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Transfer and transformation mechanism of chromium in stainless steel slag in pedosphere

  • Shuang Cai , Liguang Wang EMAIL logo , Yuzhu Zhang , Tao Li , Tielie Tian and Tianji Liu
Published/Copyright: February 3, 2023
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High Temperature Materials and Processes
From the journal High Temperature Materials and Processes Volume 42 Issue 1

Abstract

The trivalent chromium (Cr) leached from stainless steel slag can be oxidized into hexavalent Cr with strong toxicity in the natural storage process, thus causing severe pollution to the surrounding soil, water, and atmosphere. Currently, the toxicity hazards caused by high Cr concentrations in plants, animals, and humans have attracted widespread attention from across the world. In this study, an overview is presented regarding the occurrence mode, leaching mechanism, and influencing factors for the presence of Cr in the soil of stainless steel slag under natural landfilling conditions. Meanwhile, a summary is made for the research progress in Cr absorption, transport, and accumulation in the soil–plant system. Besides, allowing for the toxicity and detrimental effect of Cr(vi) in the soil as well as the application of biological and chemical methods for the remediation of Cr(vi)-contaminated soil, a review is conducted on the approach to recycling Cr from stainless steel slag and the application of chemical remediation and biological methods to remedy Cr-containing soil. Finally, a discussion is conducted about the transfer and transformation behavior of Cr in soil–plant system, the practical application of soil remediation technology and the prospect of research in this field.

Keywords: stainless steel slag; chromium; migration transformation; toxicity; repair

1 Introduction

Stainless steel slag is a by-product derived from the smelting process of stainless steel. In 2021, China’s crude steel production of stainless steel amounted to 30.632 million tons. Besides, according to the rule that 3 tons of stainless steel production yield 1 ton of stainless steel slag, the annual production of stainless steel slag is estimated to exceed 10 million tons [1]. With high silicon and calcium contents, stainless steel slag is usually recycled to produce blast furnace flux [2], sintering flux [3], slagging agent [4], Portland cement [5], ceramic material [6], and CO2 capture material [7]. However, the overall utilization rate is less than 30%, and the stainless steel slag is mostly landfilled. According to statistics, the cumulative pile of stainless steel slag in China has exceeded 50 million tons over the past decade. Stainless steel slag contains heavy metal element chromium (Cr), which will be dissolved by rain in the process to enter the soil, thus posing threat to soil, water, and human health. Approximately 1.29 × 105 t of Cr is released annually in the global environment, most of which has accumulated in soil and thus caused serious Cr pollution [8]. The content of Cr(vi) in irrigation water of agricultural land in China shall not be higher than 0.1 mg·L−1 (GB 5084-2021). The standard of Cr content in agricultural land is shown in Table 1 (GB 15618-2018).

Table 1

Limit of Cr content in agricultural soil (mg·kg−1)

Type pH ≤ 5.5 5.5＜pH ≤ 6.5 6.5＜pH ≤ 7.5 pH＞7.5
Paddy field 250 250 300 350
Other land 150 150 200 250

According to the exact smelting processes, stainless steel slag can be divided into argon oxygen decarburization (AOD) furnace slag and electric arc furnace (EAF) slag, with the Cr-contained by stainless steel slag existing mainly in zero-valent or trivalent states [9,10]. Zero-valent Cr can be recycled by crushing, fine grinding, and magnetic separation, while trivalent Cr exists mainly in soluble silicate and insoluble spinel ore phases [11], which makes it difficult to recycle Cr. In the process of landfilling, silicate ore phases will be dissolved because of rain leaching, which causes Cr(iii) to be dissolved [12]. The leaching solution of stainless steel slag is alkaline, the pH value usually exceeds 10 [13]. The dissolved Cr(iii) can be oxidized in an alkaline solution, which converts Cr(iii) into highly toxic Cr(vi) [14]. Besides, the presence of CaO facilitates the conversion into Cr(vi) [11] and increases the leachate toxicity of Cr. The accumulation of dissolved Cr in soil and the absorption of it by plants will inhibit plant growth. While Cr6+ has strong migration [15] [8] and toxicity, and can cause teratogenesis, carcinogenesis, and mutation [16,17]. Moreover, once Cr6+ seeps into the ground or groundwater source with the washing of rainwater, it can be spread and enriched through the food chain, and finally may cause fatal harm to the environment and human body [18]. Cr(vi) with strong migration can enter the respiratory tract, skin, digestive tract, and mucous membrane of human body in various forms (such as solid, liquid, and gas) [19,20,21], thereby causing harm to human health. Considering these potential risks to humans and plants, Cr contamination in soil has attracted worldwide attention. This also shows the importance and urgency of heavy metal solid waste disposal.

In this study, the research progress of Cr migration, accumulation, and toxicity in stainless steel slag soil–plant system was reviewed. The phase characteristics, leaching characteristics, migration, and transformation of stainless steel slag in soil were summarized. Finally, the remediation methods and means of Cr- contaminated soil were discussed to determine the future research direction and demand. The purpose is to provide reference for ecological risk assessment and recycling of stainless steel slag.

2 Phase characteristics of stainless steel slag and occurrence form of Cr

The phase composition of stainless steel slag and the occurrence form of Cr have a significant impact on its recycling and the level of leaching risk. The chemical composition of AOD slag and EAF slag is shown in Table 2, which shows that their chemical composition is dominated by CaO and SiO2, accounting for more than 70 wt% of the total content. Stainless steel slag is alkaline, with the binary basicity of AOD slag and EAF slag in the range of 1.7–2.8 and 1.1–1.8, respectively. The Cr content of AOD slag usually falls below 1 wt%, and the Cr content in only part of AOD slag can reach up to 3.1 wt%. The Cr content in EAF slag is considerably higher than in AOD slag, mostly in the range of 3–8 wt%, and the Cr content could reach as high as 13.8 wt% in some EAF slags.

Table 2

Chemical composition of EAF and AOD slags in wt%

Type CaO SiO2 MgO Al2O3 Cr2O3 MnO TFe Fe2O3 FeO R Ref.
EAF 46.9 33.5 6.2 2.3 2.9 2.6 1.6 0.4 1.1 1.4 [9]
47.4 31.7 7.0 4.6 4.7 2.3 1.2 1.5 [23]
45.7 32.3 5.2 3.7 4.8 1.0 3.3 1.4 [24]
43.4 24.2 8.8 2.6 13.8 6.0 1.8 [25]
49.6 33.1 5.5 2.1 4.6 1.8 1.1 1.5 [23]
47.8 28.7 7.7 4.8 4.7 0.2 3.6 1.7 [26]
43.2 33.2 8.8 3.5 6.1 0.6 1.3 [27]
36.0 32.0 4.4 7.9 10.4 5.8 1.6 1.1 [28]
46.5 28.0 7.4 4.3 8.0 1.7 2.7 1.7 [29]
41.3 29.7 10.9 3.3 7.7 0.7 3.8 1.4 [30]
41.0 28.2 9.4 2.1 13.3 1.5 2.0 1.5 [30]
Average 44.4 30.4 7.7 3.8 7.4 2.1 1.1 2.7 1.7 1.5
AOD 54.1 26.5 6.3 4.9 1.8 1.0 2.0 0.6 1.2 2.0 [9]
55.9 31.7 3.0 1.0 3.1 1.9 0.8 1.8 [31]
66.0 23.6 4.7 1.5 0.3 <0.1 2.8 [32]
55.9 24.7 5.9 1.1 0.5 0.2 1.2 2.3 [22]
56.7 29.9 8.9 1.7 1.0 0.8 1.9 [33]
55.7 33.0 7.6 1.3 0.7 0.4 0.3 1.7 [34]
53.2 28.4 7.7 1.5 0.5 0.3 1.9 [35]
59.6 25.4 4.3 1.2 0.3 0.2 0.7 2.4 [36]
65.8 24.2 6.6 1.7 0.5 2.7 [37]
55.9 24.7 5.9 1.1 0.5 0.2 1.2 2.3 [38]
Average 57.9 27.2 6.1 1.7 0.9 0.7 1.1 0.6 1.1 2.2

Wang et al. [22] carried out a study on the mineral phase composition of AOD slag, revealing that the mineral phase composition of AOD slag involved dicalcium silicate, magnesia calcite, pyroxene, calcite, spinel in tiny amounts, magnetite and trace amount of Fe x O, glass phase, RO phase, and calcium ferrite. The volume fraction of dicalcium silicate exceeded 80%, while that of magnesite, pyroxene, and calcium silicate approached 5%, respectively. As proposed by Shen et al. [9], the mineral phase composition of AOD slag involved calcium silicate (2CaO·SiO2) and lignite (2CaO·SiO2), feldspar in tiny amounts, fluorite, magnesite, CaCO3, and free CaO. Pillay et al. [11] investigated the mineral phase composition of EAF slag, revealing that the mineral phase of EAF slag was dominated by dicalcium silicate and magnesite calcium silicate, spinel solid solution in tiny amounts, RO phase, and vitreous metallic ore phase.

From above, it can be known that the mineral phases of AOD slag are dominated by dicalcium silicate (Ca2SiO4), fluorite (CaF2), magnesite (MgO), magnesite calcium silicate (C3MS2), and magnesium-chromium spinel (MgCr2O4), with Cr accumulating in the chromium-magnesium spinel phase. The mineral phase composition of EAF slag mainly involves dicalcium silicate and magnesite calcium silicate, with Cr accumulating in the chromium-containing (Fe,Mg)O(Fe,Cr,Al)2O3 phase (Table 3).

Table 3

Mineral phase composition of stainless steel slag

Type Phase composition Ref.
EAF FeCr2O4, FeFe2O4, Ni-Cr-Fe, Fe-Cr(Ni), Ca2SiO4, Ca14Mg2(SiO4)8, Ca3Mg(SiO4)2, Ca2MgSi2O7, Ca2Al2SiO7, SiO2 [9]
AOD FeFe2O4, FeCr2O4, Ni-Cr-Fe, Fe-Ni, Ca14Mg2(SiO4)8, Ca2SiO4, Ca4Si2O7F2, MgO, CaF2
EAF Glassy matrix, MgO·Cr2O3, CaO·TiO2, 2CaO·SiO2, Metallic droplets [23]
EAF Ca3Mg(SiO4)2, MgCr2O4, γ-Ca2SiO4 [24]
EAF (Fe,Mg)(Cr,Fe)2O4, Ca3Mg(SiO4)2, Ca2SiO4 [25]
EAF Ca2SiO4, Ca3Mg(SiO4)2, spinel solid solution, RO phase, Fe-Cr-Ni [17]
EAF (Ca,Mg)2SiO4, Ca2SiO4, CaCrO4, Ni-Cr-Fe, Mg(Cr,Fe)2O4 [27]
AOD Ca2SiO4, MgCr2O4, Ca4Si2O7F2, Ca3Mg(SiO4)2, Ca7MgSi4O16 [29]
AOD Ca2SiO4, MgO, Fe-Ni, Fe3O [23]
AOD Ca2SiO4, C3MS2, augite, rankinite, spinel, magnetite, Wustite, glass phase, RO phase, calcium ferrite [22]
AOD γ-Ca2SiO4, Ca3Al2O6, MgAl2O4, Mg2SiO4 [36]
AOD Ca2SiO4, CaF2, MgO, Ca3MgSi2O8, MgCr2O4 [37]
AOD Ca2SiO4, Ca3MgSi2O8, (Ca,Mg,Al)2(–Si,Al)2O6, MgO, (Si,Al)2O6 [38]
AOD Ca3Mg(SiO4)2, Ca4Si2O7F2, γ-Ca2SiO4, Ca7Mg(SiO4)4, MgO, β-Ca2SiO4, CaSiO3, CaF2 [39]

There are various valence states in which transition metal element Cr exists in slag, with oxygen partial pressure and basicity of slag as the significant influencing factors for the morphology of Cr in stainless steel slag. Morita et al. [40] explored the reaction behavior of Cr2+, Cr3+, and Cr6+ in slag, discovering that Cr existed mainly in the form of Cr(vi) in the slag with high oxygen partial pressure and alkalinity, while Cr(iii) showed a greater stability in the acidic and reductive atmospheres. The lower the oxygen partial pressure, the higher the proportion of Cr2+ in slag. In the study conducted by Mirzayousef Jadid and Schwerdtfeger [41], it was demonstrated that high alkalinity caused Cr to exhibit a higher valence state, and that there was a large amount of Cr(vi) existing in the calcium silicate slag under a strong oxidizing atmosphere.

In summary, the oxygen partial pressure of the slag is high during the oxidation period of stainless steel smelting, with the content of chromium oxide in the slag reaching as high as 5–30%, and the Cr contained in the slag exists mostly in the form of Cr2O3. In the later stage of stainless steel smelting, there is a reducing atmosphere created in the smelting furnace, which diminishes the chromium oxide content rapidly in the slag (<3%). At this time, the oxygen partial pressure of the slag declines, and Cr exists mostly in the form of CrO after the balance between slag and gold is reached. If the slag with high alkalinity is allowed to persist in the atmosphere, it is likely that Cr is oxidized into Cr(vi) at a slow pace, and Cr(vi) exhibits a clear tendency of leaching and migration in aqueous solution, which will cause severe pollution to the surrounding soil and ecological environment.

3 Form of Cr in soil and its influencing factors

The Cr present in stainless steel slag will be dissolved to enter the soil as a result of rain leaching, thus polluting the soil. The concentration and valence state of Cr are regarded as the important indexes required to evaluate the severity of soil pollution, which has immediate impacts on the migration and bioavailability of Cr in soil. Therefore, it is necessary to conduct a thorough analysis regarding the state of Cr in the soil and the influencing factors for this, which is essential for assessing environmental risks and developing appropriate remediation strategies.

3.1 Existence form of Cr in soil

In soil, Cr can exist as different chemical components, taking such forms as exchangeable state, carbonate binding state, oxidation state, reduction state, and residue state. Of these, the exchangeable and carbonate-bound fractions of Cr are bioavailable, and the residual fraction of Cr cannot be used by organisms [42]. According to some studies, residual Cr accounts for 99% of the total Cr, and the bioavailable and mobile Cr in soil accounts for as low as about 1% of the total Cr concentration. In other words, the mobility of Cr drives the combination of organic matters (OMs) with the minerals in the soil to form a strong complex, which enables its migration and transformation [43]. Although the residual Cr is difficult to ingest directly by organisms, it can still be released into the surrounding environment and soil through such physical and chemical processes as hydrolysis, oxidation, and reduction. When the low-valence Cr(iii) is oxidized to Cr(vi) with greater toxicity, solubility, and mobility, it can pose a serious risk to the ecological environment [44]. Besides, when the Cr-containing stainless steel slag is stored for a long period of time, the form taken by Cr will be affected by the physical and chemical properties of soil, such as pH [45], Eh [46], OM content [47], Fe-Mn oxide, and inorganic colloid composition [48], which brings a change in the migration and bioavailability of Cr in the soil–plant system, as shown in Figure 1.

Figure 1 Schematic diagram of influencing factors for the migration and transformation behavior of Cr in soil.
Figure 1

Schematic diagram of influencing factors for the migration and transformation behavior of Cr in soil.

3.2 Impact of pH on the form of Cr in soil

The pH value of the soil is one of the most significant influencing factors for the balance between solubility, adsorption, and the desorption of Cr in soil. By exploring the impact of pH on the form taken by Cr through leaching experiments, Chaurand et al. [49] obtained the results suggesting that Cr existed mainly in the form of Cr(iii) in slag, with a tiny amount of Cr(iii) oxidized into toxic Cr(vi) in the soil with the basicity of pH > 9. Although Cr(iii) could be oxidized by MnO2 in the soil with a pH value close to neutrality, it remains likely for Cr(vi) to be reduced to Cr(iii) in an acidic environment. As argued by Shadreck and Mugadza [50], Cr(iii) could exist in two single forms, Cr3+ and Cr(OH)4−, but only under two extreme conditions of leaching solution: pH value of 0–2.8 and 13.9–14, respectively. When the pH value of the leaching solution increases to the range of 2.8–13.9, the process of Cr(iii) releasing into the leaching solution in ionic form is effectively a dynamic equilibrium process of Cr2O3 ↔ Cr(OH)4− ↔ MgCr2O4 transformation. Cr(OH)4− exists in the intermediate form of Cr(iii), which determines the final form of Cr(iii) in the leaching solution at different pH values. Recently, Xu et al. [51,52] investigated the impact of pH value on the morphogenesis of Cr in soil by adjusting the acidity and alkalinity of the soil, which reveals that Cr(iii) migration tends to occur in acidic soil, Cr(iii) migration can be effectively inhibited in alkaline soil, and the alkaline environment is favorable for the generation of Cr(vi) [44].

These results demonstrate a complex interaction between the pH value of soil and the chemical form of Cr. In summary, lowering the soil pH level can promote the migration and release of Cr(iii), while increasing soil pH level may lead to the formation of Cr(vi) in soil, thus causing plants to uptake Cr, which could put the agricultural system and human health in jeopardy.

3.3 Impact of Eh on Cr morphogenesis in soil

As an indicator reflecting the reducibility of macroscopic oxidation for all the substances in the leaching solution, Eh determines the conversion of Cr(iii) into Cr(vi) in the soil. Under certain pH and Eh conditions, Cr(iii) and Cr(vi) can be converted into each other in soil through REDOX reaction. Therefore, soil Eh is a key influencing factor for the concentration of Cr(vi) in the aqueous phase, which depends on the mass balance between the average REDOX rates. High Eh is conducive to the formation of oxides. In this case, Cr(vi) exists in such forms as HCrO4 −, Cr2O7 2−, and CrO4 2−, showing high mobility and bioavailability [53]. In a low-Eh environment, Cr(vi) is the dominant form. It exists in the form of Cr 2 O 4 2 − when the pH value exceeds 6.0. As the pH level decreases, Cr(iii) exists in such form as Cr3+, Cr(OH)2 +, and Cr(OH)2+. When Eh falls below 100 mV, toxic Cr(vi) tends to change into relatively less toxic Cr(iii), taking the form of Cr3+, Cr(OH)2 +, Cr(OH)3, and Cr(OH)4 − [50].

Therefore, adjusting the Eh value of the soil environment is conducive to converting the toxic Cr(vi) in soil into relatively non-toxic Cr(iii) and retaining Cr(iii), which is the core idea for the key technology of remedying Cr(vi)-contaminated soil. However, the REDOX conditions in soil tend to change over time, which can be affected by various factors, such as soil moisture content, iron, manganese oxide content, OMs, and the availability of electron donors and acceptors. As argued by Masscheleyn et al. [54], increasing soil water content is conducive to creating the reduction conditions required for the conversion of Cr(vi) into Cr(iii), and REDOX remained at a low level until the water was drained from the soil. Kim and Dixon [55] discovered that the relatively high surface area and high cation exchange capacity (CEC) of manganese oxide contributed to removing heavy metal Cr from soil. Meanwhile, the oxidation of Cr(iii) increased with the rise in manganese(iv) oxide content in the soil. By analyzing experimental leachate, plant biomass, and soil, Banks et al. [39] demonstrated that OM could reduce the control conditions of soil moisture on REDOX, and that higher OMs content could exert an inhibitory effect on Cr leaching.

3.4 Impact of OM on the form of Cr in soil

The presence of OM plays a role in reducing Cr(vi) to Cr(iii) and diminishing Cr(vi) content in soil [56]. With Cr-containing basic oxygen furnace (BOF) slag added into agricultural soil for a 3 month culture experiment, Reijonen and Hartikainen [57] obtained the results suggesting that there was no soluble Cr in the experimental soil, which means neither Cr(iii) nor Cr(vi) was released into the soil from the slag. Initially, the BOF slag used in the experiment contained a small amount of soluble Cr(vi), showing that the Cr(vi) in the slag was reduced and fixed due to the presence of OM in the soil. As proposed by Bolan and Thiagarajan [58], non-humic organic substances such as carbohydrates and proteins were also effective in reducing Cr(vi) content, and the adsorption of Cr had a significant impact on the migration of Cr in the soil. In an acidic environment with a pH level of 2–7, CrO 4 2 − could be adsorbed by the mineral surface with protonation and positive position. As revealed by Jardine et al. [59], the increase in soil OM promoted the REDOX transformation of Cr(vi), while reducing the content of Cr(vi) in soil through X-ray absorption of near-marginal structure spectroscopy. Besides, Thacher et al. [60] applied the kinetic model of a biofilm reactor to conclude that humus can not only contribute to the electronic transfer of microbial metabolites to Cr(vi) but also promote the generation of Cr(iii). To sum up, these findings suggest that the OMs in the soil can not only reduce the mobility, bioavailability, and biotoxicity of Cr, but also assist the absorption and accumulation of Cr present in crops and other food chain components.

3.5 Impact of Fe-Mn oxide on Cr morphology

According to the relevant studies [45,61], Fe0, Fe2+, and S2− are capable to reduce Cr(vi) to Cr (iii) rapidly, and such capability improves with the increase in Fe2+ and S2−contents. The REDOX activity is determined by the concentration of REDOX substances (Fe0, Fe2+, S2−, Mn4+, and OMs) in the soil. A low pH value is beneficial to the release of Fe2+ from the upper soil minerals. For example, Cr(vi) is completely reduced to Cr(iii) when the Fe2+ content in the solution reaches 4 mg·L−1.

From the perspective of thermodynamics, Cr(iii) can change into Cr(vi) spontaneously during the landfilling of Cr-rich stainless steel slag and under natural aerobic conditions. However, its reaction kinetics are relatively slow (reaction equation (1)). Schroeder and Lee [62] conducted a study on the transformation of Cr(iii) and Cr(vi) in a simulated solution, which reveals that Cr(iii) started to be oxidized at a slow pace within 2 weeks when the solution containing less than 3% Cr(iii) was exposed to oxygen. According to the research results of Namgung et al. [63], there was no Cr(vi) detected 24 days after the addition of Cr(iii) into the aerobic buffer with a pH value of 7.0. However, the involvement of Mn oxide provides more active oxidants. Compared with O2 oxidation alone, Mn oxide can significantly promote the oxidation of Cr(iii) (reaction equations (2) and (3)). Besides, Fe and Mn, which can be in various REDOX states, act as electron donors or acceptors. Also, they have a large surface area and CEC, which makes them capable of removing heavy metals from the environment, thus having immediate effect on the REDOX and migration behavior of Cr. Therefore, they play an important role in the biogeochemical cycle of elements.

(1) 2 Cr ( OH ) 2 + + 1 . 5 O 2 ( aq ) + H 2 O → 2 Cr 4 2 − + 6 H + ,

(2) 3 MnOO H ( s ) + Cr ( OH ) 2 + + 3 H + → 3 Mn 2 + 2 HCr O 4 − + 3 H 2 O ,

(3) 3 Mn O 2 ( s ) + 2 Cr ( OH ) 2 + → 3 Mn 2 + + 2 HCr O 4 − .

3.6 Impact of other factors on Cr morphology

It has been shown in some studies that microorganisms and Cr ions can affect the chemical form of Cr in soil through a series of complex interactions, such as reduction, accumulation, adsorption, and precipitation [64]. On the one hand, microorganisms can end up precipitating Cr(iii) into insoluble chromium hydroxide [Cr(OH)3] as precipitant [65]. On the other hand, Cr(vi) possesses a high reduction potential, which means microorganisms can also reduce Cr(vi) into Cr(iii) either directly or indirectly through Cr reductase [66].

Clay mineral composition and soil texture have a significant impact on heavy metal migration as well. The parent materials of soil as formed by the weathering of different bedrocks vary, as does the final type of soil. Since different types of soils contain different soil OMs and clay minerals, there are differences in their physical and chemical properties [67]. The depth of vertical migration and mobility of metals are affected by the parent materials of naturally-derived soil, while the vertical migration distance and mobility of heavy metals are higher in the soil weathered by sandstone than in clay [68].

4 Mechanisms of absorption, transport, and accumulation of Cr in soil–plant systems

Since the life activities of plants are closely related to the surrounding environment, heavy metal pollution could pose a severe threat to the germination and growth of plants. As mentioned above, the landfill and long-term storage of stainless steel slag in the soil will lead to the dissolution of heavy metal Cr in large amounts. Meanwhile, plants can absorb essential trace elements from the soil as micronutrients through their roots. In this process, they also absorb other non-essential and even toxic heavy metal elements [69,70]. Therefore, the mechanism of Cr migration and transformation in soil–plant systems can be understood by determining the absorption, transport, and destination of heavy metal Cr in plants.

Cr is known as a sort of toxic heavy metal that is abundant in the earth’s crust and can enter the food chain through plants. Determined by the metal form, the phytotoxicity of Cr has a significant impact on its absorption, transport, and accumulation [52]. The contact between root and soil is the first interaction for plants to absorb Cr. As Cr is a non-essential element, plants lack the transporters intended for Cr absorption. The entry of Cr(iii) into plant roots appears to be involuntary, but Cr(vi) absorption is voluntary [71]. Most studies have shown that Cr accumulates more in roots than in stems for plants because Cr is fixed in the vacuoles of root cells [72,73].

The process of Cr being transported from the roots of plants to their body is a lengthy one, which is the primary reason for Cr to accumulate in the roots [74,75]. At the same time, Cr can suppress root growth, reduce the total length of roots, and severely disrupt the absorption of water and nutrients, thus inhibiting germination. With Pakchoi as the research object, Wu et al. [76] investigated the effects of Cr concentration on its accumulation in plants. According to the investigative results, the content of Cr in roots was about 3.02 times that in the aboveground parts of the corresponding plants, which suggest that the cell walls and vacuoles of Pakchoi can reduce the transport of these heavy metals through plants and restrict the transport from root to stem as a response to Cr stress. In a study on the places of Cr accumulation in Alternanthera philoxeroides, Borreria scabiosoides, Polygonum ferrugineum, and Eichhornia crassipes, Mangabeira et al. [77] detected the organelle changes suspected to result from the presence of metal. The results show that Cr accumulated mostly in the roots (8.6–30 mg·kg−1 dw) of the four plants, rather than in the stems and leaves (33.8–8.6 and和 0.01–9.0 mg kg−1 dw). In root tissues, Cr existed mainly in the vacuoles of parenchyma cells and xylem parenchyma cell walls.

Plants can absorb Cr(iii) and Cr(vi) through epidermal root cells, despite some significant differences in the way and efficiency of their entry into cells. Due to the higher water solubility and migration efficiency, it is easier for Cr(vi) to be absorbed by plants than Cr(iii) [78]. The absorption of Cr(iii) by plants is an involuntary process without energy consumption, and Cr(iii) enters root cells mostly through the inbound channels for essential ions or the simple diffusion on cation exchange sites [79]. In the study of Leersia hexandra conducted by Singh et al. [80,81], it was demonstrated that the absorption of Cr3+ by the root of plants may be mediated partially by Fe3+ complex vectors. As Cr(vi) has a structure similar to that of sulfate and phosphate, the absorption of Cr(vi) by plants is a voluntary process reliant on sulfate or phosphate carriers. The Cr(vi) and sulfate present in plants are transported by sulfate carriers. Aharchaou et al. [78] studied the absorption behavior of Cr3+ and Cr6+ by plants. The research results show that Cr6+ is easier to be absorbed by plants than Cr3+ because of its higher water solubility and transmembrane efficiency. Liu et al. [79] studied the absorption mechanism of Cr3+ by the roots of porphyra hexagona through pot experiment. The results showed that the absorption of Cr3+ by porphyra hexagona was carried out through the antagonism of Fe3+ complex carrier. Kim et al. [82] studied the influence mechanism of sulfate on the absorption of Cr6+ by tobacco using multi-functional MSN1 protein. The research results showed that sulfate is the main carrier for the absorption of Cr6+ by tobacco.

The Cr accumulated in soil can affect the growth of plants through migration from roots to stems and leaves, with the transport from roots to those aboveground parts as the key to regulating the accumulation of Cr in the aboveground parts of plants. Meanwhile, Cr is transported from the root to the xylem, before its diffusion through xylem ducts into the cytoplasm of cortical cells and further transport to the stems, leaves, flowers, and fruits [83,84]. As mentioned above, Cr concentrates mainly in roots for most plants, the cumulative amount of which in different parts is as follows: root > stem > leaf > fruit.

5 Effect of Cr on plant growth

Low Cr content in plant body can promote its growth, while high Cr content in plant body can significantly inhibit plant growth and development, even lead to death [85]. The enrichment of Cr in plants will have adverse effects on plant physiological metabolism, seed germination, OM synthesis, photosynthesis, enzyme activity, mineral nutrient absorption, etc. [85,86,87,88]. In addition, when Cr content in plants is high, it will increase the content of reactive oxygen species, thereby damaging the cell structure of plants [70,89].

Seed germination is the first physiological process of plant growth. The existence of Cr in soil or growth medium will adversely affect the germination rate of seeds. Nagarajan and Ganesh [88] studied the effect of Cr on rice growth. The results showed that when the concentration of Cr was more than 100 mg·L−1, the seed germination rate would be significantly reduced, and the absorption of nutrients by plant seedlings would also be inhibited, which was not conducive to rice growth. Singh et al. [90] studied the effect of Cr on chickpea growth by pot experiment. The results showed that when Cr content reached 90 and 120 μM, chickpea seed germination and seedling growth would be inhibited. Stambulska et al. [86] explored the influence mechanism of Cr on plant seed germination. The research results showed that the adverse effect of Cr on seed germination was mainly attributed to the reduction in amylase activity by Cr, which inhibited the transportation of carbohydrates and mineral nutrients in plants.

The enrichment of Cr in plants will not only affect the germination of seeds, but also affect the growth of roots, stems, leaves, and fruits. Singh and Sharma [91] showed that the enrichment of Cr in plant body can inhibit the growth of plant roots, shorten root length, reduce root area, inhibit root cell division, and then adversely affect plant growth. Mallick et al. [92] showed that the presence of Cr6+ in plants would lead to shortened root length, damaged root hair morphology, and a morbid brown appearance. The abnormal growth and development of root system is mainly due to the excess active oxygen in plant body caused by Cr enrichment, which leads to lipid peroxidation of root cell membrane, destroys the integrity of cell membrane, inhibits cell mitosis, and reduces the vitality of primary root tip cells. The research results of Rai et al. [93] show that when the Cr content reaches 0.052–5.2 mg·L−1, the growth of amaranth root system will be significantly inhibited, reducing the transportation of nutrient elements and water to the aboveground part of the plant, thereby adversely affecting the growth of amaranth stem and the synthesis of OM in the body.

6 Remediation of Cr-contaminated soil

As mentioned above, most stainless steel slags go to landfill, which presents a significant risk to the environment. Especially in the process of natural storage and rain leaching, the trivalent Cr contained in stainless steel slag may be converted into hexavalent Cr with greater mobility and toxicity, thus further increasing the risk posed to the environment. To reduce such risk, two approaches can be adopted currently for the soil–plant systems.

First of all, before recycling or landfilling, researchers once considered converting the hexavalent Cr with greater mobility and toxicity in stainless steel slag into insoluble trivalent Cr for stabilization or solidification, which can mitigate the environmental risks caused by Cr pollution significantly. For example, Cr can be extracted by reducing agents such as FeSO4, nano iron, FeS2, and Na2S, or through high-temperature reduction curing [94,95], acid leaching, or alkali leaching for recycling. Kim et al. [96] explored the selective recycling of Cr from stainless steel slag by using hydrometallurgical method (alkaline pressure leaching). However, the reaction requires an increase in pressure and reaction temperature. Besides, the artificial mechanical activation causes the maximum leaching rate of Cr to reach as high as 46%. By using sulfuric acid, Jiang et al. [97] and Zhao et al. [98] made the Cr leaching rate in chromite reach above 93% within 6 h at 160℃. Meanwhile, it was also argued that Cr leaching started with the groovy corrosion of spinel grain boundary, with spinel gradually dissolved by the leaching solution. Yu et al. [99] adopted the method of first desilicating and then extracting Cr to treat Cr-containing slag (Cr2O3 content: 12.85%), with the Cr extraction rate reaching 98.41% after desilication. To sum up, the above methods are applicable to promote the oxidation of Cr in slag and reduce the ecological risk presented by Cr leaching from the slag.

Second, the soil used to landfill stainless steel slags can also be restored. Currently, there are various methods available for removing heavy metal Cr from soil, including chemical reduction, biological remediation, and physical remediation. The chemical reduction method, which is most used to treat Cr-contaminated soil, is characterized by quick remediation, high efficiency, low cost, relatively simple operation, and high effectiveness in transforming Cr(vi) into an insoluble Cr(iii) without the generation of polluting by-products [100]. The commonly used reducing agents include FeS, FeS2, Fe0, calcium polysulfide, and sodium sulfite. Yang et al. [101] adopted two test soils and different reducing agents to treat Cr(vi)-contaminated soil, revealing that both the reduction rate and the total reduction efficiency of the soil exceeded 99% when Na2S was taken as a reducing agent to treat the Cr(vi) in soil. Chrysochoou and Ting [102] investigated the impact of soil pH level and oxygen content on the reduction of Cr(vi) by calcium polysulfide from the perspective of reaction kinetics, with the results suggesting that the reaction rate improved when the pH value was 8.5–5.5. Bioremediation can be divided into microbial remediation and phytoremediation. Biological remediation refers to the reduction and repair of Cr(vi) through various organisms capable of Cr(vi) decontamination, which is cost-effective and environmental friendly. Gandhimathi [103] applied the ex situ remediation method and Bacillus sp. to remedy the Cr(vi)-contaminated soil by adjusting pH value, temperature, carbon source type, and other factors, revealing that Cr(vi) was completely removed. Phytoremediation refers to a technique that can be applied to fix and degrade the pollutants in the contaminated soil through different plant species. Chrome-contaminated soil is remedied by hyperaccumulators. Currently, it has been reported that foreign hyperaccumulators can be divided into Di-comaniccolifera Wild and Suterafodina Wild, with Cr accumulation reaching up to 1,500 and 2,400 mg·kg−1, respectively [104]. Among the domestic studies on this subject, the Cr hyperaccumulator plant, discovered by Zhang et al. [105] shows a high capacity of Cr adsorption.

7 Conclusion and prospects

In this study, a review was conducted on the occurrence form of Cr in stainless steel slag and its migration and transformation behavior in soil–plant systems, as well as the measures of remedying Cr(vi)-contaminated soil. The ternary evaluation system of Cr migration and transformation in the stainless steel slag soil plant system was innovatively constructed, and a new remediation technology for Cr-contaminated soil was proposed, so as to better understand the ecological risks of Cr in stainless steel slag in soil and plants and effective remediation strategies. According to the research results, the solubility, mobility, adsorption/desorption, toxicity, bioavailability, and transformation of Cr in stainless steel slag varied by the chemical forms, with the physical and chemical properties (such as pH, Eh, OM, Fe, and Mn oxides) of soil having significant effects on Cr absorption and transport in soil–plant systems. To address the threat posed by Cr(vi) to the soil–plant systems, the Cr(vi) with greater mobility and toxicity in stainless steel slag was transformed into insoluble Cr(iii) for stabilization or solidification. As an alternative, the soil deposited by stainless steel slag was remedied through chemical reduction or biological restoration, which contributes a novel idea to the remediation of Cr(vi)-contaminated soil.

At present, despite some progress made in the research on Cr-containing stainless steel slag, there remains some unresolved problems, including the soil–plant accumulation of Cr and the distribution patterns of Cr in plants. Moreover, to increase the rate of Cr leaching from stainless steel slag, most researchers adopt a pressurized oxidation method to extract valuable metals on the basis of acid leaching and alkali leaching. However, it is necessary to increase pressure to dozens of atmospheric pressures, which makes it difficult to meet such harsh conditions for the landfilled stainless steel slag and other Cr-containing solid wastes. Thus, there is little research focusing on the selective oxidation of Cr-bearing mineral phases in stainless steel slag and the mechanism of trivalent Cr oxidation in leach solution. Besides, there is a lack of understanding of the potential risks posed to the environment by the remediation of Cr(vi)-contaminated soils through reducing agent, which requires further research. In practice, it is necessary to develop the most-suited joint remediation technology by combining the properties of stainless steel slag soil with the future plan on land use, for the remediation of Cr-contaminated soil.

Acknowledgements

The authors would like to thank North China University of Science and Technology for providing the materials and testing equipment for the experiments.

  1. Funding information: This work was financially supported by the National Natural Science Foundation of China (No. U20A20271), Natural Science Foundation of Hebei Province (No. E2020209184); Science and Technology Research Project of University in Hebei Province (No. ZD2021084); and Graduate Student Innovation Foundation of Hebei Province (No. CXZZBS2019140).

  2. Author contributions: S.C.: methodology, investigation, and writing – original draft; L.W.: methodology, investigation, visualization, writing – review and editing, and funding acquisition. Y.Z.: conceptualization, supervision, project administration, and funding acquisition. T.T.: methodology. T.L.: investigation. All authors have read and agreed to the published version of the manuscript.

  3. Conflict of interest: Authors state no conflict of interest.

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Received: 2022-06-20
Revised: 2022-10-30
Accepted: 2022-11-02
Published Online: 2023-02-03

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/htmp-2022-0252
Keywords for this article
stainless steel slag; chromium; migration transformation; toxicity; repair
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. First-principles investigation of phase stability and elastic properties of Laves phase TaCr2 by ruthenium alloying
  3. Improvement and prediction on high temperature melting characteristics of coal ash
  4. First-principles calculations to investigate the thermal response of the ZrC(1−x)Nx ceramics at extreme conditions
  5. Study on the cladding path during the solidification process of multi-layer cladding of large steel ingots
  6. Thermodynamic analysis of vanadium distribution behavior in blast furnaces and basic oxygen furnaces
  7. Comparison of data-driven prediction methods for comprehensive coke ratio of blast furnace
  8. Effect of different isothermal times on the microstructure and mechanical properties of high-strength rebar
  9. Analysis of the evolution law of oxide inclusions in U75V heavy rail steel during the LF–RH refining process
  10. Simultaneous extraction of uranium and niobium from a low-grade natural betafite ore
  11. Transfer and transformation mechanism of chromium in stainless steel slag in pedosphere
  12. Effect of tool traverse speed on joint line remnant and mechanical properties of friction stir welded 2195-T8 Al–Li alloy joints
  13. Technology and analysis of 08Cr9W3Co3VNbCuBN steel large diameter thick wall pipe welding process
  14. Influence of shielding gas on machining and wear aspects of AISI 310–AISI 2205 dissimilar stainless steel joints
  15. Effect of post-weld heat treatment on 6156 aluminum alloy joint formed by electron beam welding
  16. Ash melting behavior and mechanism of high-calcium bituminous coal in the process of blast furnace pulverized coal injection
  17. Effect of high temperature tempering on the phase composition and structure of steelmaking slag
  18. Numerical simulation of shrinkage porosity defect in billet continuous casting
  19. Influence of submerged entry nozzle on funnel mold surface velocity
  20. Effect of cold-rolling deformation and rare earth yttrium on microstructure and texture of oriented silicon steel
  21. Investigation of microstructure, machinability, and mechanical properties of new-generation hybrid lead-free brass alloys
  22. Soft sensor method of multimode BOF steelmaking endpoint carbon content and temperature based on vMF-WSAE dynamic deep learning
  23. Mechanical properties and nugget evolution in resistance spot welding of Zn–Al–Mg galvanized DC51D steel
  24. Research on the behaviour and mechanism of void welding based on multiple scales
  25. Preparation of CaO–SiO2–Al2O3 inorganic fibers from melting-separated red mud
  26. Study on diffusion kinetics of chromium and nickel electrochemical co-deposition in a NaCl–KCl–NaF–Cr2O3–NiO molten salt
  27. Enhancing the efficiency of polytetrafluoroethylene-modified silica hydrosols coated solar panels by using artificial neural network and response surface methodology
  28. High-temperature corrosion behaviours of nickel–iron-based alloys with different molybdenum and tungsten contents in a coal ash/flue gas environment
  29. Characteristics and purification of Himalayan salt by high temperature melting
  30. Temperature uniformity optimization with power-frequency coordinated variation in multi-source microwave based on sequential quadratic programming
  31. A novel method for CO2 injection direct smelting vanadium steel: Dephosphorization and vanadium retention
  32. A study of the void surface healing mechanism in 316LN steel
  33. Effect of chemical composition and heat treatment on intergranular corrosion and strength of AlMgSiCu alloys
  34. Soft sensor method for endpoint carbon content and temperature of BOF based on multi-cluster dynamic adaptive selection ensemble learning
  35. Evaluating thermal properties and activation energy of phthalonitrile using sulfur-containing curing agents
  36. Investigation of the liquidus temperature calculation method for medium manganese steel
  37. High-temperature corrosion model of Incoloy 800H alloy connected with Ni-201 in MgCl2–KCl heat transfer fluid
  38. Investigation of the microstructure and mechanical properties of Mg–Al–Zn alloy joints formed by different laser welding processes
  39. Effect of refining slag compositions on its melting property and desulphurization
  40. Effect of P and Ti on the agglomeration behavior of Al2O3 inclusions in Fe–P–Ti alloys
  41. Cation-doping effects on the conductivities of the mayenite Ca12Al14O33
  42. Modification of Al2O3 inclusions in SWRH82B steel by La/Y rare-earth element treatment
  43. Possibility of metallic cobalt formation in the oxide scale during high-temperature oxidation of Co-27Cr-6Mo alloy in air
  44. Multi-source microwave heating temperature uniformity study based on adaptive dynamic programming
  45. Round-robin measurement of surface tension of high-temperature liquid platinum free of oxygen adsorption by oscillating droplet method using levitation techniques
  46. High-temperature production of AlN in Mg alloys with ammonia gas
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  48. Advances in ultrasonic welding of lightweight alloys: A review
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  50. Compositional and thermophysical study of Al–Si- and Zn–Al–Mg-based eutectic alloys for latent heat storage
  51. Corrosion behavior of a Co−Cr−Mo−Si alloy in pure Al and Al−Si melt
  52. Al–Si–Fe alloy-based phase change material for high-temperature thermal energy storage
  53. Density and surface tension measurements of molten Al–Si based alloys
  54. Graphite crucible interaction with Fe–Si–B phase change material in pilot-scale experiments
  55. Topical Issue on Nuclear Energy Application Materials
  56. Dry synthesis of brannerite (UTi2O6) by mechanochemical treatment
  57. Special Issue on Polymer and Composite Materials (PCM) and Graphene and Novel Nanomaterials - Part I
  58. Heat management of LED-based Cu2O deposits on the optimal structure of heat sink
  59. Special Issue on Recent Developments in 3D Printed Carbon Materials - Part I
  60. Porous metal foam flow field and heat evaluation in PEMFC: A review
  61. Special Issue on Advancements in Solar Energy Technologies and Systems
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  64. Topical Issue on Focus of Hot Deformation of Metaland High Entropy Alloys - Part I
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  66. Three-dimensional transient heat transfer analysis of micro-plasma arc welding process using volumetric heat source models
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