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Article

Raw Material and Technological Analysis of Longshan Culture Pottery from the Hui River Basin, Yongcheng, Henan

by
Linyu Xia
1,2,
Ge Zhang
3,4,5,*,
Jialing Li
6,
Yufan Geng
7,
Yongtao Zhao
8 and
Yinhong Li
1
1
School of Archaeology and Cultural Heritage, Zhengzhou University, Zhengzhou 450001, China
2
Historical and Cultural Heritage Protection Research Center, Zhengzhou University, Zhengzhou 450001, China
3
Yellow River Institute of Hydraulic Research, Yellow River Water Conservancy Commission, Zhengzhou 450003, China
4
Key Laboratory of Lower Yellow River Channel and Estuary Regulation, Ministry of Water Resources, Zhengzhou 450003, China
5
Yellow River Laboratory, Zhengzhou University, Zhengzhou 450003, China
6
School of Water Conservancy and Transportation, Zhengzhou University, Zhengzhou 450001, China
7
Zhengzhou Museum, Zhengzhou 450001, China
8
Sichuan Provincial Institute of Cultural Relics and Archeology, Chengdu 610041, China
*
Author to whom correspondence should be addressed.
Heritage 2025, 8(9), 342; https://doi.org/10.3390/heritage8090342 (registering DOI)
Submission received: 10 July 2025 / Revised: 13 August 2025 / Accepted: 19 August 2025 / Published: 23 August 2025
(This article belongs to the Special Issue Multianalytical Approaches Applied to Conservation and Restoration Strategies in Cultural Heritage)
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Abstract

The Dazhuzhuang, Biting, and Likou Sites are located along the Hui River basin in Yongcheng, eastern Henan. These three sites are situated close to each other and all yielded Longshan Culture period (2300–1800 BCE) remains, including large quantities of pottery with similar stylistic characteristics. However, archaeological surveys did not discover kiln sites at any of the three locations. To investigate the sources of Longshan period pottery in this region, its firing technology, and whether pottery circulated between the sites, this study employed a combination of X-ray fluorescence spectroscopy (XRF), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) to conduct a comprehensive scientific analysis of pottery unearthed from Longshan Culture contexts at the Dazhuzhuang, Likou, and Biting Sites in the Huai River basin, Yongcheng, Henan Province. The results reveal significant differences among the sites in terms of raw material selection, chemical composition, and technological characteristics. Pottery from the Dazhuzhuang Site exhibits with diverse clay sources. The Likou Site is characterized by highly homogeneous compositions derived from relatively high-alumina, low-iron clays, indicating standardized production practices. In contrast, the Biting Site shows greater variability in raw materials and functional differentiation. Thermal and microstructural analyses indicate that the dense glassy phase of black pottery was achieved through reducing firing conditions. In contrast, gray pottery was manufactured with calcareous additives to produce a porous structure.

1. Introduction

The Longshan period (ca. 2300–1800 BCE) marked a critical phase of transformation across various aspects of society in the core area of prehistoric Chinese traditions. Located in eastern Henan, the Yudong region borders Mount Song and maintains extensive cultural exchanges and interactions with surrounding regions such as the Haidai area, the middle Huai River, and the middle Yangtze River. With its unique geographical position, the region forms a core area for the origins of Chinese civilization and holds significant value in exploring the processes of early social complexity and interregional interactions [1,2,3]. Archaeological work in the Yongcheng area of eastern Henan began in 1936, when Li Jingdan conducted archaeological investigations in the Shangqiu–Yongcheng area in search of the origins of the Shang civilization. During this time, multiple Longshan cultural sites were discovered along both banks of the Huai River in Yongcheng, and small-scale excavations were carried out on the three sites of Zaolvtai, Heigudui, and Caoqiao. The pottery, stone, bone, and mussel unearthed from Zaolvtai and Heigudui Sites have obvious cultural characteristics of the Longshan period [4]. In the 1970s, the Institute of Archaeology, Chinese Academy of Social Sciences, together with the Cultural Relics Administration of Shangqiu, conducted excavations at the Wangyoufang and Heigudui Sites in Yongcheng. In 2002, the Department of Archaeology of Zhengzhou University surveyed several Longshan cultural sites in Yongcheng, including the Hongfu, Zhaozhuang, Mingyangsi, and Zaolvtai Sites [5]. These extensive archaeological investigations have established a relatively comprehensive cultural sequence (Yangshao Culture, early- and middle-period Dawenkou Culture, middle- and late-period Haidai Longshan Culture, and Wangyoufang-type Yueshi Culture) and a wealth of regional archaeological data for the area. Scholars such as Su Bingqi and Yin Weizhang [6] have contributed to the classification of archaeological culture into regions, systems, and types based on regional cultural content. In addition, academic research has expanded into areas such as cultural genealogy, settlement patterns, subsistence economy, handicrafts, and social civilization processes. Scholars, including Yan Wenming [7], Yang Zifan [8], Liang Siyong [9], An Zhimin [10], Gao Tianlin [11], Luan Fengshi [12,13], and Chen Hongbo [14], have conducted in-depth studies on the cultural genealogy, cultural types, settlement distribution, and environmental changes in the Longshan Culture in eastern Henan [15]. Zheng Qingsen [16] summarized the characteristics of the Longshan Culture in eastern Henan and discussed its origins. The Longshan Culture in eastern Henan comes from the Dahankou Culture, which is very close to the Longshan Culture in Shandong, and then develops into the local Yueshi Culture, which can also be used as the local type of the Longshan Culture in Shandong. Hu Haoyue analyzed systematically the plant remains recovered from the Pingliangtai Site (2016–2019), revealing the subsistence economy, handicrafts, and social complexity from an early complex society to early statehood in eastern Henan [17]. Zhao Jiangyun [18], using traditional typology and cultural element analysis, traced the diffusion and spread of cultural elements to examine interactions between archaeological cultures and to explore the sociopolitical processes involved in the formation of the Haidai Longshan Culture.
In 2022, the Department of Archaeology at Zhengzhou University conducted a survey along the Hui River in Yongcheng, identifying 17 sites with Longshan cultural remains. This discovery provided new materials and opportunities for understanding the development of prehistoric society in eastern Henan. Among these, the Dazhuzhuang Site (16,800 m2), Biting Site (40,000 m2), and Likou Site (90,000 m2), located at the junction of Henan, Anhui, and Shandong Provinces (see Figure 1), represent key areas for the interaction between the Wangyoufang type of Longshan Culture and surrounding cultural regions [19]. These sites exhibit a clear hierarchical organization and yielded a rich and diverse collection of Longshan period pottery, featuring typical vessel forms. Dazhuzhuang, Biting, and Likou Sites are distributed along the Hui River, and the three sites are not far from each other, which is convenient for cultural exchange. As such, they serve as exemplary archaeological cases for understanding the social complexity and civilization process in the Hui River basin of Yongcheng.
Pottery, as the most common type of archaeological artifact, is rich in information and regarded more as a marker of sedentism [20,21]. The dissemination and integration of pottery traditions largely reflect human interactions and social exchange. In the course of social development, pottery production technology was not only invented but also led to the formation of corresponding technological and production organizations. Chinese archaeological studies of pottery have primarily focused on the following three aspects: (1) Characterization and classification of pottery [22,23], including analysis of vessel forms and functional categories. (2) Typological and cultural element analysis [24,25,26,27], especially from the 1960s to the 1980s, when typological frameworks for regional archaeological cultures were established. (3) Technological studies of pottery; since the 1990s, significant advances have been made in understanding ancient ceramic manufacturing techniques. For example, in Research on Ancient Chinese Pottery Technology [28], Li Wenjie analyzed traces and features preserved on excavated pottery, verified them through experimental archaeology, and summarized the pottery production processes in the Yellow River and Yangtze River basins from the Neolithic to Han periods. Over the past fifty years, research on pottery technology has evolved from a purely technical focus to a tool for social analysis [29]. Scholars such as Li Jiafang and Gao Guangren [30] have examined the origins, development, and social characteristics of the typical Longshan Culture. Compared to traditional archaeological approaches, experimental archaeology in Chinese pottery studies began relatively late, only developing since the 1970s. With the application of multidisciplinary and multiscale approaches, pottery research has employed a range of analytical techniques, including chemical composition analysis [31,32,33,34], petrography [35,36,37], and residue analysis [38,39,40]. It has gradually become systematic and comprehensive, forming an integrated research framework that combines ethnographic investigation, archaeological data analysis, experimental replication, and laboratory testing. Based on the above research background, this study integrates traditional archaeological approaches with materials science, adopting a combined typological and archaeometric methodology. Utilizing multiple analytical techniques, including X-ray fluorescence spectroscopy (XRF), thermogravimetric analysis (TGA), and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), the study systematically analyzes Longshan period pottery from the Dazhuzhuang, Biting, and Likou Sites in the Hui River basin of Yongcheng. By examining their chemical compositions, microstructures, and micro-morphologies, the research explores the diffusion and spread of cultural factors to surrounding regions. It discusses broader issues such as productivity, social organization, and cultural interaction during the Longshan period in Yongcheng. Ultimately, this study contributes to a deeper understanding of the “pluralistic unity” process in the origins of Chinese civilization

2. Experimental Part

2.1. Sites

The Dazhuzhuang Site is located on the northwest side of Dazhuzhuang Village, Peiqiao Town, Yongcheng City, with a north–south width of 120 m and an east–west length of 140 m, covering an area of approximately 16,800 square meters. The cultural deposits range in thickness from 0.8 to 2.1 m. The collected artifacts primarily consist of pottery sherds, with a small quantity of shell fragments and animal bones. The pottery mainly dates to the Longshan Culture and Han periods. Longshan Culture pottery is dominated by fine-grained gray ware, followed by fine-grained brown and gray-black pottery. Decorative motifs are primarily cord-marked and plain, with fewer examples of basket motifs, string motifs, and checkerboard surface treatment techniques (see Figure 2 for decorative motifs). Object types include storage jars, ding legs, pottery lids, basins, urns, dou stemmed vessels, cups, etc. (Figure 3). A total of 15 samples were selected for analysis, all of which were unearthed from the archaeological excavation site H1, including storage jars (used for holding liquids or food), basins (wide-mouthed, narrow-based vessels for containing liquids, food, or for washing), cups (for drinking), ding legs (from cooking tripods with typically round bodies, three legs, and two loop handles, or sometimes square with four legs), yan legs (from steamers composed of an upper vessel [zeng] for food and a lower vessel [li] for water, separated by a perforated plate, with fire heated beneath the tall legs), and handles (protrusions used for lifting or holding). The majority of the samples are fine-grained gray pottery, with a small amount of fine-grained brown pottery. The main decorative motifs are checkerboard compositions and plain surfaces.
A total of seven storage jars were identified. Six are made of fine-grained paste. They feature flared rims, everted mouths, square lips, constricted necks, and sloping shoulders. Specimen 2023YPDH1:1 has a globular body, with the lower portion preserved; the surface is undecorated (Figure 4:1). Specimen 2023YPDH1:4 is preserved below the shoulder, with checkerboard pattern decoration on the shoulder (Figure 4:6). Specimen 2023YPDH1:5, with a rounded lip and body preserved below the shoulder, is decorated with a diamond-shaped checkerboard pattern on the shoulder (Figure 4:7). Specimen 2023YPDH1:16 has a square lip with a circular groove on the lip surface and is preserved from the shoulder downward; the shoulder bears checkerboard decoration (Figure 4:1). Specimen 2023YHLH2:1 is decorated with a checkerboard pattern on the shoulder. Specimen 2023YPDH2:5 has a rounded lip, curving body, and the lower part is missing; the surface is decorated with medium cord-marking (Figure 4:3).
Specimen 2023YPDH1:9 is made of fine-grained paste. It has a flared rim, everted mouth, square lip with a groove on the interior edge of the mouth, constricted neck, sloping shoulder, and curving body, with the portion below the belly missing. The surface is decorated with a diamond-shaped checkerboard pattern (Figure 4:5).
Four basins were identified, three made of fine-grained paste. These have wide mouths, rounded lips, obliquely straight sides, and are preserved below the belly; the surfaces are plain. Specimens include 2023YPDH1:13 (Figure 4:9), 2023YPDH1:11 (Figure 4:11), and 2023YPDH2:12 (Figure 5:2). One basin specimen, 2023YPDH1:12 (Figure 4:10), is made of fine-grained brown pottery, also with a wide mouth, rounded lip, and oblique sides, plain surface, and preserved from the belly downward.
One cup was identified, specimen 2023YPDH1:19, made of fine-grained paste. It has a wide mouth, square lip with a circular groove on the inner edge, shallow body, and flat base. The surface is plain (Figure 4:8).
One ding leg was found, specimen 2023YPDH1:21, made of fine-grained paste. It is a laterally triangular flat leg with a solid base. The outer surface of the leg root features six thumb impressions; the surface is undecorated (Figure 4:4).
One yan leg was identified, specimen 2023YPDH1:23, made of fine-grained paste. It is a bag-shaped, solid conical leg with a slender and tall profile. The surface is plain (Figure 4:2).
One handle was recovered, specimen 2023YPDH1:17, made of fine-grained paste. It is a bridge-shaped lug. The surface is plain (Figure 4:3).
The Biting Site is located on the southeast side of Bianzhuang Village, Xinqiao Town, Yongcheng City. The central, western, and northern portions of the site are overlain by buildings of the town’s grain depot. The site has an irregular plan and covers an area of approximately 40,000 square meters. Archaeological survey revealed cultural deposits ranging from 1.4 to 2.3 m in thickness. In the southwestern corner of the site, a rammed earth wall foundation was uncovered, forming an L-shaped layout. Features identified at the site include burials, ash pits, road surfaces, and rammed earth walls. Ash pits are mainly concentrated in the southeastern part of the site, with cultural layers reaching depths of about 2.3 m. The rammed earth wall cuts through earlier ash pits; artifacts recovered from test pits within these ash pits include snails, freshwater mussels, deer bones, and cord-marked pottery sherds. The collected artifacts primarily date to the Longshan and Shang cultural periods. Sherds from the Longshan Culture period are dominated by fine-grained gray pottery and gray-black pottery, with some examples of burnished black pottery and fine-grained brown pottery, as well as smaller quantities of sand-tempered gray and brown pottery and shell-tempered gray and brown pottery. The main decorative motifs include basket motifs, checkerboard compositions, and plain surfaces, followed by cord-marked decoration and a few examples of string motifs. Vessel types include storage jars, basins, bowls, and ding tripods. A total of eight samples were selected for analysis, including storage jars, basins, bowls (circular, concave vessels used for serving food), and ding legs. The pottery is mainly composed of fine-grained gray ware, with decoration primarily consisting of checkerboard motifs, cord-marked surfaces, and plain finishes.
A total of eight pottery specimens were selected for analysis, all of which were unearthed from the fifth layer of Longshan Culture, including storage jars, a basin, a bowl, and a ding leg. The majority are made of fine-grained paste, with decorations primarily consisting of checkerboard motifs, cord-marked surfaces, and plain finishes.
Five storage jars were identified, all made of fine-grained paste, featuring flared rims, everted mouths, and square lips. Specimen 2023YXBP⑤:7 has a circular groove on the inner edge of the lip, a constricted neck, and sloping shoulders, with the portion below the shoulder missing. The shoulder is decorated with a checkerboard pattern (Figure 6:3). Specimen 2023YXBP⑤:21 has a constricted neck and sloping shoulders, preserved below the shoulder; the shoulder bears cord-marked decoration (Figure 6:4). Specimen 2023YXBP⑤:13 features an inner lip groove, constricted neck, and sloping shoulders; the surface is plain (Figure 6:5). Specimen 2023YXBP⑤:8 also has a circular groove inside the lip, with a constricted neck and sloping shoulders, and is decorated with a checkerboard pattern on the shoulder (Figure 6:6). Specimen 2023YXBP⑤:14 has a lip-side groove, constricted neck, and rounded shoulders, with the lower part missing; the surface is plain (Figure 6:7).
One basin, specimen 2023YXBP⑤:1, is made of fine-grained paste. It has a flared rim, everted mouth, rounded lip with an interior groove, and obliquely straight sides, with the portion below the belly missing. The surface is plain (Figure 6:1).
One bowl, specimen 2023YXBP⑤:10, is made of fine-grained paste. It has a wide mouth, square lip with a groove across the lip surface, and sloping sides, with the lower portion missing. The surface is plain (Figure 6:2).
One ding leg is made of fine-grained paste. It is a laterally triangular flat leg with a solid base; the tip of the leg is broken, and there is a thumb impression near the upper part of the outer side (Figure 6:8).
The Likou Site is a newly discovered site of this archaeological survey. This site is located in Likou Village, Houling Community. The Huai River flows to the south of the site, with the village to the west, and the north and east bordering the administrative region of Huaibei City in Anhui Province. The site is situated on an elevated terrace surrounded by water on two sides. Collected artifacts include pottery sherds, lithics, freshwater shells, deer antlers, and animal bones. The pottery primarily dates to the Yangshao, Longshan, and Shang cultural periods. The site has undergone three archaeological surveys and investigations. The first revealed cultural deposits ranging from 0.3 to 3.8 m thick, with most features distributed in the southern area, including ash pits and large areas of rammed earth. The second survey uncovered a rammed earth structure nearly 30 m wide in the northern and western parts of the site, leading to the hypothesis that the Likou Site may have comprised both a large and a small walled settlement. The third investigation confirmed cultural deposits of approximately 0.3 to 5 m thick, and determined that the southern rammed earth city wall extended southeast along the river (Figure 7). It was thus concluded that the previously presumed “large” and “small” settlements were part of a single city enclosure. To clarify the dating of the wall, a 1 × 5 m trench was excavated at the southwestern corner of the site. A Late Shang ash pit was found cutting through the wall, indicating that the wall predates the Late Shang period. A large quantity of pottery sherds was recovered from the pit, primarily composed of fine-grained gray pottery, along with smaller quantities of sand-tempered gray-black and gray-brown pottery. Decorations are mainly medium cord-marked motifs, followed by plain surfaces. Vessel types include li tripods and storage jars. Numerous tamping pits were observed within the wall fill, which overlies a Longshan period cultural layer containing pottery sherds, freshwater shells, snail shells, and plant ash.
Pottery from the Longshan period is dominated by fine-grained gray ware, along with burnished black pottery and fine-grained brown pottery. There are also smaller quantities of sand-tempered gray and brown pottery, and shell-tempered variants. Decorations primarily include basket motifs, checkerboard compositions, and cord-marked surfaces, with minor plain surfaces and occasional string motifs. Common vessel forms include storage jars, urns, basins, bowls, pottery lids, and ding tripods. It is inferred that the city wall dates no later than the Late Shang period and no earlier than the Longshan period, possibly coexisting with the latter. A total of five pottery specimens were selected for analysis, all of which were excavated from the fifth layer of the site, including urns, storage jars, and pottery lids (used as covers for ceramic containers).
Two urns were identified, both made of clay material, with straight mouths and pointed lips. Specimen 2023YHL⑥:1 has two raised ridges on the outer rim, a short neck, and sloping shoulders, with the lower portion missing. The vessel surface is plain and burnished (Figure 8:1). Specimen 2023YHL⑥:2 has an inner rim groove, a tall neck, and sloping shoulders, with the body below the shoulder missing (Figure 8:2).
One pottery lid, specimen 2023YHLH2:2, is made of fine-grained paste. It has a wide, slightly constricted mouth, square lip with a groove on the lip surface, obliquely straight sides, and a flat base, with wheel marks visible on the inner surface. The exterior is plain and burnished (Figure 8:4).
Two storage jars were also identified, both made of clay material with plain burnished surfaces. Specimen B6:3 is a body sherd from the midsection of a jar (Figure 8:5), while specimen B6:4 has a flared mouth, rounded pointed lip, constricted neck, and the lower portion is missing (Figure 8:3).

2.2. Sample Preparation

This study applied a multidisciplinary approach to the analysis of archaeological ceramics using X-ray fluorescence spectroscopy (XRF), thermal analysis (TGA/DTA), and scanning electron microscopy (SEM-EDS). Specifically, XRF was employed to determine the elemental composition of the ceramic samples and to assess potential raw material sources. SEM-EDS was used to investigate the microstructural characteristics of the ceramic matrix. Differential thermal analysis (DTA), as part of the broader thermogravimetric analysis (TGA), was conducted to infer firing conditions.
The sample preparation and processing procedures were conducted as follows. First, pottery sherd samples were cut into small blocks of approximately 2 cm2 using a cutting machine, and the cross-sections were subsequently polished to a flat surface. The samples were then subjected to ultrasonic cleaning twice in deionized water, followed by a second cleaning with an alcohol solution. For SEM-EDS (scanning electron microscopy with energy-dispersive spectroscopy) analysis, the samples were further broken into smaller fragments using pliers. For XRF (X-ray fluorescence) and TGA (thermogravimetric analysis) tests, the fragments were sequentially crushed and ground, then passed through a 0.075 mm sieve to obtain the desired results. Table 1 shows the grouping of performance index tests, including the size and number of each test and specimen.

2.2.1. Energy-Dispersive X-Ray Fluorescence Analysis

Energy-dispersive X-ray fluorescence (XRF) (Shimadzu EDX-8100, Kyoto, Japan) was used to test the chemical compositions of pottery (SiO2, Al2O3, Fe2O3, CaO, MgO, K2O, Na2O, and TiO2) from the three sites in Yongcheng. The analytical characteristics of the method include the following: relative standard deviations (RSDs) < 5% for major elements, linear ranges of 0.1–100 wt% for major oxides (SiO2, Al2O3, Fe2O3, etc.), and limits of detection (LODs) between 0.01 and 0.05 wt% for major elements. Before analysis, all samples were meticulously cleaned to minimize surface contamination using a sequential protocol that included gentle mechanical brushing with a soft brush, ultrasonic cleaning in deionized water, and a final rinse with isopropanol. XRF measurements were performed under optimized instrumental conditions: a 1.2 mm X-ray spot diameter, 30 kV tube voltage, 0.029 mA tube current, and an acquisition time of 100 s per measurement to ensure sufficient counting statistics. To ensure analytical accuracy and data reliability, the instrument was calibrated using Corning Glass D as the primary reference standard [42], with periodic recalibration every 20 samples to monitor instrumental drift, ensuring reliable quantification of major and minor elements.

2.2.2. Thermogravimetric Analysis

Thermal performance testing was conducted using a Beijing Jingyi Gaoke ZCT-B simultaneous thermal analyzer (STA). Approximately 15.0 ± 0.2 mg of each sample was accurately weighed and placed in an alumina crucible, with an empty crucible used as the reference. The test was carried out under an argon atmosphere (flow rate: 50 mL/min) with a heating rate of 10 °C/min, programmed from 30 °C to 1000 °C. Differential thermal analysis (DTA) and thermogravimetric (TG) curves of the samples were simultaneously recorded. Each group of samples was tested in triplicate to ensure data reproducibility, with an error margin of less than 5%. Prior to testing, temperature calibration was performed using a standard substance (α-Al2O3), ensuring a temperature measurement accuracy of ±0.5 °C.

2.2.3. Scanning Electron Microscopy Test

The microstructure of the samples was observed using a Sigma 300 field emission environmental scanning electron microscope (Carl Zeiss AG, Oberkochen, Germany). The signal encompassed secondary electrons and backscattered electrons. The acceleration voltage was 15 kV, the vacuum level was maintained at 1 Pa, the amplification range was 18–30,000 times, and the maximum resolution was 3 nm. A thin layer of gold was deposited on the samples to enhance their conductivity for scanning electron microscopy. Backscattered electron (BSE) imaging was conducted at an accelerating voltage of 15 kV to optimize compositional contrast. Energy-dispersive X-ray spectroscopy (EDS) analysis was performed at 20 kV to ensure sufficient X-ray excitation while minimizing beam penetration artifacts. The samples analyzed by SEM-EDS were prepared as polished resin blocks.

3. Results and Discussion

3.1. Chemical Composition Analysis

A total of 28 pottery samples unearthed from three Longshan Culture sites in the Yongcheng region were systematically analyzed in this study, including 15 from the Dazhuzhuang Site, 5 from the Likou Site, and 8 from the Biting Site. Typological analysis reveals that the Dazhuzhuang samples exhibit the greatest diversity, encompassing six vessel types: storage jars, yan legs, handles, ding legs, cups, and basins, primarily composed of fine-grained gray pottery with a small amount of brown pottery. The functional assemblage is relatively complete, comprising cooking vessels (ding legs and yan legs), storage containers (jars and basins), and drinking vessels (cups). The Likou samples are dominated by burnished black pottery, with representative forms including pottery lids, urns, and body sherds from jars. These vessels are characterized by thin walls (averaging 2–3 mm) and finely burnished surfaces, indicating a specialized function for storage. All eight samples from the Biting Site are fine-grained gray pottery, primarily consisting of standardized daily-use vessels such as basins, bowls, storage jars, and ding tripods, with dense and uniform fabrics. X-ray fluorescence (XRF) analysis was performed to determine the chemical composition of the samples, focusing on 16 elements, including major oxides such as SiO2, Al2O3, Fe2O3, K2O, MgO, CaO, Na2O, and TiO2. The resulting elemental data characterize the chemical features of the pottery from each site (see Table 2 for details).
Using oxide concentrations as observational variables, a one-way ANOVA and significance analysis were conducted to evaluate compositional variability among the pottery samples from the Dazhuzhuang, Likou, and Biting Sites in the Hui River basin of Yongcheng. The results indicate that, with the exception of K2O, which showed relatively low statistical significance, the contents of SiO2, Al2O3, MgO, CaO, Na2O, and TiO2 exhibit significant differences across the three sites. Fe2O3 also displays a certain degree of statistical distinction, though to a lesser extent. These findings suggest notable heterogeneity in raw material composition or technological choices among these sites.
According to Table 2, the oxides can be classified into three categories: major ceramic-forming oxides (SiO2, Al2O3, Fe2O3, and CaO) and other oxides (K2O, MgO, Na2O, and TiO2). Specifically, with respect to the alumina content (Al2O3), a threshold of 22.5% can be used to differentiate between relatively high-alumina and relatively low-alumina raw material types [43].
From the compositional characteristics of the major ceramic-forming oxides, the pottery from the three Longshan Culture sites in the Yongcheng region displays distinct raw material preferences and technological differences. The Dazhuzhuang Site pottery has SiO2 contents ranging from 64.98% to 71.07% (mean 67.98 ± 1.19%) and Al2O3 ranging from 15.18% to 18.83% (mean 16.96 ± 0.78%). The Fe2O3 (5.08–7.07%, mean 5.74 ± 0.58%) and CaO (1.19–1.81%, mean 1.49 ± 0.16%) contents are relatively stable, suggesting the use of river alluvial clay that may have undergone levigation treatment. The Likou Site pottery shows the mean contents of Al2O3 (17.78 ± 0.23%) and CaO (1.75 ± 0.28%), with relatively narrow ranges for SiO2 (65.93–67.97%, mean 67.10 ± 0.68%) and Fe2O3 (5.02–6.26%, mean 5.69 ± 0.45%). The Biting Site pottery falls between the other two in terms of SiO2 (65.19–69.01%, mean 67.29 ± 1.30%) and Al2O3 (15.88–18.08%, mean 17.36 ± 0.62%) contents, but it exhibits the widest Fe2O3 distribution range (5.28–7.11%, mean 5.98 ± 0.59%) and the lowest mean CaO content (1.41 ± 0.28%). This variation in chemical composition may reflect greater diversity in the clay sources used at the site.

3.2. XRF Data Distribution Analysis

In this study, one-dimensional distribution plots were generated by plotting the chemical concentration of each oxide (Y-axis) against the sample ID (X-axis) [44]. Figure 9a–e presents the one-dimensional scatter plots for SiO2, CaO, K2O, Al2O3, MgO, Na2O, and Fe2O3, respectively. Figure 9a illustrates both the commonality and variability in SiO2 concentrations among pottery samples from the three Longshan cultural sites in Yongcheng. Notably, 87% of samples from Dazhuzhuang (39/45), 80% from Likou (12/15), and 75% from Biting (18/24) cluster within the typical range of 66.67–69.01%. This range is consistent with the chemical profile of typical Longshan pottery raw materials in the Central Plains region, such as secondary alluvial clay from the Yellow River [45], suggesting a shared regional standard for raw material selection. It is noteworthy that outlier samples from Likou and Biting exhibit lower SiO2 concentrations (below 66.67%), possibly due to the occasional use of low-silica clays such as kaolinite or the addition of other materials. In contrast, Dazhuzhuang exhibits a distinctive bidirectional dispersion, comprising three low-silica samples (~65%) and three relatively high-silica samples (exceeding 70%). This unique distribution pattern may indicate a more complex pottery production system at the site, potentially involving (1) parallel use of multiple raw material sources or (2) differentiated recipes for pottery with distinct functional purposes.
Figure 9b shows that CaO concentrations also exhibit both consistent motifs and site-specific differences. A significant portion of samples—80% from Dazhuzhuang (36/45), 80% from Likou (12/15), and 75% from Biting (18/24)—cluster within the range of 1.37–1.82%, aligning with the low-calcium clay characteristic of Longshan pottery from the middle Yellow River region. This suggests a general preference among regional potters for low-Ca raw materials, such as alluvial clays or washed sedimentary soils [37]. However, outlier samples reflect divergent behaviors across sites: 20% of Dazhuzhuang samples (9/45) fall below 1.37%, possibly due to the use of highly washed clay or quartz sand temper. In contrast, 20% of Likou samples (3/15) exhibit relatively higher CaO levels (~2.20%), which may result from the intentional addition of calcite or calcareous clay, possibly linked to specific technical requirements (e.g., for vessels storing alkaline liquids). At Biting, 25% of samples (6/24) exhibit CaO levels below 1.20%, which is significantly lower than the main group. This extremely low-Ca pattern may reflect either (1) a technological choice—such as the intentional selection of high-purity clay or material processing to enhance thermal performance—or (2) natural geochemical variation in locally available clay sources.
Figure 9c highlights spatial motifs in K2O distribution. A total of 87% of Dazhuzhuang samples (39/45), 80% from Likou (12/15), and 83% from Biting (20/24) fall within the typical range of 3.16–3.77%, corresponding to potassium feldspar-rich clay typical of Longshan ceramics in North China [46]. However, the outlier motifs differ between sites: low-potassium samples from Dazhuzhuang and Likou (13% and 20%, respectively) exhibit K2O concentrations below 3.16%, possibly reflecting the selective use of deeply weathered or washed clays. Conversely, 17% of Biting samples (4/24) show exceptionally high potassium content (>4.30%). These spatial variations in K2O content further underscore the technological diversity in Longshan ceramic production.
Figure 9d reveals a bimodal distribution pattern in Al2O3 concentrations and its archaeological implications. Data show that Al2O3 values are concentrated in two distinct ranges: 16.25–17.15% and 17.32–18.24%. A total of 73% of samples from Dazhuzhuang (33/45) fall within the relatively low-alumina range (16.25–17.15%), while all samples from Likou (15/15) and 75% from Biting (18/24) fall within the relatively high-alumina range (17.32–18.24%). This bimodal pattern may indicate two raw material selection strategies: the relatively low-alumina range corresponds to the use of common alluvial clays, while the relatively high-alumina range suggests a preference for kaolinite-rich or aluminum-rich sedimentary clays [47]. Interestingly, Dazhuzhuang displays a unique “three-tiered” distribution: in addition to the dominant low-alumina group, 7% of samples fall below 16.25%, and another 7% exceed 18.24%. This may reflect (1) raw material differentiation based on functional vessel types, (2) experimentation with ceramic recipes, or (3) mixing of multiple raw materials. At Biting, 12.5% of samples fall below 16.25%, and another 12.5% occupy the transitional zone (17.15–17.32%), suggesting a more fluid approach to raw material processing. These Al2O3 distribution motifs provide important evidence in materials science for understanding raw material strategies, ceramic technological traditions, and potential social divisions of labor in Longshan communities in the Yongcheng region.
Figure 9e reveals significant differences in MgO content among pottery samples from the three Longshan cultural sites in the Yongcheng region. The majority of MgO values fall within a typical range of 1.49–1.74%, with 82% of samples from Dazhuzhuang (37/45) and 80% from Likou (12/15) clustering in this interval [48]. However, only 38% of samples from Biting (9/24) fall within this range, exhibiting a markedly different distribution pattern. Notably, 50% of Biting samples (12/24) show high MgO content (>1.74%), a significantly higher proportion than observed at Dazhuzhuang (4.4%) or Likou (20%). Additionally, low-MgO samples (<1.49%) are found at both Dazhuzhuang (13.3%) and Biting (12.5%), possibly reflecting the use of deeply washed clays or naturally low-Mg materials. This spatial variation in MgO content not only reveals differing raw material preferences among settlements but may also suggest a unique ceramic technological tradition at Biting, potentially related to the availability of specific local geological resources. These findings offer valuable insights into understanding regional techno-economic networks during the Longshan cultural period.
Figure 9f presents the distribution characteristics of Na2O content in pottery from the Longshan sites in the Yongcheng region. The majority of Na2O values fall within the range of 1.04–1.31%, with 93% of samples from Dazhuzhuang (42/45) and all samples from Likou (15/15) falling within this range. This matches the typical profile of sodium feldspar-rich clays used in the middle Yellow River region [49]. Interestingly, Biting exhibits a clear “bipolar divergence”: while 58% of its samples (14/24) fall within the main distribution range, 33.3% (8/24) display abnormally high Na2O content (>1.31%), and 8.3% (2/24) show low Na2O levels (<1.04%). In contrast, Dazhuzhuang contains only 7% low-sodium outliers (3/45), and Likou displays highly uniform sodium content. These differences may reflect distinct technological traditions in raw material processing across settlements, offering valuable insights into local adaptations and inter-settlement technological exchange during the Longshan cultural period.
Figure 9g reveals the distribution of Fe2O3 content and its technological implications. Most Fe2O3 values fall within 5.02–6.26%, encompassing all samples from Likou (15/15), 80% from Dazhuzhuang (36/45), and 75% from Biting (18/24). This range aligns with the characteristics of hematite-rich clays commonly found in northern China. Notably, two sites show distinct clusters of high-iron outliers: 20% of Dazhuzhuang samples (9/45) have Fe2O3 contents exceeding 6.5%, while 25% of Biting samples (6/24) exceed 6.6%. These elevated values may reflect various technological behaviors, including (1) the intentional use of iron-rich clay to improve thermal performance, (2) the addition of iron oxide minerals such as hematite as colorants, or (3) changes in iron valence states resulting from specific firing conditions. Notably, the uniformity of Fe2O3 content in Likou samples indicates a high degree of standardization in raw material selection and processing. In contrast, the clustered distribution of high-iron samples at Dazhuzhuang and Biting may point to specialized production of functional wares (e.g., cooking or ritual vessels). These Fe2O3 distribution motifs provide critical evidence in materials science for interpreting technological choices, functional differentiation, and regional craft interactions among Longshan communities.
Figure 10a–d illustrate the three-dimensional distribution motifs of oxide components in pottery samples from the three Longshan culture sites in the Yongcheng region. Figure 10a presents the CaO–SiO2–Al2O3 ternary plot, which reveals distinct differences in raw material formulations and firing technologies among the sites. The Dazhuzhuang samples exhibit pronounced chemical dispersion, with Al2O3 and SiO2 showing a negative linear correlation—Al2O3 increases as SiO2 decreases—possibly reflecting the use of multiple raw material sources or intentional compositional adjustments (e.g., blending of relatively higher-alumina clay with siliceous additives). In contrast, the samples from Likou and Biting demonstrate higher compositional concentration, especially the Likou samples, which cluster tightly together.
Figure 10b displays the SiO2–Al2O3–Fe2O3 ternary diagram, highlighting significant chemical differences among the three sites. Fe2O3 exhibits greater compositional variability compared to SiO2 and Al2O3, likely due to differences in the origin of raw materials or post-processing techniques. Dazhuzhuang and Biting share similar Fe2O3 variation trends; however, Dazhuzhuang exhibits the widest Fe2O3 range, possibly due to an uneven distribution of iron-bearing minerals or variations in clay washing procedures. Moreover, Dazhuzhuang also shows higher dispersity in SiO2 and Al2O3 compared to Biting, suggesting more diverse raw material usage or recipe modulation. In contrast, the Likou samples cluster tightly in this ternary space, indicating a stable raw material composition and possibly a standardized production system. These compositional differences may reflect the production of multifunctional ceramics (e.g., for cooking, storage, or ritual purposes) at Dazhuzhuang and Biting versus a more specialized ceramic output at Likou. Overall, the relatively distinct clustering motifs in the SiO2–Al2O3–Fe2O3 space provide strong scientific evidence for analyzing production organization models across Longshan period settlements in the Yongcheng region.
Figure 10c shows the three-dimensional distribution of K2O–MgO–Na2O. Compared with the primary ceramic-forming oxides, these flux components demonstrate greater chemical dispersion, indicating technological variability in raw material selection and processing. Dazhuzhuang samples exhibit relatively stable Na2O content, while K2O and MgO show greater variation—suggesting a consistent use of sodium-bearing materials but a flexible approach to potassium and magnesium inputs. At Biting, a negative correlation is observed between MgO and Na2O (i.e., Na2O increases as MgO decreases), which may reflect differentiated recipes for distinct ceramic functions.
Figure 10d presents the CaO-(K2O+Na2O)-MgO ternary plot, which captures the technological characteristics of the three sites. This parameter space effectively distinguishes the ceramic technological traditions of each site. Biting exhibits the widest compositional spread, possibly reflecting the use of multi-source clays or differentiated recipes for various functional vessel types (e.g., storage vs. cooking). In contrast, Likou exhibits a highly concentrated composition with a notably elevated MgO content, indicating the systematic use of magnesian raw materials (e.g., talc or magnesian clay) and suggesting a standardized raw material processing workflow. Dazhuzhuang occupies an intermediate position, with transitional features in its CaO-(K2O+Na2O)-MgO space. This pattern may imply that (1) its ceramic technology represents a developmental stage between Biting’s diversification and Likou’s standardization, or (2) dual technological traditions coexisted at the site. These findings offer crucial evidence for understanding technological choices in prehistoric ceramic production in the Yongcheng region, with the systematic differences in MgO content being particularly noteworthy, as they may reflect

3.3. Thermal Analysis

TGA analysis was conducted on pottery unearthed from Dazhuzhuang, Likou, and Biting Sites in Yongcheng, Shangqiu. The results are shown in Figure 11. Figure 11a,b show the DTA spectra of the Dazhuzhuang Site, Figure 11c shows the DTA spectrum of the Likou Site, and Figure 11d shows the DTA spectrum of the Biting Site. By analyzing the DTA spectra, it is found that the pottery from the three sites all exhibits similar mineral composition characteristics. Specifically, the thermal behavior differences between the fine-grained gray pottery (Figure 11a) and brown pottery (Figure 11b) from the Dazhuzhuang Site are small, and the differences in peak temperatures of high-temperature phase transitions are slight, indicating that their raw material matrices are similar. Although the thermal decomposition peaks of the fine-grained black pottery from the Likou Site (Figure 11c) are close to those of the gray pottery, the discreteness of its thermal reactions is significantly reduced [50]. On the one hand, relevant studies have shown that black-fired pottery typically exhibits a denser vitrified matrix, fewer pore structures, and lower pore size variability compared to gray-fired pottery, as further discussed in the following Section 3.4. This structural feature endows black pottery with both good mechanical strength and thermal stability. On the other hand, this is related to its more uniform reduction firing process, which enables the full conversion of Fe2O3 to Fe3O4 and promotes liquid-phase sintering. The different types of utensils from the Biting Site (Figure 11d) exhibit obvious differentiation in thermal behavior: the peak temperatures of jars and ding tripods in the high-temperature region are 1280.6 °C and 1245.4 °C, respectively, while those of basins and bowls are 1180.0 °C and 1149.2 °C, respectively.
In comparison, the peak temperatures of jars and ding tripods are significantly higher than those of basins and bowls. On the one hand, this difference may be attributed to the functional requirements of the vessel types (cooking utensils need to resist thermal shock, while containers focus on being lightweight); on the other hand, it is also plausible that these characteristics reflect thermal exposure during prolonged use over fire rather than differences in initial firing conditions. For cooking utensils, high-calcium raw materials and fluxes such as MgO may be incorporated to influence the sintering behavior and promote vitrification at lower firing temperatures through fluxing effects. It should be noted that the TGA-DTA data serve only as supplementary observations rather than primary evidence for determining firing temperatures or mineral phases. For more accurate investigation of the firing temperatures of archaeological ceramics in future studies, integration with thermal expansion analysis is recommended.

3.4. Microstructural Characteristics

3.4.1. Dazhuzhuang Site

SEM-EDS, referring to the combined application of scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), was employed to observe microstructural features and obtain elemental composition at the microscale. In this study, SEM-EDX was primarily used for qualitative and semi-quantitative analysis of microstructural characteristics, such as matrix homogeneity, pore distribution, and inclusion types.
Figure 12 shows the SEM images of the Dazhuzhuang Site. The types of artifacts in shown in Figure 12a–f are a storage jar, yan leg, handle, ding leg, cup, and basin, in sequence. In terms of pottery quality, all are fine-grained gray pottery, except that the ding leg is fine-grained brown pottery. As shown in Figure 12, clay matrix, clay aggregates, and incompletely melted clay platelets are generally present within the matrix, exhibiting typical characteristics of the Longshan Culture. Different vessel types present obvious technological differences in microstructure. It can be seen from the figures that the microstructures of the storage jar (Figure 12a), yan leg (Figure 12b), and ding leg (Figure 12d) all show fold-like aggregates, but there are still differences. The overall arrangement of clay platelets in the storage jar is relatively orderly, but there are large pores inside. The internal structure of the yan leg is uniform and dense. Compared with the storage jar and yan leg, although the inside of the ding leg also shows fold-like aggregates, its matrix structure is denser. It can be seen from Figure 12c that a large number of regular plate-like products are present inside the handle, which are arranged within the internal structure of the matrix in a stacking or intercalation form. It is found from Figure 12e that there are a large number of plate-like products in the microstructure of the cup, which exist in the matrix in a piled manner, and a large number of particles or tiny flake particles are observed around them. It can be observed from Figure 12f that a large number of platelet-like products are piled on the surface of the matrix within the basin, but the product sizes vary significantly and the shapes are irregular.
In summary, these differences in microstructure reflect the differentiated technological treatments applied by potters at the Dazhuzhuang Site to artifacts with different functions: cooking utensils (ding legs, and yan legs) emphasize structural compactness and thermal stability; the production of storage vessels such as jars and basins may have favored manufacturing techniques that enabled the efficient shaping and firing of larger, utilitarian forms—such as coiling and open firing—rather than more labor-intensive processes like fine surface finishing or decorative treatment; accessory-type artifacts (handles and cups) show special raw material processing techniques, suggesting the existence of specialized raw material selection strategies.

3.4.2. Likou Site

Figure 13a–d show SEM images of the Likou Site, with the artifact types in sequence being a pottery lid, an urn, a body sherd, and another body sherd. In terms of pottery quality, all are fine-grained black pottery, except that the pottery lid is fine-grained gray pottery. The microscopic analysis results show that the pottery lid sample (Figure 13a) exhibits a typical porous structure, characterized by a wide distribution range of pore sizes and irregular pore shapes; it is worth noting that the plate-like products in the pottery lid are arranged in a relatively disorderly manner with a low stacking density.
In contrast, fine-grained black pottery samples show significantly different structural characteristics: the urn sample (Figure 13b) displays a highly dense microstructure, composed of well-developed flaky clay minerals closely packed together. These flaky products exhibit an obvious preferred orientation, characterized by tight interlayer bonding and a high proportion of vitrified areas, which is closely related to their reduction firing process (firing temperature of approximately 950 °C). This is confirmed by the significant enhancement of the Fe3O4 characteristic peak in the thermal analysis results. Although the two body sherds (Figure 13c,d) are both fine-grained black pottery, their microstructures are between those of the lid and the urn, presenting a unique honeycomb structure with moderately oriented plate-like products and pores of relatively uniform size.
In summary, the analysis reveals that the porosity of fine-grained black pottery samples (urn and body sherds) is significantly lower than that of the fine-grained gray pottery lid, and the pore size distribution is more concentrated. This structural difference may mainly stem from the following factors: (1) more refined raw material processing; (2) stricter control of the firing process (the transformation of Fe2O3→Fe3O4 in a reducing atmosphere promotes liquid-phase sintering); (3) the use of different admixture formulae.

3.4.3. Biting Site

Figure 14 shows the SEM images of the Biting Site, with the artifact types being a basin, bowl, storage jar, and ding leg, in sequence, all of which are fine-grained gray pottery. It can be seen from the figures that, although all belong to fine-grained gray pottery, microscopic structural analysis reveals significant technological differences. The fine-grained gray pottery basin (Figure 14a) and bowl (Figure 14b) exhibit a unique “block–thin plate” cooperative stacking structure, where the block phase and thin-plate phase form an interlocking network.
Figure 14c,d display the typical microstructural characteristics of the fine-grained gray pottery jar: Figure 14c shows that its matrix structure is dense, with well-crystallized blocky products distributed on the surface, and these products present a typical hexagonal flake morphology; Figure 14d observes a special folded intercalation structure, where flaky products (with a thickness of 100–200 nm) are staggered at an angle of approximately 30° inside the matrix, forming a multi-layer structure of folded intercalations. This unique microstructure enhances performance through the following mechanisms: (1) the folded intercalations effectively hinder crack propagation, contributing to improved fracture toughness; (2) the interlayer nano-pores (10–30 nm) can buffer thermal stress, increasing the residual strength retention rate after thermal shock to over 85%.
Figure 14e,f present the microstructural characteristics of the fine-grained gray pottery ding tripod. The interior of the matrix (Figure 14e) is composed of highly oriented plate-like products (with an aspect ratio > 8:1) closely packed together, with clear grain boundaries. XRD analysis indicates that they are mainly transformed phases of illite–montmorillonite mixed-layer minerals; the surface (Figure 14f) is covered with porous flaky products, and this layer, with a thickness of approximately 10–15 μm, is composed of a three-dimensional network of nano-sheets (with a thickness < 100 nm). This gradient structure design of “dense core + porous surface layer” has dual advantages: (1) the dense matrix provides high compressive strength; (2) the porous surface layer can not only act as a thermal barrier coating but also release thermal stress during the firing process through pores, reducing the thermal cracking rate of ding tripod products at high temperatures.

4. Conclusions

This study adopted techniques such as X-ray fluorescence spectroscopy (XRF), thermal analysis (TGA), and scanning electron microscopy (SEM) to conduct a systematic scientific and technological analysis of pottery unearthed from three Longshan Culture sites—Dazhuzhuang, Likou, and Biting—in the Hui River basin of Yongcheng, Henan. Combining archaeological typology with materials science research methods, a systematic interdisciplinary study was carried out on the pottery from these three Longshan Culture sites in the Yongcheng area, leading to the following key conclusions:
(1) Raw material selection and regional technical characteristics: The Dazhuzhuang Site preferred clay with low aluminum and high silicon content; the Likou Site utilized kaolinitic clay with high aluminum and low iron content; and the Biting Site, located between the two, had diverse sources of raw materials. Such differences reflect the differences stemming from the use of locally available clays for developing local resources and technical traditions among different settlements during the Longshan Culture period.
(2) Technological standardization and functional differentiation: The chemical compositions (e.g., MgO and Na2O) and microstructures of pottery from the Likou Site exhibit high uniformity, indicating a standardized production model. In contrast, the Dazhuzhuang and Biting Sites show obvious chemical dispersion, which may be related to the differentiated formulations of multifunctional pottery (cooking utensils, storage vessels, etc.). For example, the microstructure of cooking utensils (ding tripods) from the Biting Site features a gradient design of a dense core and a porous surface layer, which is specifically optimized for thermal stability.
(3) Using oxide concentrations as observational variables, a one-way ANOVA and significance analysis were conducted to evaluate compositional variability among the pottery samples from the Dazhuzhuang, Likou, and Biting Sites in the Hui River basin of Yongcheng. The results indicate that, with the exception of K2O, which showed relatively low statistical significance, the contents of SiO2, Al2O3, MgO, CaO, Na2O, and TiO2 exhibit significant differences across the three sites. Fe2O3 also displays a certain degree of statistical distinction, though to a lesser extent. These findings suggest notable heterogeneity in raw material composition or technological choices among these sites.
(4) Refined control of firing technology: Thermal analysis (TGA) and microstructural (SEM) results indicate that black pottery (such as the urn from the Likou Site) forms a dense vitrified structure through reduction firing, while gray pottery lids are made porous and lightweight by adding calcareous materials [51,52,53].
(5) Although certain spatial distribution motifs in chemical composition and microstructural features—such as the concentration of high-iron ceramics at the Biting Site and the relatively standardized pottery production at the Likou Site—may offer preliminary indications of localized differences in resource use and ceramic production practices, the current dataset is insufficient to support definitive conclusions about organized production systems or the social division of labor. To substantiate such interpretations, additional multidisciplinary evidence is required, including petrographic analysis, spatial analysis of production-related features, and integration with broader archaeological context.

Author Contributions

Conceptualization, L.X. and G.Z.; methodology, L.X. and G.Z.; validation, L.X. and G.Z.; formal analysis, G.Z., L.X. and Y.L.; investigation, J.L., Y.G., Y.Z. and Y.L.; data curation, L.X. and J.L.; writing—original draft preparation, L.X.; writing—review and editing, L.X., G.Z., Y.G. and Y.Z.; funding acquisition, L.X. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Natural Science Foundation of Henan (grant number 242300421462), the Science and Technology Development Fund of the Yellow River Institute of Hydraulic Research (202112), and the Henan Provincial Special Fund for Cultural Heritage Conservation (Yu Wen Wu Han [2021] No. 114).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The original contributions presented in the study are included in the article; further inquiries can be directed to the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. Schematic map of site distribution locations.
Figure 1. Schematic map of site distribution locations.
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Figure 2. Pottery ornamentation rubbings of Longshan Culture period. 1–3. Rope lines; 2,6. Basket lines; 4,5. Basket and string; 7. small square pattern; 8,9. rhombus square pattern [41].
Figure 2. Pottery ornamentation rubbings of Longshan Culture period. 1–3. Rope lines; 2,6. Basket lines; 4,5. Basket and string; 7. small square pattern; 8,9. rhombus square pattern [41].
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Figure 3. The Dazhuzhuang Site Identifiable Objects types figure. 1–3. Storage jar (2023YPDH2:5, 2023YPDH1:4, 2023YPDH1:14); 4. urn (2023YPD②:3); 5. dou (2023YPD①:12); 6. basin (2023YPDH1:13); 7. pottery lid (2023YPD③:1); 8. cup (2023YPDH1:19); 9. ding leg (2023YPDH1:18).
Figure 3. The Dazhuzhuang Site Identifiable Objects types figure. 1–3. Storage jar (2023YPDH2:5, 2023YPDH1:4, 2023YPDH1:14); 4. urn (2023YPD②:3); 5. dou (2023YPD①:12); 6. basin (2023YPDH1:13); 7. pottery lid (2023YPD③:1); 8. cup (2023YPDH1:19); 9. ding leg (2023YPDH1:18).
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Figure 4. Analyzed pottery specimens from the Longshan Culture period at the Dazhuzhuang Site. 1. Storage jar (2023YPDH1:1); 2. yan leg (2023YPDH1:23); 3. handle (2023YPDH1:17); 4. ding leg (2023YPDH1:21); 5. storage jar (2023YPDH1:9); 6. storage jar (2023YPDH1:4); 7. storage jar (2023YPDH1:5); 8. cup (2023YPDH1:19); 9. basin (2023YPDH1:13); 10. basin (2023YPDH1:12); 11. basin (2023YPDH1:11).
Figure 4. Analyzed pottery specimens from the Longshan Culture period at the Dazhuzhuang Site. 1. Storage jar (2023YPDH1:1); 2. yan leg (2023YPDH1:23); 3. handle (2023YPDH1:17); 4. ding leg (2023YPDH1:21); 5. storage jar (2023YPDH1:9); 6. storage jar (2023YPDH1:4); 7. storage jar (2023YPDH1:5); 8. cup (2023YPDH1:19); 9. basin (2023YPDH1:13); 10. basin (2023YPDH1:12); 11. basin (2023YPDH1:11).
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Figure 5. Analyzed pottery specimens from the Longshan Culture period at the Dazhuzhuang Site. 1. Storage jar (2023YPDH1:16); 2. basin (2023YPDH2:12); 3. storage jar (2023YPDH1:5).
Figure 5. Analyzed pottery specimens from the Longshan Culture period at the Dazhuzhuang Site. 1. Storage jar (2023YPDH1:16); 2. basin (2023YPDH2:12); 3. storage jar (2023YPDH1:5).
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Figure 6. Analyzed pottery specimens from the Longshan Culture period at the Biting Site. 1. Basin (2023YXBP⑤:1); 2. bowl (2023YXBP⑤:10); 3. storage jar (2023YXBP⑤:7); 4. storage jar (2023YXBP⑤:21); 5. storage jar (2023YXBP⑤:13); 6. storage jar (2023YXBP⑤:8); 7. storage jar (2023YXBP⑤:14); 8. ding leg (2023YXBP⑤:19).
Figure 6. Analyzed pottery specimens from the Longshan Culture period at the Biting Site. 1. Basin (2023YXBP⑤:1); 2. bowl (2023YXBP⑤:10); 3. storage jar (2023YXBP⑤:7); 4. storage jar (2023YXBP⑤:21); 5. storage jar (2023YXBP⑤:13); 6. storage jar (2023YXBP⑤:8); 7. storage jar (2023YXBP⑤:14); 8. ding leg (2023YXBP⑤:19).
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Figure 7. Biting Site investigation and exploration relics distribution map. Note: K1–K8 are ash pits (garbage pits of ancient human activity).
Figure 7. Biting Site investigation and exploration relics distribution map. Note: K1–K8 are ash pits (garbage pits of ancient human activity).
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Figure 8. Analyzed pottery specimens from the Longshan Culture period at the Likou Site. 1. Urn (2023YHL⑥:1); 2. urn (2023YHL⑥:2); 3. storage jar rim (B6:4); 4. pottery lid (2023YHLH2:2); 5. storage jar body sherd (B6:3).
Figure 8. Analyzed pottery specimens from the Longshan Culture period at the Likou Site. 1. Urn (2023YHL⑥:1); 2. urn (2023YHL⑥:2); 3. storage jar rim (B6:4); 4. pottery lid (2023YHLH2:2); 5. storage jar body sherd (B6:3).
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Figure 9. One-dimensional scatter analysis of XRF data in the Yongcheng area.
Figure 9. One-dimensional scatter analysis of XRF data in the Yongcheng area.
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Figure 10. Three-dimensional scatter plot of chemical compositions of unearthed artifacts from the Hui River basin in Yongcheng.
Figure 10. Three-dimensional scatter plot of chemical compositions of unearthed artifacts from the Hui River basin in Yongcheng.
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Figure 11. Thermal analysis curves of artifacts unearthed from the Hui River basin in Yongcheng.
Figure 11. Thermal analysis curves of artifacts unearthed from the Hui River basin in Yongcheng.
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Figure 12. SEM images of artifacts unearthed from the Dazhuzhuang Site.
Figure 12. SEM images of artifacts unearthed from the Dazhuzhuang Site.
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Figure 13. SEM images of artifacts unearthed from the Likou Site.
Figure 13. SEM images of artifacts unearthed from the Likou Site.
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Figure 14. SEM images of artifacts unearthed from the Biting Site.
Figure 14. SEM images of artifacts unearthed from the Biting Site.
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Table 1. Grouping of the Performance Index tests.
Table 1. Grouping of the Performance Index tests.
Performance IndexSpecimen SizeSpecimen Size
Energy-dispersive X-ray fluorescence (XRF)40 mm × 40 mm × 40 mm36
Thermogravimetric analysis (TGA)40 mm × 40 mm × 40 mm36
Scanning electron microscopy (SEM)40 mm × 40 mm × 40 mm36
Table 2. Results of XRF experimental data for pottery sherds in Yongcheng area (%).
Table 2. Results of XRF experimental data for pottery sherds in Yongcheng area (%).
SiteStatistical MeasuresSiO2Al2O3Fe2O3K2OMgOCaONa2OTiO2
Dazhuzhuang
Site		Sample Size4545454545454545
Average67.9316.965.743.491.601.491.140.75
Maximum71.0718.837.073.771.801.811.310.80
Minimum64.9815.185.082.901.331.190.950.71
Standard Deviation1.190.780.580.260.110.160.080.02
Likou SiteSample Size1515151515151515
Average67.1017.785.693.391.711.751.150.81
Maximum67.9718.116.263.601.912.221.270.83
Minimum65.9317.375.023.011.581.461.060.78
Standard Deviation0.680.230.450.200.100.280.060.01
Biting SiteSample Size2424242424242424
Average67.2917.365.983.491.721.411.250.81
Maximum69.0118.087.114.321.981.811.520.93
Minimum65.1915.885.283.111.410.840.960.70
Standard Deviation1.300.620.590.340.190.280.160.06
ANOVAF-value4.119.081.760.797.9011.129.0936.70
Significance0.020.000.180.460.000.000.000.00
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Xia, L.; Zhang, G.; Li, J.; Geng, Y.; Zhao, Y.; Li, Y. Raw Material and Technological Analysis of Longshan Culture Pottery from the Hui River Basin, Yongcheng, Henan. Heritage 2025, 8, 342. https://doi.org/10.3390/heritage8090342

AMA Style

Xia L, Zhang G, Li J, Geng Y, Zhao Y, Li Y. Raw Material and Technological Analysis of Longshan Culture Pottery from the Hui River Basin, Yongcheng, Henan. Heritage. 2025; 8(9):342. https://doi.org/10.3390/heritage8090342

Chicago/Turabian Style

Xia, Linyu, Ge Zhang, Jialing Li, Yufan Geng, Yongtao Zhao, and Yinhong Li. 2025. "Raw Material and Technological Analysis of Longshan Culture Pottery from the Hui River Basin, Yongcheng, Henan" Heritage 8, no. 9: 342. https://doi.org/10.3390/heritage8090342

APA Style

Xia, L., Zhang, G., Li, J., Geng, Y., Zhao, Y., & Li, Y. (2025). Raw Material and Technological Analysis of Longshan Culture Pottery from the Hui River Basin, Yongcheng, Henan. Heritage, 8(9), 342. https://doi.org/10.3390/heritage8090342

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