | 1.61 | 0.87 | Scarce raw materials—environmental concerns | | |
Triple superphosphate | 0.00% | 46.00% | 0.00% | 1.28 | 0.69 |
Potassium chloride | 0.00% | 0.00% | 50.00% | 0.38 | 0.19 |
Phosphoric acid | Liquid fertilizer | 85.00% | 0.00% | 0.00% | 0.00 | 0.13 |
As it can be observed, with the current production costs and market prices, the TVANS of our products are somewhat less economically profitable and still not convenient as opposed to traditional inorganic alternatives (TVANS 0.18 for raw sludge application vs. 0.58 for average NPK simultaneous application (€ Kg-1)). Also, transport distance and spreading costs need to be thoroughly evaluated to address the economic feasibility of these novel products. Nonetheless, production costs tend to decrease as more research and scaling up of the novel processes are developed. Also, current global scenario reveals problems such as rising food, fuel, and feedstocks prices together with input costs, highlighting the need for EU agriculture and food supply chains to become more resilient and sustainable. As such, biobased fertilizer production strikes as an attractive alternative to avoid economic uncertainties and supply risks. At the same time legal constraints are becoming stricter and EU’s environmental strategy strongly points to zero waste and circular economy strategies. All these combined elements will continue to generate a more favorable scenario for novel fertilizer products derived from waste valorization approaches.
In terms of potential application as ingredients for livestock feeds, the nutritive quality of the product must be checked against commercially available meals (i.e., soybean meal) and the cost can be compared in terms total protein content [
123] in a similar way as it was proposed for the fertilizer value (Table
7).
Table 7
Protein availability and protein value of this study’s products compared against commercially available livestock feed formulations
MA biomass | 45.30% | 53.00% | 2.16 | 0.73 | 1.43 | This study | | |
PPB biomass | 65.40% | 53.00% | 2.16 | 1.30 | 0.86 | This study | | |
Soybean meal | 46.00% | 45.00% | 1.18 | 0.53 | 0.65 | | |
Rape meal | 36.00% | 42.00% | 1.11 | 0.47 | 0.64 | |
As can be observed, both the protein content and the essential amino acids in MA and PPB biomass are in line with commercially available meals, making our products suitable for this purpose. Moreover, when considering the market prices of available products, it turns out that MA and PPB biomass are more convenient that traditional meals with similar protein content and similar amino acid quality. Hence, if installed as a side stream of a WWTP where a drying facility already exists (i.e., thermal valorization of the sludge), this technology’s production costs would drop dramatically making this alternative even more economically attractive. Moreover, the reduction of the potential sludge-related environmental impacts helps boost the sustainability of the wastewater treatment sector. Nonetheless, it is noteworthy that our results were obtained in lab-scale trials, and the scaling up of this type of processes can make the CAPEX and OPEX to increase leading to a less favorable economic scenarios. Particularly, artificial illumination, centrifugal harvesting/dewatering, and drying are the crucial operational parameter for MA and PPB cultures. These elements will need to be considered when scaling the process.
All in all, the studied sludge and the derived biomass production included in this study meets the physicochemical characteristics to be used as a BBF, as a biofuel, bioplastic precursor, and/or as growing mediums to produce ingredients for animal feed formulations as promising valorization routes.