In the present study two analytical methods are applied to characterize chert artefacts and raw materials from northeastern Bulgaria (Ludogorie region): petrographic observation and laser ablation inductively coupled plasma mass spectrometry). Archaeological samples from 12 Chalcolithic sites from Bulgaria are analyzed as well as raw material from 6 outcrops in northeastern Bulgaria are identified and documented during a survey in 2012 when many raw material samples were collected. The chert raw material mostly occurs in various Quaternary secondary deposits, originating from destruction and disintegration of the Lower Cretaceous (Aptian) limestones in the area. The paper is aimed at tracing the provenance of the artefacts based on their petrographic characteristics and geochemical composition. The archaeological evidence shows a wide distribution of the Ludogorie chert throughout the country.On the basis of micropetrographic observations, Gurova and Nachev (2008) described two main chert types (Ravno and Kriva Reka). Our petrographic study confirmed the previous results and an additional chert type was distinguished, originating from primary and secondary deposits (quarries in Koprivetz and Krasen villages) and is represented by silicified limestones (bioclastic-peloidal packstones or grainstones). It is noteworthy that the first two types of chert were largely used for prehistoric artefact manufacturing while the last one is not attested among studied assemblages at all.

Geochemical features of the deep-sea sediments from a high polymetallic nodule area in the eastern part of the Clarion-Clipperton Fractures Zone (CCZ), NE Pacific were studied. Box-corer samples from six stations in individual depth layers 0–3, 3–5, 5–10, 10–20 cm were collected from 4300–4500 m depth. The deep-sea sediments were classified as clayey-siliceous oozes according to the mineral and grain-size analyses. The chemical composition of the studied samples is compatible with that of pelagic sediments. Manganese content varies from 0.16% to 0.70% being the highest in the geochemically active layer (top 7–12 cm) and decreases with depth. The Mn/Fe ratio, Ba, Co, Ni and Cu have the highest values in the first (0–3) and second (3–5) layers and decrease with depth. REE range is 195.84–357.79 ppm showing low variation between the layers. PAAS-normalized REE patterns show significant enrichment of MREE and HREE with strong negative Ce anomaly and weak positive Eu and Y anomalies. The geochemical characteristics of the studied sediments infer polygenic origin. The redox sensitive oxides and barite presense, Eh values and negative Ce anomaly, indicate oxidizing environment of sediment formation.

The Elatsite–Chelopech ore field in the northern part of the Panagyurishte district in Central Bulgaria comprises numerous spatially associated porphyry copper and epithermal gold deposits and prospects. In addition to the mineralization and alteration features, trace elements, lead and sulfur isotope signatures of sulfide minerals from porphyry copper, base metal and gold-base metal deposits/prospects have been studied. LA-ICP-MS analyses of pyrite, arsenopyrite and sulfosalt minerals validate them as major carriers for Au, Ag, Sb, Se and Co. Pyrite from the three types of mineralization has specific geochemical characteristics. Pyrite from the porphyry copper deposits/prospects has generally lower total trace element content compared to pyrite from the epithermal prospects, except for Se, Co and Ni. Pyrite from the base metal and gold-base metal veins is enriched in As, Au, Ag, Sb and Pb. In pyrite from the base metal deposits, Co and Ni have contents comparable to the pyrite from the porphyry copper deposits, while pyrite from the gold-base metal veins shows lower Co and Ni. Arsenopyrite from these deposits shows similar features. Similarly, sphalerite from the gold-base metal veins also has lower Co content compared to sphalerite from the base metal veins but higher In and Cu contents. In addition to the close spatial relationships between the Elatsite and Gorna Kamenitsa porphyry Cu deposits and Negarstitsa-West and Dolna Kamenitsa base metal prospects, as well as similarities in the mineralization and alteration styles, the lead isotopic (²⁰⁶Pb/²⁰⁴Pb = 18.61–18.68, ²⁰⁷Pb/²⁰⁴Pb = 15.64–15.65 for porphyry and ²⁰⁶Pb/²⁰⁴Pb = 18.55–18.67, ²⁰⁷Pb/²⁰⁴Pb = 15.64–15.68 for base metal) and sulfur isotopic (δ³⁴S values of −3 to +1‰ for porphyry and δ³⁴S values of −1.7 to +3.5‰ for base metal) signatures of sulfides support the idea of a genetic link between these two types of deposits. The porphyry and base-metal mineralization result from a common major ore-forming event during the Late Cretaceous, corresponding to deep/higher-temperature and shallower/distal/lower-temperature environments, respectively. In particular, more radiogenic lead (²⁰⁶Pb/²⁰⁴Pb = 18.41–18.47, ²⁰⁷Pb/²⁰⁴Pb = 15.67–15.76) and slightly different sulfur isotopic compositions (δ³⁴S values of +3.5 to +10.6‰) of sulfides from the distal gold-base metal veins of Kordunsko Dere, Svishti Plaz and Shipkite might be a consequence of the interaction of the ore-forming fluids with an external older crustal and isotopically positive S source. Alternatively, a different fluid source/event for the formation of these gold-base metal veins may be suggested.

Deep-sea Fe-Mn polymetallic nodules formed nowadays at the deep-sea ocean floor were evaluated as promising critical raw materials (CRMs). Here, we report results of polymetallic nodules from the H22_NE block of the Interoceanmetal (IOM) exploration area in the eastern part of the Clarion–Clipperton Zone (CCZ), NE Pacific Ocean. The polymetallic nodules were studied with X-ray Diffraction, Raman spectroscopy, SEM-EDS, and LA-ICP-MS (bulk nodules and in situ nodule layers). Additionally, we combine geochemical data of polymetallic nodules with the previously reported data of pore waters and sediments from six stations. Our study aims to define the mineral composition and determine the content of CRMs in the polymetallic nodules and to assess the main factors controlling metal deposition and nodule enrichment in some CRMs. Mn content and the Mn/Fe ratio of the nodules classify them mostly as mixed hydrogenetic–diagenetic type. They are also enriched in Ni, Cu, Co, Zn, Mo, W, Li, Tl, and REE. The in situ REE patterns exhibit MREE and HREE enrichment and a variable Ce anomaly that argues for a changing oxic/suboxic environment and periodically changing of diagenetic and hydrogenetic nodule growth. The results of the joint study of the bottom sediments, pore waters, and polymetallic nodules show a complexity of processes that influence the formation of these deposits. The changing oxic and anoxic conditions are well documented in the chemistry of the nodule layers. Probably the most important controlling factors are sedimentation rate, bioturbation, adsorption, desorption, and oxidation. In addition, growth rates, water depth variations, electro-chemical speciation, phosphatization, and the structures of the Fe-Mn adsorbents are also considered. The polymetallic nodule deposits in the IOM contract area are estimated for future mining for Ni, Cu, Co, and Mn resources. They, however, contain additional metals of economic importance, such as REE and other trace elements (referred to as CRMs) that are potential by-products for metal mining. They can significantly increase the economic importance of exploited polymetallic nodules.