Table 1 presents the results of the elemental analysis, pH, and loss of ignition (LOI) of the tested waste. All waste samples were characterized by different pH levels. A low pH was found for the dust samples (SGD, RD, and PBCD). Excessively high or low pH may influence the biotoxicity of the waste (Phoungthong et al. 2016); for example, the toxicity of heavy metals may increase at low pH (Emamverdian et al. 2015; Phoungthong et al. 2016). Seneviratne et al. (2017) found that phytotoxicity is the result of a combination of several factors that inhibit plant growth. For example, fluoride phytotoxicity increases at low pH (Stevens i in. 2000), while heavy metal cations in solution may reduce the phytotoxicity of fluorides (Palmieri et al. 2014).
Table 1
The characteristic of tested foundry waste (Bożym and Klojzy-Karczmarczyk 2020, 2021)
sample
|
Elementar analysis [% wt.]
|
pH
|
LOI
[% wt.]
|
C
|
H
|
N
|
S
|
LFW
|
2.7 ± 1.2
|
0.05 ± 0.05
|
0.04 ± 0.02
|
0.09 ± 0.02
|
7.9 ± 0.4
|
4.0 ± 2.0
|
SGD
|
5.3 ± 0.0
|
0.11 ± 0.00
|
0.03 ± 0.02
|
0.40 ± 0.00
|
5.1 ± 0.1
|
7.1 ± 0.6
|
RD
|
11.4 ± 4.1
|
0.12 ± 0.03
|
0.08 ± 0.01
|
0.65 ± 0.07
|
5.4 ± 0.5
|
13.8 ± 3.2
|
TD
|
6.1 ± 3.3
|
0.12 ± 0.04
|
0.07 ± 0.02
|
0.40 ± 0.14
|
6.0 ± 0.2
|
7.9 ± 5.2
|
EAFD
|
7.8 ± 1.0
|
0.13 ± 0.04
|
0.04 ± 0.00
|
1.05 ± 0.21
|
7.6 ± 1.5
|
10.0 ± 0.7
|
PBCD
|
2.1 ± 0.3
|
0.11 ± 0.03
|
0.04 ± 0.02
|
0.37 ± 0.13
|
5.4 ± 0.5
|
2.5 ± 0.4
|
The LOI value is an indicator of the presence of organic matter in the waste. Among the tested wastes, EAFD and RD samples demonstrated the highest LOI values. The dust from the regeneration section (RD) contained organic binder residues, hence its high LOI value (Bożym 2018). While EAFDs, similar to dust from thermal regeneration, may contain organic compounds from organic pollutants – such as adhesives, paints, or lubricants – contained in scrap, which may evaporate at high temperature during the metal melting process (Zanetti and Godio 2006; Salihoglu and Pinarli 2008). The elemental composition of the tested waste was similar to the foundry dust analyzed by Chirila and Ionescu Luca (2011).
Foundry waste usually contains metal residue from castings. Waste from steel and iron foundries is characterized by the highest iron content (Skvara et al. 2002; Sofilic et al. 2004; Li et al. 2010; Gengel et al. 2010). This finding was confirmed in the current research. The percentage of Fe varied within a wide range: 35.9–41.9% for EAFD, 16.0–19.4% for SGD, 12.7–13.0% for TD, 10.4–84.0% for PBCD, 4.1–9.8% for RD (Bożym and Klojzy-Karczmarczyk 2020), and 14.1% for LFW (Bożym 2020). Iron is not a toxic metal, so its content in waste is not limited. Foundry waste may also contain heavy metals. The content of metals, metalloids, and nutrients in foundry waste was investigated in previous studies (Bożym 2020). Figure 1 shows the sum of heavy metals (Co, Mo, Ni, Cr, Zn, Cu, Pb, and Cd) in the tested foundry waste.
Among the heavy metals tested in this study, zinc characterized the highest percentage (23–81%), then copper (6–31%) and chromium (4–27%) for most wastes, and lead (33%) for EAFD. The highest content of all heavy metals was found in EAFD dust. It is known that EAFDs are the most problematic waste in foundries due to the toxic content of heavy metals and organic pollutants (Salihoglu and Pinarli 2008; Bożym and Zalejska 2014; Chirila and Ionescu Luca 2011; Mymrin et al. 2016; Bożym 2020). As Salihoglu and Pinarli (2008) found, metals such as Zn and Pb are very volatile at the temperature of molten steel and therefore accumulate in the furnace dust (Salihoglu and Pinarli 2008). Disposal of EAFD is problematic for foundries, as this dust may be generated in large quantities. It is estimated that in the typical operation of an electric arc furnace, about 2% of the input is converted into dust and 10–20 kg of EAFD are produced per 1 ton of castings. Worldwide, foundries produce about 8 million tons of EAFD annually; in the USA it is about 0.7 million tons, in Europe up to 1 million tons, and in Poland 4,000 tons of EAFD (Chirila and Ionescu Luca 2011; Bożym and Klojzy-Karczmarczyk 2020). One method of utilizing EAFD with a high percentage of iron is to recycle it back into the foundry furnace. In addition, some heavy metals are recovered from the EAFD, but the cost-effectiveness of the process depends on the amount of metal in the dust. In the current study, a large amount of heavy metals, especially Zn, was also found in the dust from the shot blasting section (PBCD) (Strobos, and Friend 2004; Miyoshi et al. 2008; Chirila and Ionescu 2011; Bożym and Zalejska 2014; Bożym and Klojzy-Karczmarczyk 2020). Moreover, PBCDs were characterized by the highest variability of heavy metal content, which was caused by the variability in the composition of the castings. The lowest metal content of all tested dust samples was found in RD and TD, i.e. dusts from the regeneration and transport units. On the other hand, the lowest heavy metal content of all waste samples was found in the LFW. The tested LFWs also demonstrated low leachability of heavy metals (Bożym 2017, 2019, 2020). LFW consisted mainly of SFS; therefore, this waste may be used for the production of road aggregates or other applications.
Phytotoxicity Tests
The assessment of phytotoxicity is based on the GI test, plant growth, leaf size and color, chlorophyll content, biomass, and the accumulation of pollutants (Gyuricza et al. 2010; Awasthi et al. 2017). The phytotoxicity assessment of the tested wastes based on the condition of the L. sativum L. (cotyledons, biomass, heavy metal accumulation) and the GI test is presented below. The GI results obtained in the direct test were compared with the leachate test performed in the previous study (Bożym 2020).
Accumulation Test
According to Phoungthong et al. (2016), an excess of heavy metals in the substrate causes stress in plants and leads to reduced germination, delayed growth, and leaf chlorosis. For this reason, the condition of L. sativum L. (cotyledon color, shoot length, and biomass) was additionally assessed during the accumulation test. A blackening of the seed coat of L. sativum L. from the EAFD, SGD, and RD substrates was found. The same effect was observed in previous studies on leachate from this waste (Bożym 2020). Presumably, the cause of this effect was the high iron concentration and the low pH. Some authors have reported that heavy metals may cause seeds, roots, and leaves to blacken. Mossor-Pietraszewska (2001) noted that Al inhibited root growth and darkened them, while Emamverdian et al. (2015) found blackened plants with a high Mn content in the substrate. However, in other studies with L. sativum L. growing on slag from copper and zinc smelters with high concentrations of Zn, Cu, and Pb in the substrate, this effect was not found. In the current research, L. sativum L. sprouts died after 2–3 days of the accumulation test on EAFD, SGD, and RD substrates (Bożym et al. 2020). In previous studies on leachate from the same foundry waste (Bożym 2020), however, plant material was collected from all variants in an accumulation test. Another parameter of L. sativum’s condition was shoot length, which was measured from the end of the root to the cotyledons. The longest shoots for L. sativum L. were from the control (mean: 13.5 cm) and LFW (mean: 14.5 cm) groups. The length of the shoots from the dust substrate ranged from 12 to 13 cm (TD) and from 5 to 12 cm (PBCD). In the case of PBCD, the large variance of the results depended on the composition of the samples (n = 10). The best condition (cotyledon color, stem length, and biomass) of L. sativum L. was found in the LFW and control groups. On the other hand, the cotyledons of L. sativum L. of the control, LFW, TD, and PCBD groups were colored well, indicating no negative effect of those substrates on chlorophyll. It is known that increased accumulation of heavy metals in the aerial parts may cause leaf chlorosis, a reduction in yield, leaf area, relative growth rate, and assimilation rate (Wahid et al. 2007; Keser 2013; Gill et al. 2013; Emamverdian et al. 2015; Masarovičová and Kráľová 2017). On the other hand L. sativum L. is resistant to negative environmental factors, including heavy metals (Dursun et al. 2018) and it is used as a bioindicator of soil contamination, as it shows changes in protein expression even at low concentrations of heavy metals (Janecka and Fijalkowski 2008; Seneviratne et al. 2017).
In addition to the assessment of the condition of the plants, a yield analysis was performed. The aerial parts of L. sativum L. from the LFW, TD, and PCBD substrates and the control group were collected. The roots were not analyzed due to the potential for contamination by the substrate, especially with dust, which could have affected the results. Figure 2 presents the dry mass of L. sativum L. shoots obtained during the 7-day accumulation test. The results were compared with the control (sand). No plants were taken from the SGD, RD, and EAFD substrates. On the basis of the results, it may be stated that the biomass of L. sativum L. was significantly higher from the LFW substrate than in the control (p ≤ 0.05), which may indicate that LFW stimulated the growth of L. sativum L.. This is confirmed by the results of the GI test. The reason for this effect could be the low content and leachability of heavy metals and the neutral pH of LFW compared to foundry dust samples (Bożym 2020). Moreover, the higher biomass of L. sativum growing on the TD substrate compared to the control (p ≤ 0.05) were also analyzed. Keser (2013) found a reduction in the biomass of the edible parts of Eruca sativa irrigated with wastewater in comparison with the control, influenced by high heavy metal content. The author did not note these effects for L. sativum L., which explains the higher resistance of cress to heavy metals. Many studies have confirmed the negative effect of heavy metals on the biomass of plants (Wahid et al. 2007; Kachout et al. 2009; Farouk et al. 2011; Vijayarengan and Mahalakshmi 2013).
The phytoaccumulation of heavy metals from waste and soil depends on the total content, leachability, pH, and metal interactions in substrate. For example, Keser (2018) found slight differences in the content of Cd, Pb, and Ni in the edible parts and roots of L. sativum L .after 20 days of the test. In the case of Cr and Cu, an accumulation of these metals in the root and a low content in the edible parts was reported. The distribution of heavy metals in plant organs is determined by the species and age of the plant, the transport mechanism, the degree of environmental pollution by heavy metals, and the interaction between metals (Seregin and Ivanov 2001; García-Lorenzo et al. 2014; Seneviratne et al. 2017). In the current study, a wide range of heavy metal content was found in L. sativum L. after 7 days of the experiment. The results are presented in Fig. 3. No plants were collected for analysis from the SGD, RD, or EAFD substrates due to the atrophy of the sprouts. This effect was not found in the leachate test (Bożym 2020). his may suggest that an accumulation test carried out on leachate may not be sufficient for phytotoxicity assessment of waste. Similar results were obtained for hazardous waste from zinc and copper smelters in previous studies (Bożym et al. 2020).
Zinc displayed the highest accumulation out of all heavy metals in L. sativum from all substrates (Fig. 3). This effect may be influenced by the high percentage of this metal in the waste under analysis. In previous studies on leachate from foundry waste, the content of Zn, Cu, and other metals in L. sativum L. was lower than in the current study (directly on the substrate). For example, Zn and Cu accumulation in both experiments differed by 5–37% and 48–66%, respectively. Based on the heavy metal content in L. sativum L., the BCF value was calculated (Table 2). No metal accumulation by L. sativum L. in any substrate was found in the current study (BCF < 1.0). Slightly higher BCF values were calculated for Cu and Zn from LFW, Zn from TD, and Cd and Pb from PBCD (BCF = 0.27–0.67).
Table 2
Bioconcentration factors (BCF) in shoots of L. sativum L.
metal
|
LFW
(n = 18)
|
SGD
(n = 6)
|
RD
(n = 6)
|
TD
(n = 6)
|
EAFD
(n = 6)
|
PBCD
(n = 30)
|
Cd
|
<LOQ
|
nd
|
nd
|
0.19
|
nd
|
0.44
|
Pb
|
0.07
|
nd
|
nd
|
0.18
|
nd
|
0.63
|
Cu
|
0.27
|
nd
|
nd
|
0.05
|
nd
|
0.08
|
Zn
|
0.67
|
nd
|
nd
|
0.28
|
nd
|
0.03
|
Cr
|
0.06
|
nd
|
nd
|
0.01
|
nd
|
0.02
|
Ni
|
0.02
|
nd
|
nd
|
0.01
|
nd
|
0.02
|
Mo
|
0.02
|
nd
|
nd
|
0.03
|
nd
|
0.08
|
Co
|
0.05
|
nd
|
nd
|
0.05
|
nd
|
0.03
|
nd – no data (no plants to analyze) |
<LOQ - the metal content of the substrate or plants was below the limit of quantification |
Germination Index Directly On The Substrate
The GI was calculated from the values for L. sativum L. germination and root elongation in the direct test on the substrate compared to the control (sand). Due to the fact that the root length has a direct impact on the GI value, Fig. 4 shows the GI value while Fig. 5 shows the root length of L. sativum L. in the direct test (GI 1) and on the leachate (GI 2) (Bożym 2020). Additionally, Fig. 4 shows the ranges of the inhibitory/stimulating action of waste on plants according to Zucconi et al. (1985). A GI value of < 50% indicates high phytotoxicity, 50–80% indicates medium phytotoxicity, and 80–100% no phytotoxicity. On the other hand, a GI of > 100% suggests a stimulating effect of the waste or leachate on the plant.
Seeds from some substrates had blackened in the GI test, similar to the effect in the accumulation test and previous leachate tests (Bożym 2020). The L. sativum L. growing on these substrates was also characterized by shortened and blackened root tips. It is known that heavy metals in the substrate may shorten the roots and shoots of plants (Shanker et al. 2005; Zou et al.; Emamverdian et al. 2015; Sharma et al. 2010; Vijayarengan and Mahalakshmi 2013; Janecka and Fijalkowski 2008; Courtney and Mullen (20019; Phoungthong i in. (2016). An additional phytotoxic factor may be a low pH, which increases the toxicity of heavy metals (Emamverdian et al. 2015; Phoungthong et al.2016; Courtney and Mullen 20019). At the same time, some metals may stimulate seed germination and root elongation at lower concentrations, while at higher concentrations they are phytotoxic (Phoungthong et al.2016). Many scientific reports indicate the effect of some toxic substances contained in the substrate – e.g. phenols, cyanides, salinity, fluorides, ammonia, or low-weight carboxylic acids – on the germination and elongation of L. sativum L. roots (Hoekstra et al. 2002; Himanen et al. 2012; Palmieri et al. 2014; Manas and De las Heras 2018).
The leachate test showed a stimulating effect of LFW, TD, and PBCD leachate on L. sativum in a previous study (Bożym 2020). This effect was not observed in the current study, directly on the substrate. The contact test showed that LFW were characterized by moderate or no phytotoxicity; the dust samples, SGD, TD, RD, and PCBD, demonstrated high phytotoxicity (Fig. 4). EAFD was characterized by the highest phytotoxicity, in both the leachate and direct tests. In a previous study, SGD and RD leachate were less phytotoxic than the substrate in a direct test. This effect could have been influenced by the dilution of pollutants in the leachate (liquid/solid, L/S, 1/10); at the same time, in the direct test L/S was 1/1. The presence of organic pollutants, for example, phenol and formaldehyde, could also have contributed to the phytotoxicity of the tested wastes. An additional phytoxic factor could have been the low pH. In a study of hazardous wastes from a zinc and copper smelter, higher phytotoxicity of the waste was also found in the direct test than in the leachate test (Bożym et al. 2020).
The root length of L. sativum L. from the control, LFW, and PBCD substrates was higher in the direct test than in the leachate test (Fig. 5). These results may suggest that L. sativum r L. root elongation is faster on a solid substrate than on leachate. On the other hand, for SGD, RD, TD, and EAFD substrates, a much shorter root length of L. sativum L. was observed in the contact test than in the leachate test. Nevertheless, the final GI value was lower due to the considerable root length of L. sativum L. from the control (sand) in the direct test.
Summarizing the current research, it may be concluded that L. sativum L. is useful for assessing the phytotoxicity of foundry wastes. In addition, different phytotoxicities were found for waste in the direct and leachate tests. Phytotoxicity tests have an impact on the assessment of the use of foundry waste, especially SFS in road engineering and for agrotechnical purposes, e.g. for the production of Technosols (Bożym and Klojzy-Karczmarczyk 2021). Studies have shown that LFW with SFS was characterized by low phytotoxicity, because of the low content of heavy metals and neutral pH; its leachate may stimulate the growth of L. sativum L. Tests on foundry dusts showed different phytotoxicities, depending on the composition of the waste and the type of the test. Higher phytotoxicity was observed in the direct test than in the leachate test. For this reason, it is recommended to use both the leachate and the direct tests simultaneously to assess the phytotoxicity of waste.