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 distribution of major and trace elements in hydrothermal alteration zones (propylitic, argillic, sericitic and advanced argillic) from the Asarel porphyry copper deposit is studied. Strontium was found to demonstrate the most characteristic behaviour among all studied elements – it is depleted from propylitic, argillic and sericitic rocks and concentrates in advanced argillic rocks where it is included in alunite and APS minerals. Manganese, Co, Ni, Zn, Cs, Y, MREE and HREE are strongly mobile and are depleted with increasing of alteration degree, while Rb concentrates in sericitic rocks. Titanium, Zr, V, Ta, Nb, Th, U and LREE have inert behaviour during alteration. Alunite, APS minerals and rutile are the minerals that control the geochemistry of trace elements in the zones of advanced argillic alteration.

Our study is focused on REE and yttrium (REY) geochemistry of pore waters from core-box sediments. The samples were collected from the 0–5 cm, 10–15 cm, 25–30 cm, and 35–40 cm depth intervals of four stations of the eastern part of block H_22 of IOM license area of the Clarion-Clipperton Fracture Zone, NE Pacific. The REE studies in marine pore fluids were limited by analytical challenges. The pore water analysis we applied is based on a modern, improved analytical technique (ICP-MS, Perkin-Elmer SCIEX Elan DRC-e) with a cross-flow nebulizer and a spectrometer optimized (RF, gas flow, lens voltage) using a quadrupole cell in a DRC (Dynamic Reaction Cell) mode that allowed us to define the whole suite of REE. The ƩREY values of the samples vary from 4.05 μg/l to 106.34 μg/l. The REE content is at least one order of magnitude higher than the oceanic water. We followed the natural variations of La, Lu, Ce, and Y in absolute concentrations for station 3607. Cerium and Y are slightly enriched around the water-sediment interface, while La and Lu are enriched in the deeper layers. PAAS normalized REY patterns show a pronounced negative Ce/Ce* ratio together with a little MREE and HREY enrichment. The relatively “flat” REE patterns are typical for the shallow open ocean and characterize REE released from the organic matter degradation. We assume that the decomposition of and adsorption on organic matter and oxidation conditions are the main factors for REE fractionation in the pore water. The reason for some scatter in our REY data might be linked to bioturbation that has affected the sediment profiles.

The distribution and behaviour of major and trace elements in the main zones of hydrothermal alteration (propylite, sericite and advanced argillic) in the area of Breznik Town have been studied, coupled with the chemical composition of alunite group minerals and their isotope geochemistry. The content of Sr decreases in propylite and especially in sericite rocks, and increases significantly in advanced argillic altered (AAA) rocks, which is connected with the formation of aluminium phosphate-sulphate (APS) minerals. Rubidium has high content in sericitic rocks, whereas the element is almost depleted in AAA rocks. The Rb/Sr ratio increases in sericitic rocks and strongly decreases in AAA rocks. Zirconium, Ti, Cr, V, Ga, Hf, Nb, Ta, Th, U and partially Sn and Ba have comparatively inert behaviour during alteration. Manganese, Zn, Ni, Co, Cs and Y are mobile in different degree, with a trend toward complete extraction in the most altered rocks. Arsenium concentrates in AAA rocks, while Li is concentrated only in kaolinite AAA rocks. LREE are comparatively inert in AAA rocks, while MREE and HREE are very mobile, especially in alunite rocks. Alunite has Na-K composition, with permanent admixtures of Ca, Sr, Ba and LREE. APS minerals themselves are woodhouseite and svanbergite-woodhouseite solid solutions (s.s.). Stable isotopes of alunite are characteristic for magmatic-hydrothermal alunite, whereas δ34S of jarosite is intermediate between δ34S of alunite and sulphides, which confirms its supergene origin. All these features define a high-sulphidation epithermal environment, and a possible porphyry mineralization at deeper part of the system is suggested.

Increase of pollution of surface water and water sediments with hazardous substances (HSs) in the Danube River Basin requires implementation of systematic monitoring and evaluation of the sediment quality. The present study is focused on the ’South Danube’ Test Area (SDTA) that covers parts of the Lower Danube Basin in Romania, Serbia and Bulgaria. The SD area represents an extended region where Danube reaches its largest widths and depths and where pollution (industrial, mining, agricultural, waste etc.) from tributaries and land is supposed to accumulate in the sediments. Sampling of river bottom sediment (BS), suspended sediment (SS) and overbank (floodplain) sediment at two layers (0-5 cm in the top layer (FS TS) and 40-50 cm in the bottom layer (FS BS)), was carried out at 11 locations in order to analyze the concentration and distribution of 8 metal(oid)s (Cu, Pb, Zn, Cd, Hg, Ni, Cr, As), 6 polycyclic aromatic hydrocarbons (PAHs) and 6 pesticides as hazardous substances. The 2013/39/EU Directive and EU Water Framework Directive standards were used to sediment quality assessment. As a whole, the concentrations of heavy metals in the sediments are comparatively low and are around the normal values for soils. On the other hand, some sampling sites and sediment types have high or very high metal concentrations which exceed intervention levels. Our study well recognizes mining pollution sources in the Danube tributaries Borska Reka, Timok, Ogosta, Malak Iskar and Iskar from past and/or recent mining activity. This pollution is limited to the Danube tributaries and around their confluences into the Danube River. The concentration of heavy metals is strongly diluted in the Danube River and drops around normal values. The studied sediments reveal low concentrations of PAHs. Only fluoranthene content is higher in most of the sediment types and sampling sites on the Danube River, but exceeds the interventional level only at Pristol and at Hârșova. Our results show that the sediments in the Danube River are more polluted with PAHs than its tributaries. The identified organic compounds are assumed to be generated during incomplete or low temperature combustion processes or during road transportation and/or the navigation on the Danube River.

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.