After carefully removing the glasses using a tungsten drill bit, the porcelain bodies, underwent grinding using an electric agate mortar, and the resulting powders were subsequently dried at 80°C for 24 hours. These prepared samples, amounting to 200 mg each, were then subjected to a two-hour irradiation process within the Triga Mark III nuclear reactor located at the Nuclear Center of Mexico. This irradiation took place under the influence of a thermal neutron flux measuring 1\(\times\)10\(^{13}\) cm\(^{-2}\) s\(^{-1}\). Reference materials, specifically SRM 278—Obsidian Rock from the National Institute of Standards and Technology and Ancient Chinese Ceramic (Shakhashiro et al., 2006) were concurrently irradiated alongside the archaeological samples.

Subsequent measurements of both the samples and reference materials occurred after a decay period of 10–12 days, with each measurement lasting 2 hours. The gamma detection system consisted of an HPGe detector (GEM 40190, ORTEC\(®\)) boasting a resolution of 1.7 keV at the 1.33 MeV gamma peak of \(^{60}\)Co. This detector was coupled to a multi-channel analyzer (MCA, MAESTRO-32, ORTEC\(®\)). All recorded radioactivity values underwent meticulous correction, accounting for half-life and decay time considerations.

Under these conditions, 16 elements (Sc, Cr, Fe, Co, Rb, Sb, Cs, La, Ce, Eu, Tb, Yb, Lu, Hf, Th, and U) were examined. To ensure accuracy, concentrations of Ce and La were adjusted, taking into consideration the presence of fission products from \(^{235}\)U (Glascock et al., 1986; Ribeiro Jr. et al., 2013). Lanthanum exhibited negligible discrepancies, while cerium demonstrated minor variations due to the low uranium content in the samples.

The Missouri University Research Reactor (MURR) procedures refer to the use of a specific software, which is written in the GAUSS language and provided by that institution. This software serves to perform statistical analyses, calculating probabilities of sample membership in different clusters via Mahalanobis distance. Elemental concentrations undergo a logarithmic scale transformation for analysis. Additionally, the software facilitates visual representation by generating principal component diagrams, effectively clustering artifacts. Furthermore, it aids in illustrating vectors representing elemental concentrations that delineate cluster boundaries (Glascock, 2021; Guerrero-Rivero et al., 2020; Terreros-Espinosa et al., 2021).

Results and discussion

The principal component diagram of the 60-sample assemblage established four separated clusters and two un-clustered samples, shown in Figure 2 and in detail in Table 1. Table 2 displays the mean values and standard deviations of the porcelain bodies.

Among the studied porcelain fragments, distinct compositions emerged in various clusters, Figure 2.

Cluster C1, comprising 28 samples, stood out for its elevated levels of Co, Rb, Sb, and Cs while containing lower concentrations of Cr, rare earth elements (REEs), and Th.

A separate group, Cluster C2, consisting of 10 Japanese samples, was characterized by notably reduced levels of Cr, Co, Rb, and Cs.

Cluster C3, with 9 samples, exhibited low Fe and Sb levels but surprisingly elevated La concentrations, nearly twice that of Ce a departure from Chinese porcelain patterns.

The iron content significantly influences porcelain color; lower concentrations yield a purer white shade in oxidizing firing, while higher levels darken the paste in reducing firing (Li et al., 2011; Li et al., 2011).

Cluster C4, with 11 samples, was characterized by markedly high concentrations of iron and, in contrast, white C3 exhibited a low iron level.

For a visual representation of these clusters and un-clustered samples, refer to Figures 8(a)-(f), which features some photographs.

(a)	(b)	(c)
(d)	(e)	(f)

The analytical results were compared across data obtained from various porcelain kilns and periods. These included:

1. samples from Dapu, Jingdezhen, and Zhangzhou kilns (Zhu et al., 2016).

2. 23 specific Chinese samples (Dias et al., 2013).

3. Chinese artifacts from the Ming, Late Qing, and Qing dynasties (Tripati et al., 2017).

4. Specimens from Fengdongyan kilns spanning the Early Ming, Middle Ming, and Ming dynasties (Li et al., 2016).

5. Artifacts from the Yuan and Ming dynasties (Xie et al., 2009).

6. Four distinct groups from the Song Dynasty (Niziolek, 2015).

7. Five groups traced back to the Zhangzhou kiln (Ma et al., 2012).

Figure 9 illustrates the principal component diagram constructed with data from 60 specimens, juxtaposed with existing literary data. The figure displays ellipses corresponding to the four clusters alongside both un-clustered samples. Two ellipses include data points from the literature correlating with the information within those ellipses, while the other two ellipses lack literature data, including those of the un-clustered samples.

*\(^1\)Data of the present study. *\(^2\)Adapted from the following studies: *\(^3\)“Tracing the origin of blue and white Chinese Porcelain ordered for the Portuguese market during the Ming dynasty using INAA” by Dias et al., 2013, Journal of Archaeological Science, 40, 3046-3057. *\(^4\)“The provenance of export porcelain from the Nan’ao One shipwreck in the South China” by Zhu et al., 2016, 2016, Antiquity, 90(351), 798-808. *\(^5\)“Chemical composition and provenance of Chinese porcelain shards recovered from Old Goa, west coast of India” by Tripati et al., 2017, Journal of Archaeological Science: Reports, 14, 467-478. *\(^6\)“Provenance of Zhangzhou export blue-and-white and its clay source” by Ma et al., 2012, Journal of Archaeological Science, 39(5), 1218-1226. *\(^7\)“The provenance of export porcelain from the Nan’ao One shipwreck in the South China Sea” by Zhu et al., 2016, Antiquity, 90(351), 798-808.

The elemental composition of C1 bears a striking resemblance to the data associated with blue-and-white porcelains crafted in the renowned Jingdezhen kilns throughout the Ming, Qing, and Late Qing dynasties (Dias et al., 2013; Tripati et al., 2017; Zhu et al., 2016), see Figure 9. Moreover, the findings from C1 align significantly with the white Jingdezhen porcelain records from the Ming Dynasty, as detailed by Xie et al., 2009, exhibiting close correlation across nearly all analyzed elements, apart from some disparities, including lower Fe content and the absence of recorded Cr and Sb concentrations. This comparative analysis, drawn from existing literature, strongly implies that the porcelain specimens represented by C1 were likely crafted within the confines of the Jingdezhen kilns during either the Ming (1368-1644 AP) or the Qing (1644-1912 AP) Dynasties.

The comparison between C2 (Japanese porcelain) and existing literature data was confined to a limited number of elements. In the examination of Japanese porcelain using pXRF (Hsieh & Fischer, 2019), the Fe, Rb, and Th levels closely mirrored those observed in our current research.

While the Fe content values documented for Arita kiln porcelain (Byungsun, 1999) resembled those of C2, there were no other matching elements between their study and ours. Therefore, these data were not included in Figure 9.

The elemental composition of the blue-and-white porcelain in C4 exhibited a significant resemblance to the Zhangzhou porcelain data reported in previous studies (Ma et al., 2012), Figure 9. In addition, the Fe, Rb, and Th concentrations obtained from the pXRF analysis of Zhangzhou porcelain by Fischer & Hsieh, 2017 were consistent with our findings. Therefore, it is inferred that the C4 samples were produced in the Zhangzhou kilns. On the contrary, there is no matching porcelain data in the existing literature to corroborate the origin (allegedly Zhangzhou) of the un-clustered samples (P50 and P51), leaving their source undetermined.

Cluster C3 comprises white porcelain pieces characterized by high rare earth element (REE) content and low levels of iron (Fe), resulting in a lack of color in the material. Thus, the white Dehua samples in this collection achieved a particularly pristine white hue. Numerous studies in the literature have examined Dehua porcelain using EDXRF (spectrometry) (Juan et al., 2007; Leung & Luo, 2000; Leung et al., 2000; Li et al., 2011; Li et al., 2011; Zhou et al., 2019). The data from these analyses do not necessarily align with the findings presented in this study using INAA, which is why those data were not included in Figure 4. Interestingly, one of these reports, Li et al., 2011 observed periodic decreases in ferric oxide content in Dehua porcelains across the Yuan (1280–1368 AP), Ming (1368–1644 AP), and Qing Dynasties (1644–1912 AP). Considering the timeline, it is plausible that the C5 specimens, produced in the Dehua kilns during the late Ming and Qing Dynasties, might have reached Mexico City between the late 17th and early 18\(^{th}\) centuries. Several elements in C3 also share similarities with a collection of 11 Dehua and three Jingdezhen porcelain artifacts retrieved from the Java Sea shipwreck dating back to the Song Dynasty (960-1279) (Niziolek, 2015). While this chronology does not agree with New Spain (16\(^{th}\) to 19\(^{th}\) centuries), the chemical composition of the Dehua porcelain pieces does.

Porcelain items from the Ming and Qing dynasties were amassed between the 16\(^{th}\) and 18\(^{th}\) centuries. They were in large quantities acquired by individuals belonging to various European monarchies or the high nobility, who curated splendid collections. These collections were widely regarded as symbols of opulence, authority, and prestige (Tian, 2020).

Historically, the arrival of foreign goods had a transformative effect on the economy, culture, and artistic traditions of people (Tripati et al., 2017). Chinese and Japanese porcelain arrived at Manila port in the Philippines in exchange for silver from New Spain, facilitated by the Nao de China trade route. Subsequently, these goods journeyed to Acapulco, becoming central to a bustling trade fair. From there, they were transported by mule to the capital of New Spain and other cities, including Veracruz, before continuing on to Spain.

Research by Carrera, 1959 illustrates how opulent Chinese items became commonplace in Spanish residences, churches, convents, and other prominent settings. The high cost of porcelain, surpassing that of other ceramics, cemented its status as a symbol of prestige, reflecting social and economic standing. Silver from New Spain played a crucial role in supporting this trade. This is evident throughout the Viceroyalty period (Fournier, 1990; Fournier & Otis Charlton, 2015; Junco & Fournier, 2008). Significantly, the impact of Chinese porcelain designs played a crucial role in shaping the evolution of the Talavera ceramic style in Puebla, among various others. Throughout history, the introduction of foreign goods has had a transformative effect on the economy, culture, and artistic traditions of communities.

According to research by Carrera, 1959 trade between the Philippines and New is, opulent Chinese items became commonplace in Spanish residences, churches, convents, and other prominent places. The steep prices of porcelain, especially, surpassed those of other ceramics, establishing itself as a symbol of prestige for owners, mirroring their social and economic status. Silver from New Spain played a pivotal role in supporting this trade. This pattern was observable across the Viceroyalty period (Fournier, 1990; Fournier & Otis Charlton, 2015; Junco & Fournier, 2008). Significantly, the impact of Chinese porcelain designs played a crucial role in shaping the evolution of the Talavera ceramic style in Puebla, among various others. Throughout history, the introduction of foreign goods has had a transformative effect on the economy, culture, and artistic traditions of communities.

In Mexico, porcelain or other objects have been found and documented that appear in inventories usually with the general qualifier “from China” and the same thing happens in the data of those merchandise that left Veracruz for Spain (Curiel, 2013). Possibly not all these goods were from China, but from other Asian countries; some of these objects may not have arrived via the Nao of China through the Pacific Ocean but instead could be imitations produced in other countries, particularly in Europe, and arrived via Veracruz. Examples of such imitations include ceramics and fine crystals with Asian designs. Hence, it is crucial to conduct research that can help identify the origins of these objects, providing insights into the social and cultural contexts of their creation, irrespective of the time and location. A reliable method for tracing the origins of archaeological materials, such as the porcelains examined in this study, is through precise techniques like neutron activation analysis, which can determine the content of trace elements.

Analysis of the collection’s samples through methods like INAA and statistical analysis unveiled noteworthy differences in their chemical makeup. These discrepancies proved instrumental in pinpointing the origin of the specimens, shedding light on the intricate commercial past of porcelain in New Spain. Such precise archaeometric measurements were essential to achieving this investigative goal.

Conclusions

The blue-and-white pieces in cluster C1 originated from the Jingdezhen kilns during the late Ming (1368–1644 AP) and/or Qing (1644–1912 AP) Dynasties. A separate set of blue-and-white items, Cluster C4, highlighted distinct characteristics divergent from Jingdezhen kiln products, bearing similarities to porcelains crafted in the Zhangzhou kilns. These specimens showed reduced levels of Sb and Cs, but elevated quantities of iron and rare earth elements compared to those originating from the Jingdezhen kilns.

The chemical composition of Japanese blue-and-white porcelain differs from its Chinese counterparts. Specifically, the Japanese pieces exhibit lower levels of cobalt, rubidium, and cesium compared to other blue-and-white porcelain pieces within the same collection. While only a few elements were compared based on available literature data, these specimens originated from the Arita kilns during the 17\(^{th}\) and 18\(^{th}\) centuries.

To the best of our knowledge, prior to this study, no nuclear activation analyses had been conducted on Chinese Dehua or Japanese Arita porcelains. This groundbreaking research unveiled the presence of sixteen chemical elements, primarily in trace amounts, offering valuable insights for the identification of these specific types of porcelain.

Comparatively, the iron content in Dehua white porcelain is notably lower than that found in blue-and-white porcelain. The white porcelain pieces within the current collection are highly likely to have originated from the Dehua kilns and were transported to Viceregal Mexico City during the late Ming and Qing Chinese Dynasties.

The present study provides insight into the trade of consumer goods, specifically porcelain, during the Viceroyalty period in Mexico City. Furthermore, it reinforces the evidence of the continuous and important trade of both China and Japan with New Spain using the Nao of Chine. Other relevant aspect is to offer analytical data on some types of porcelain that were not available until now and that will be useful later for their identification.

Author contributions

E. Terreros-Espinosa participated in: Conceptualization, supervision, and writing. M. Jiménez-Reyes and D. Tenorio participated in: Conceptualization, Formal analysis, Methodology Validation, preparation of the original draft, and editing. S. de la Vega-Doria participated in: Conceptualization and editing.

Conflicts of interest

The authors certify that there is not a commercial or associative interest that represents a conflict of interest in relation to the manuscript.

Acknowledgments

The authors express their gratitude to the Programa de Arqueología Urbana and the Templo Mayor-Programa de Mejora de la Gestión (Instituto Nacional de Antropología e Historia, Mexico) for supplying samples of ancient Chinese and Japanese specimens. The authors appreciate the technical support from Nuclear Reactor staff and Mr. Jesús Muñoz Lujano. Special thanks are extended to the anonymous reviewers for their insightful suggestions for this manuscript.

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