A Metallurgical Technology Investigation of the Wangxiangping Ancient Smelting Sites at Daye County

doi:10.21203/rs.3.rs-3123237/v1

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A Metallurgical Technology Investigation of the Wangxiangping Ancient Smelting Sites at Daye County

https://doi.org/10.21203/rs.3.rs-3123237/v1

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During the spring of 2022, an archaeo-metallurgical survey was conducted by the Beijing University of Science and Technology at the Wangxiangping site in Daye County. This subsequent testing excavation uncovered pottery and metal smelting relics from the Shang and Zhou dynasties. Charcoal samples extracted from the third stratification can be dated using ¹⁴C to as early as the late Shang Dynasty. The SEM-EDS method was employed to analyze the metallurgical relics found in each stratification layer of the site. The analysis revealed that pure copper smelting and tin bronze smelting activities coexisted at this location. Research results suggest that secondary copper oxide ore was used for reduction smelting, resulting in the production of red copper and high-grade 'white' matte. Additionally, tin ore was incorporated to create bronze, with tin serving as the alloy composition. However, no residual artifacts from casting activities were discovered. The survey and detection analysis conducted at this site offer significant evidence and data supporting further research into copper smelting activities in the Daye area during the Shang and Zhou dynasties.

Daye County

Shang Dynasty

Copper

Smelting

Alloying

Archaeometallurgy

The Daye area in Hubei is abundant in copper, lead, and other mineral resources, making it well-known for its mining and smelting activities during the Bronze Age. Previous research has demonstrated that the area and its surroundings contain numerous diverse smelting sites. Notable examples include the ancient Tonglüshan copper mine smelting site and related mining and smelting surveys. Research indicates that mining at Daye Tonglüshan evolved from open-pit to underground operations during the Shang and Zhou periods[1]. Studies on the nearby Xianglushan site have suggested that it refined antimony bronze, lead-tin bronze, and red copper, among other technologies[2, 3]. Numerous smelting sites have also been reported in surrounding areas such as Yangxin Dalupu site[4], Jiangxi Ruichang Tongling area[5], and Anhui Zongyang area[6]. Recent work has revealed numerous Shangzhou lead smelting sites in the Yangxin area[7], which have introduced new methods for studying mining and smelting sites, such as identifying micro-slag at casting locations[8]. Research on mining and smelting sites has covered an extensive geographical range, with numerous investigations and excavations conducted in locations such as Oman, the Sinai Peninsula, the Arab Valley, Cyprus, the Balkan Peninsula, the Danube River middle reaches region, the Austrian Alps, the Spanish Rio Tinto mining area, Thailand Banqing, and South America's Peru. In-depth studies have also been carried out at sites like Shiqmim in southern Israel[9], the Feynan site in Jordan[10], and the Massa Marittima site in southern Tuscany, Italy[11].

On February 4th, 2022, the Beijing University of Science and Technology carried out a special investigation of mining and metallurgical sites in the Daye area. The investigation primarily focused on understanding the occurrence and distribution of mining and metallurgical remains, as well as the scale and characteristics of smelting activities in the region. The WXP (Wangxingping for short) site, discovered during the survey, is an exemplary representation of early smelting activities in the area. ¹⁴C dating of a charcoal sample taken from the site's bottom layer (the ③ layer) places it in the late Shang Dynasty period. This report offers valuable insights into local smelting sites from the late Shang Dynasty to the early Western Zhou Dynasty by examining the WXP site and analyzing its metallurgical artifacts and technology.

The WXP (Wangxiangdun) site is situated 50 meters southeast of Xiashoupu Bay in Dazhuang Village, Liurenba Town, Daye County, Huangshi City, Hubei Province. According to the 3rd national official archaeological survey, the settlement site is thought to belong to the Western Zhou period. The WXP site is located 300 meters southeast of Dazhuangwu in Dongshan Village, Liurenba Town, and spans an area of approximately 12,000 square meters with an archaeological stratigraphy thickness of 1.5-2 meters. The pottery found at the site is predominantly yellow-brown temperless pottery, accompanied by red sand tempered pottery. Decorative elements on the pottery include rope patterns and string patterns featured on li-tripods, yan-steamers, dou-stemmed bowls, and guan-jars[12].

The Straitification Structure and Radiocarbon Dating Result

During this survey, a new profile was discovered at the mountain top terraces. The profile faces west and spans a width of 240cm. It can be divided into three layers:

The first layer ①, found below the surface soil, is the disturbance layer. It is 20-30cm thick and consists of gray-brown soil with fine sand particles. The soil in this layer is relatively loose.

The second layer ② is the cultural layer, which is 70-110cm thick. It contains fine sand particles within blue-gray clay. The color is lighter than that of the first layer, and it includes furnace slag, charcoal shavings, pottery fragments, and other cultural artifacts.

The third layer ③ is another cultural layer, mainly composed of yellow clay with a thickness of 15-30cm. This layer contains sandstone red pottery, sandstone gray pottery, furnace slag, charcoal shavings, and numerous pottery fragments. Charcoal samples were extracted from this layer for ¹⁴C dating.

To collect charcoal shavings near the pottery fragments at the bottom of the WXP site in Daye, adhere to the following standardized collection method to prevent contamination by foreign carbonaceous substances[13]:

Use a metal shovel to carefully extract the surrounding soil along with the charcoal shavings.

Wrap the collected samples in aluminum foil to avoid exposure to contaminants.

Ensure that the collection and extraction process strictly adheres to relevant national standards.

Once the samples have been collected, they were sent to the scientific archaeology laboratory at Peking University's School of Archaeology and Museology. The age of the charcoal shavings sample was determined to be from the late Shang Dynasty, as shown in Table 1.

The Sampling Strategy and Investment Methods

In smelting sites, various relics and artifacts can be used to study smelting technology. One of the easiest to obtain is slag, the waste product created during smelting. In copper smelting activities, slag production is a core process. Slag is discharged from the furnace in a molten state at smelting temperatures and solidifies into a dense solid, permanently sealing the metallurgical reaction information within. The properties of slag directly affect the success of the smelting process. As a result, detecting and analyzing slag can help reveal ancient copper smelting technology. At the WXP site, the metallurgical content was investigated through surface and section surveys. The smelting slag found neither accumulated nor distributed sparsely, and the quantity was small. The slag blocks came in various shapes and had mostly dark gray surfaces. The size of the slag bodies ranged from 2–5 cm in length and width, and some larger pieces were approximately 10 cm in length and width, with a thickness of 1-2.5 cm. The slag was relatively small and did not accumulate. To better understand the metallurgical content of the WXP site, 10 samples were selected for testing.

As shown in Fig. 4, there is no significant difference in color between the slag samples from the WXP site. The lighter portions of the slag may be due to the burial environment and difficulties in external cleaning. Most of the slag is small in size, with no large blocks of slag residue present at the site. The length of most slag pieces is about 10cm. The fluidity of most slag is poor, and some slag samples have many pores, The sample WXP③-02 has more pores and is lighter. Overall, the slag collected from the surface has lower viscosity than the slag unearthed from the cultural layer, and its density is also higher. The stratum slag is more irregular due to its poor fluidity, its surface is more uneven, and it adheres to more heat-treated sandy soil and the like. There are a small number of slag pieces with traces of having flowed out, such as smelting slag collected from the surface. It is not difficult to find this kind of slag in the field, as it varies in characteristics like color, appearance, texture, and specific gravity. Fortunately, almost all ancient metallurgical slags are ferrous silicates, whether they are by-products of iron or non-ferrous metal production. This fact helps in identifying and distinguishing them from non-metallurgical slags found on site.

The analysis parts of the slag and furnace wall were selected and cut using a diamond band saw. The cut samples were fixed and embedded using TROJAN epoxy resin. The porous samples were vacuum-embedded to ensure structural stability and reduce secondary contamination of the samples during processing. The samples were then polished with waterproof sandpaper and polishing fabrics. The surface of the samples was coated via vacuum carbon sprayed before the scanning electron microscope energy spectrum analyzer (SEM-EDS) was performed for analysis. The scanning electron microscope model TESCAN VEGA3 XMU was equipped with a Bruker Nano GmbH 610M energy spectrometer to measure the composition of the matrix and metal particles, etc. The instrument working conditions were an excitation voltage of 20kV, a working distance of 15 ± 0.1mm, a collection number of > 2kcps, and a valid scanning time of 60s were set. When scanning the slag matrix, large metal particles and holes were avoided. The matrix composition was normalized by the context of the structure of the SEM observations and the results is shown in the table below:

Table 2

Matrix chemical composition of the slag from WXP(reported in wt%)
Lab No	MgO	Al₂O₃	SiO₂	K₂O	CaO	FeO	Cu	Sn
wxp②01	—	7.6	34.9	0.9	4.2	52.4	1.8	—
wxp③01	0.7	6.9	30.4	1.0	5.0	56.0	0.6	—
wxp③02	1.8	4.7	27.2	1.3	12.7	51.8	1.0	0.3
wxp③03	—	5.8	26.4	0.8	3.5	63.5	1.4	—
wxp③04	0.6	6.6	19.0	—	1.3	72.5	0.2	—
wxpc01	1.0	5.8	38.8	2.0	7.4	45.1	0.9	—
wxpc02	0.9	3.9	24.9	0.3	1.8	68.3	1.1	—
wxpc03	2.0	3.5	34.6	1.1	7.4	51.4	0.3	—
wxpc04	2.0	3.5	34.6	1.1	7.4	51.4	0.3	—
wxpc05	0.5	4.8	29.3	1.3	5.5	58.6	1.4	—

The Constitution and Content Data of the Relics

In addition to iron and silicon as the main components, the slag composition contains relatively high levels of calcium and aluminum. To better determine its thermodynamic parameters, the slag matrix composition is marked on two ternary slag phase diagrams. As illustrated in these Fig. 5–6, most of the slag falls within the ideal melting area of the ternary phase diagram[15]. This indicates a high level of technical proficiency, such as ore selection processes and smelting technology at that time, ensuring stable operation of smelting activities in the furnace. Good atmosphere control during smelting is also achieved through the matrix phase of the slag. The slag matrix is primarily composed of dark gray dendritic or chain-like iron olivine and black-brown glass phase. Additionally, there are obvious capillary iron olivine crystals precipitated. This is consistent with the phases precipitated in the melting area where each component is located in the diagrams mentioned above.

While it is generally believed that the metallurgical process represented by slag composition cannot be directly determined, it is possible to infer the probable products of smelting production based on the metal particles encapsulated in the slag. As a result, the copper smelting slag collected and unearthed at the WXP site can be roughly divided into two categories. Class A is red copper smelting slag, and Class B is tin bronze alloy slag. This classification gives a basic understanding of the types of smelting processes and products that may have taken place at the site.

Five of the samples (WXP②-01, WXP③-01, WXP③-04, WXP C-01, WXP C-02, WXP C-05) were identified as Type A and represent the red copper smelting activity. Red copper metallurgical technology analysis Class A involves red copper smelting, and the resulting slag is red copper smelting slag. This slag is primarily irregular in shape, gray-black, and abundant at the site. The matrix composition of the slag reveals a high iron content, ranging from 50–70%, and a large number of metal particles. No other metal particles are highly enriched in the slag. The slag is generally dense, with some fluidity (although not ideal). The internal phase mainly consists of iron olivine and fayalite, indicating that this type of slag is copper smelting slag. The analysis area of metal particles is shown in Fig. 6. Aa1 represents pure copper particles, and Aa2, wrapped around Aa1, signifies white bronze particles. In Fig. 7, A2, B2, C1, and D1 are all red copper particles. A1 and B1 in Fig. 7 illustrate pure copper particles wrapped around white bronze particles, while D2 and D3 in Fig. 7 denote oxidized red copper particles.

Table 3

Composition of metal prill in WXP slag(reported in wt%)
Sample code	Testing area	Composition (wt%)
Sample code	Testing area	Cu	Fe	S	O
WXP②-01	Figure 6.Aa-1	100.0	—	—	—
	Figure 6.Aa-2	77.3	—	22.0	0.7
	Figure 6.Aa-3	79.2	—	20.8	—
WXP③-01	Figure 6.Bb-1	97.9	—	—	2.1
	Figure 6.Bb-2	75.8	0.3	21.7	—
	Figure 6.Bb-3	71.8	3.2	23.4	1.6
	Figure 6.Bb-4	75.8	—	23.3	0.8
WXP③-04	Figure 7.A1	75.4	3.0	21.4	0.3
WXP③-04	Figure 7.A2	98.9	—	—	1.1
WXPC-01	Figure 7.B1	76.5	2.2	21.3	—
WXPC-01	Figure 7.B2	99.4	—	—	0.6
WXPC-02	Figure 7.C1	100.0	—	—	—
WXPC-05	Figure 7.D1	100.0	—	—	—
	Figure 7.D2	81.8	—	0.6	17.6
	Figure 7.D3	86.3	—	—	13.7

Class B represents tin bronze alloy smelting slag, which is relatively limited in quantity at the site and is closely related to the early supply of tin and the amount of slag produced during alloying. The smelting technology can be deduced based on the typical phase information of the tin bronze smelting slag.

Only two furnace slags in the stratum exhibit relevant phenomena associated with tin bronze smelting activities. The tin bronze slag discovered in the late Shang Dynasty stratum primarily features a slag matrix structure composed of iron olivine, with large particles of iron ore residue remaining. The largest iron ore particle exceeds 2mm. The light gray strip area in the slag matrix represents this situation. In Fig. 8, analysis area Aa1 consists of copper oxide particles, while the surrounding Aa2 and Aa3 analysis areas show different brightness levels depending on the Sn content. However, the basic composition remains primarily Sn-Fe (Cu), and there are tiny Cu pure copper particles inside (Fig. 8.Aa4 position). This indicates that the material is at the reaction stage after adding ore, and the reaction has not yet been fully carried out.

Type B (including WXP③-02 and WXP③-03) is tin bronze alloy smelting slag, which are rare at the site, related to the early supply of tin and the amount of slag produced by alloying. Only 2 pieces of slag in the stratification were excavated from Layer ③ with plenty of pottery shards of the late Shang Dynasty. Most of the slag matrix is fayalite structure, and there are still large particles of ore remaining. The largest ore remainder over 2mm, which can be observed as light gray elongated area in the slag matrix.

The circular particles in Fig. 8.Ab are high-tin particles, and the overall tin content of the particles is above 53%. According to the different tin contents, they are divided into two phases, but they are basically metal particles formed by heating after tin ore is added to the copper smelting furnace. Ac1 in Fig. 8.Ac is iron-tin ore residue with small particle size. Ac2 and Ac3 are white ice copper particles wrapped on the outside. Ac4 has similar properties to Ac1, but has a higher copper content. They are all wrapped in high-ice copper particles. Ac5 and Ac7 are close to the slag matrix composition, mainly Fe-Si. Ac6 is high-ice copper particles after successful smelting. In Fig. 8.Ad, Fig. 8.Ad1, Ad2, and Ad3 are similar to the particles in Ac1 and Ac4. They are all wrapped in ice copper particles (Ad5) mainly wrapped in iron-tin ore residue by high-ice copper particles. The outer gray phase (Ad4, Ad6) is a floating phase.

Ba1 in Fig. 9.Ba1 is ice copper particles, Ba3 on the inside is pure copper particles wrapped up, and there are also pure copper particles Ba2 growing. Ba4 contains about 6% Sn and is a tin bronze alloy. Bb1, Bb2, and Bb3 are high-tin unmelted mineral residues. Due to different tin contents, they have different brightness. The overall tin content is about 40%, with some characteristics of yellow tin ore (Cu2FeSnS4). The analysis area Bc is unmelted tin mineral residues (Bc2) wrapped in ice copper particles (Bc1).

Based on the phase composition of this batch of slag which is similar to other areas in the Yangtze River Basin, it is speculated that the bronze metallurgical process is similar to that of Xianglushan in Daye. It should be a two-step method: first produce red copper and discharge red copper slag; then add tin ore to the furnace containing Cu liquid to smelt bronze and discharge bronze slag. Considering that many sites have discovered copper minerals containing Sn-Fe, it is speculated that tin materials are added in the form of associated Cu stannite (SnO₂, Sn-Fe minerals) rather than metallic tin.

Table 4

Composition of metal prill in WXP slag(reported in wt%)
Sample code	Testing area	Composition (wt%)
Sample code	Testing area	O	Si	S	Fe	Cu	Sn
WXP③-02	Figure 8.Aa-1	15.4	—	—	—	84.6	—
	Figure 8.Aa-2	40.4	5.4	—	26.0	2.5	25.6
	Figure 8.Aa-3	41..2	5.1	0.5	38.0	4.8	10.4
	Figure 8.Aa-4	—	—	19.3	—	80.7	—
	Figure 8.Aa-5	30.4	4.2	—	8.9	40.0	16.5
	Figure 8.Ab-1	28.7	2.2	—	—	15.9	53.2
	Figure 8.Ab-2	26.4	2.7	—	1.5	13.4	55.9
	Figure 8.Ab-3	28.8	2.9	—	1.1	11.0	56.3
	Figure 8.Ac-1	32.7	4.6	—	20.0	7.7	35.0
	Figure 8.Ac-2	—	—	22.7	—	77.3	—
	Figure 8.Ac-3	—	—	22.0	—	78.0	—
	Figure 8.Ac-4	27.6	2.4	—	7.0	42.6	20.4
	Figure 8.Ac-5	39.8	8.6	—	43.9	—	—
	Figure 8.Ac-6	—	—	20.5	—	79.5	—
	Figure 8.Ac-7	36.7	16.0	—	26.8	9.0	—
	Figure 8.Ad-1	27.1	2.1	0.5	3.9	40.3	26.1
	Figure 8.Ad-2	26.5	1.2	0.5	10.0	41.8	20
	Figure 8.Ad-3	2.6	—	3.9	4.1	76.7	12.8
	Figure 8.Ad-4	27.4	—	—	72.1	—	—
	Figure 8.Ad-5	20.7	1.0	9.7	32.2	35.1	—
	Figure 8.Ad-6	26.4	—	—	72.6	—	—
WXP③-02	Figure 9.Ba-1	—	—	22.7	—	77.3	—
	Figure 9.Ba-2	16.5	—	—	—	83.5	—
	Figure 9.Ba-3	18.5	—	—	—	81.5	—
	Figure 9.Ba-4	30.8	0.8	0.7	28.7	32.6	5.9
	Figure 9.Bb-1	35.5	2.9	—	15.3	2.1	40.7
	Figure 9.Bb-2	33.5	3.3	—	17.0	0.6	41.9
	Figure 9.Bb-3	36.9	2.5	—	27.7	3.1	25.9
	Figure 9.Bc-1	1.1	—	20.8	3.5	74.6	—
	Figure 9.Bc-2	33.0	2.1	1.8	14.5	26.1	16.1

The Technology of Smelting

Compared to the slag composition of furnace slag at locations such as Sifangtang, Donglike, and Nonghang in the Daye area, the average aluminum content of the slag from WXP site and Tonglüshan site is half of the average composition of the aforementioned sites. This difference may be attributed to the longer duration of mining in the Tonglüshan mining area, leading to the presence of more sulfide ores or vein components when mining deep oxidized ore beds, or perhaps due to Tonglüshan using lower-grade copper ore.

The average copper content of the WXP site is 0.9%. Analyzing the properties of smelting slag by examining metal particles such as red copper particles and white bronze particles reveals that this type of red copper smelting slag is all reduction slag smelted using the direct method. The slag matrix contains a large amount of ferrous olivine. Some slag matrices contain a small amount of floating Shi, which are common by-products in the smelting process.

The smelting process follows an oxide ore-copper technology type, consistent with various locations in Tonglüshan. It may be determined according to different regions that the use of ores with different grades contains some sulfide copper metal particles that may be oxidized ores containing some sulfide ores.

Tin bronze alloy technology can be traced back to various sites around WXP, including the Daye Xianglushan site[3], Anhui Tongling Shigudun[17] and Xiajiadun sites[18]. Bronze alloy slag from the Western Zhou period has been found at all these sites, indicating that bronze alloy smelting technology was present in the middle and lower reaches of the Yangtze River during the Shang and Zhou dynasties. This suggests a relatively broad distribution of this technology. Yangxin County, a well-known neighboring county, has numerous cultural relics from the Shang and Zhou dynasties, such as bronze Nao-bells, Ge-dagger-axes, bronze axes, and other bronze artifacts. These items are mainly housed in the Yangxin County Museum, indicating that the region had a substantial bronze smelting and casting industry during the Shang and Zhou periods. An earlier instance of this is the Yangxin Dalupu site, where bronze smelting and casting relics dating back to the end of the Neolithic period have been found. Alloy bronze pieces were discovered during the Hou Shijiahe culture period at the Yangxin Dalupu site[4]. However, large-scale evidence of this technological advancement has not been uncovered yet.

The Provenance of Copper Raw Material

Cultural relics survey data indicate that during the Shang and Zhou dynasties, the central government of China placed great importance on the southeastern Hubei region's management. The region, where the Daye WXP site is located, is a crucial large-scale mining area in the middle and lower reaches of the Yangtze River, abundant with copper-iron-gold-lead and other mineral resources. The Tongshankou copper mine, a large copper mining area, is less than 5 kilometers away from the WXP site. The characteristics of mineral resources in the Daye area suggest that there are indeed numerous copper polymetallic ore spots in this region. In the Jiguanzui-Longjiaoshan copper polymetallic survey area within Daye City, over ten copper-lead-zinc-molybdenum-iron ore deposits and more than 50 physical and chemical exploration anomalies have been identified. The Shizishan mining area, adjacent to the Tongshankou Copper Mine, primarily consists of the N1 and N2 ore bodies. The upper part of the N1 ore body is mostly made up of oxidized or mixed ore, with a brown honeycomb-shaped, loose soil-like copper-containing iron cap and a copper grade ranging from 0.7–6.2%. The N2 ore body primarily contains two types of ores: oxidized ore and primary ore, with an average copper grade of 2.6%. Oxidized ore accounts for 82.7% of the N2 ore body[19]. The vertical depth of the ore body reaches − 408.5 meters, with the main ore volume found between − 50 and − 150 meters. The deposit is mainly controlled by the contact zone, belonging to a typical medium-temperature hydrothermal alteration skarn polymetallic copper deposit[20]. In 1961, a large deposit was discovered nearby, identified as a contact alteration skarn type deposit[21].

The Tongshankou mining area is situated approximately 18 kilometers southwest of Daye County in Hubei Province. It is located on the eastern side of the northern part of the Dongting Depression, between the Jiangnan Ancient Land and Huaiyang Shield. The area lies on the favorable polymetallic mineralization belt extending in the Daye-Tongshankou northeast direction.

The main minerals in the ore include chalcopyrite and pyrite, with magnetite, chalcocite, sphalerite, and galena also present in smaller amounts. The industrial reserves of copper mines in Copper Mine Mountain, Bangke Mountain, and Shizishan all exceed 500 thousand tons[20].

The Provenance of Tin Raw Material

There have been no reports of tin ore exploration in Hubei Province, particularly in the southeastern Hubei region. Consequently, the Daye area, where the WXP site is located, lacks tin resources and depends on imports from other regions. If this type of slag is traced back to the smelting process, the most probable process, given the characteristics of this smelting product, would involve first using copper oxide ore with high iron content (in which some copper or iron sulfide minerals remain) for reduction smelting. Near the end of smelting, most slag is removed (i.e., pure copper smelting slag), and tin material is added to the furnace to continue reduction smelting. Finally, a small amount of slag containing tin bronze particles is discharged to obtain bronze with tin as the main alloying element. Tin minerals with higher copper and iron content may be residues of stannite desulfurization and cassiterite dehydration, respectively, and could serve as indicators of tin ore origin. Similar signs have been found at the Chenjiashan site in Zongyang, Anhui Province. The northern part of Jiangxi, adjacent to eastern Hubei, has been identified as a tin-producing region along the middle and lower reaches of the Yangtze River. This area offers strong evidence in terms of geographical location and metallurgical archaeological background of early sites. Numerous renowned mining sites are present, with four sites distributed across De'an, Fuliang, Yongxiu, and Yifeng-Shanggao counties[22]. Besides the discovery of minerals such as cassiterite (SnO₂) and stannite (Cu₂FeSnS₄), Varlamoffite (Sn-Fe)(O-OH)₂ has also been identified numerous times[23]. This mineral is found in the oxidized zone of skarn iron-copper deposits, medium-low temperature cassiterite sulfide deposits, and tin-containing skarn positive contact zones. Based on the above observations, the source of tin ore used in tin bronze smelting sites, such as the Yujia'ao site in eastern Hubei, could be traced to the Jiangxi tin ore area. However, further archaeological investigations, exploration, and excavation work are required to confirm this.

Technology of Copper Smelting Industry during the Shang and Zhou Dynasties at Hubei

During the Shang and Zhou dynasties, the characteristics of the copper smelting industry in Hubei can be discussed based on the findings from the Daye WXP and Daye Xianglushan sites. These sites share similarities in terms of unearthed relics and are mainly concentrated during the late Shang-Western Zhou period. This suggests that mining and smelting activities were prevalent in the local area at that time, with most sites being located on the outer edge of valleys near mountains and water sources. These areas provided not only convenient transportation resources but also met the necessary requirements for water and fuel for smelting operations.

Moreover, the management of mining and metallurgy during that time appeared to be relatively loose, with no large-scale unified mining and smelting activities occurring in major mines. However, subsequent periods saw a more stringent management approach to mining and metallurgy at sites such as Tonglüshan in Daye. The investigation of the Daye WXP site and analysis of metallurgical technology revealed a well-preserved site with clear evidence of metallurgical processes and diverse technical types. This makes the site suitable for further investigation and excavation, as well as expanding the exploration of surrounding sites. Sites like WXP contribute to our understanding of the metallurgical industrial production in Hubei during the Shang and Zhou dynasties. However, it is important to note that this information comes from a single site, and further site investigations are needed to reveal a comprehensive picture of the copper smelting industry in southeastern Hubei during that time.

The investigation and analysis of mining and metallurgy sites and their associated metallurgical technology have highlighted the importance of the Daye WXP site in Hubei during the Shang and Zhou dynasties. The stratigraphic profile ¹⁴C chronology analysis indicates that the site dates back to the late Shang Dynasty and has a significant time span. Numerous living relics have been discovered at the site, and the slag extracted from the cultural layer and collected from the surface demonstrates that the metallurgical technology of this site consisted of both copper smelting and tin bronze alloying. This indicates the presence of copper metallurgy activities in Daye during that period.

In recent years, our team has conducted extensive research on mining and metallurgy sites in the middle reaches of the Yangtze River. We have discovered nearly a hundred related metallurgical sites within southeastern Hubei. Representative mining and metallurgy sites are awaiting further investigation and documentation, and future reports will include laboratory testing and analysis. The examination of mining and metallurgy sites provides a direct method for investigating local metallurgical technology, particularly the comprehensive extraction of scientific and technological information during these investigations. Research conducted from this perspective holds great value and is worth further exploration and promotion.

Ethics approval and consent to participate

Not applicable

Consent for publication

Not applicable

Availability of data and material

The datasets used and/or analysed during the current study are available from the corresponding author on reasonable request.

Competing interests

The authors declare that they have no competing interests.

Funding

This research was funded by the National Key R&D Program of China with the Grant number 2020YFC1521606. and the ‘Huangshi Industrial Heritage Survey’ project in cooperation with the Huangshi Cultural Relics Protection Center and Beijing University of Science and Technology.

Authors' contributions

S P and C L is the major contributor to writing the manuscript. Y L are supervisors of C L and S P. All authors read and approved the final manuscript.

Acknowledgements

Professor Chen Shuxiang and Professor Qu Yi, who work in Hubei Province, assisted in a large amount of field work; Mr. Hu Xinsheng and Mr. Xia Peng gave strong support to the overall work. At the same time, Ma Peng, a doctoral student at Beijing University of Science and Technology, and Hou Wang participated in related investigations and expressed their gratitude.

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A Metallurgical Technology Investigation of the Wangxiangping Ancient Smelting Sites at Daye County

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Abstract

Figures

Introduction

The Background of the Site and Result

The Straitification Structure and Radiocarbon Dating Result

The Sampling Strategy and Investment Methods

The Constitution and Content Data of the Relics

Discussion

The Technology of Smelting

The Provenance of Copper Raw Material

The Provenance of Tin Raw Material

Technology of Copper Smelting Industry during the Shang and Zhou Dynasties at Hubei

Conclusion

Declarations

Ethics approval and consent to participate

Consent for publication

Availability of data and material

Competing interests

Funding

Authors' contributions

Acknowledgements

References

Table 1

Additional Declarations

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