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Microbial and hydrothermal venting activities on the seafloor are important for the formation of sediment-hosted stratiform sulfide (SHSS) deposits. Fe isotopic compositions are sensitive to both microbial and hydrothermal activities and may be used to investigate the formation of these deposits. However, to the best of our knowledge, no Fe isotopic studies have been conducted on SHSS deposits. In the Devonian Dajiangping SHSS-type pyrite deposit (389 Ma), South China, laminated pyrite ores were precipitated from exhalative hydrothermal fluids, whereas black shales were deposited during intervals with no exhalation. Pyrite grains from black shales mostly display positive δ56Fe-py (0.01–0.73‰), higher than marine sediments (ca. 0‰), due to pyrite deriving Fe from basinal shuttled Fe(III) (hydr-)oxides and slowly crystallizing in pores of sediments with equilibrium fractionation, except for negative δ56Fe-py (−0.17‰ to −0.24‰) of two samples caused by mixing of Fe from underlain laminated ores. The positive δ34S-py (3.50–24.5‰) of black shales reflect that sulfur of pyrite originated from quantitative reduction of sulfate in closed pores of sediments. In contrast, pyrite grains of laminated ores have negative δ56Fe-py (−0.60‰ to −0.21‰), which were not only inherited from the negative δ56Fe of hydrothermal fluids but also caused by kinetic fractionation during rapid precipitation of a pyrite precursor (FeS) in hydrothermal plumes. These ores have negative δ34S-py (−28.7‰ to −1.82‰), because H2S for pyrite mineralization was produced by bacterial sulfate reduction (BSR) in a sulfate-rich seawater column or shallow sediments. The δ56Fe-py values of laminated ores co-vary positively with δ34S-py and δ13C-carbonate along the ore stratigraphy, with δ13C-carbonate values ranging from −12.0‰ to −2.50‰. However, they correlate negatively with aluminum-normalized total organic carbon (TOC/Al2O3). Organic carbon is thus considered to enhance the production of H2S by BSR activities, increase pyrite precipitation rates and promote the expression of kinetic fractionation of Fe isotopes. Intriguingly, in the ore units with vigorous hydrothermal venting activities, δ56Fe-py, δ34S-py and δ13C-carbonate values display a consistently increasing trend. Such results suggest that venting hydrothermal fluids significantly inhibited the H2S production of BSR, which then reduced the pyrite crystallization rate and decreased the kinetic fractionation of Fe isotopes. Our study reveals that the formation of SHSS deposits relies on H2S from microbial activities and metals from hydrothermal exhalation on the seafloor, but that vigorous exhalation can inhibit microbial activities and thus sulfide precipitation rates. The integrated use of Fe, S, and C isotopes can effectively elucidate these dynamic interactions between hydrothermal venting and microbial activities during the formation of SHSS deposits.

The occurrence of endocrine disrupting chemicals (EDCs) is a major issue for marine and coastal environments in the proximity of urban areas. The occurrence of EDCs in the Pearl River Delta region is well documented but specific data related to Macao is unavailable. The levels of bisphenol-A (BPA), estrone (E1), 17α-estradiol (αE2), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2) were measured in sediment samples collected along the coastline of Macao. BPA was found in all 45 collected samples with lower BPA concentrations associated to the presence of mangrove trees. Biodegradation assays were performed to evaluate the capacity of the microbial communities of the surveyed ecosystems to degrade BPA and its analogue BPS. Using sediments collected at a WWTP discharge point as inoculum, at a concentration of 2 mg l−1 complete removal of BPA was observed within 6 days, whereas for the same concentration BPS removal was of 95% after 10 days, which is particularly interesting since this compound is considered recalcitrant to biodegradation and likely to accumulate in the environment. Supplementation with BPA improved the degradation of bisphenol-S (BPS). Aiming at the isolation of EDCs-degrading bacteria, enrichments were established with sediments supplied with BPA, BPS, E2 and EE2, which led to the isolation of a bacterial strain, identified as Rhodoccoccus sp. ED55, able to degrade the four compounds at different extents. The isolated strain represents a valuable candidate for bioremediation of contaminated soils and waters.

The on-board identification of ore minerals during a cruise is often postponed until long after the cruise is over. During the M127 cruise, 21 cores with deep-seafloor sediments were recovered in the Trans-Atlantic Geotraverse (TAG) field along the Mid Atlantic Ridge (MAR). Sediments were analyzed on-board for physicochemical properties such as lightness (L*), pH and Eh. Selected samples were studied for mineral composition by X-ray powder diffraction (XRD). Based on XRD data, sediment samples were separated into high-, low- and non-carbonated. Removal of carbonates is a common technique in mineralogical studies in which HCl is used as the extraction agent. In the present study, sequential extraction was performed with sodium acetate buffer (pH 5.0) to remove carbonates. The ratio between the highest calcite XRD reflection in the original samples (Iorig) vs its XRD-reflection in samples after their treatment with the buffer (Itreat) was used as a quantitative parameter of calcite removal, as well as to identify minor minerals in carbonated samples (when Iorig/Itreat > 24). It was found that the lightness parameter (L*) showed a positive correlation with calcite XRD reflection in selected TAG samples, and this could be applied to the preliminary on-board determination of extraction steps with acetate buffer (pH 5.0) in carbonated sediment samples. The most abundant minerals detected in carbonated samples were quartz and Al- and Fe-rich clays. Other silicates were also detected (e.g., calcic plagioclase, montmorillonite, nontronite). In non-carbonated samples, Fe oxides and hydroxides (goethite and hematite, respectively) were detected. Pyrite was the dominant hydrothermal mineral and Cu sulfides (chalcopyrite, covellite) and hydrothermal Mn oxides (birnessite and todorokite) were mineral phases identified in few samples, whereas paratacamite was detected in the top 20 cm of the core. The present study demonstrates that portable XRD analysis makes it possible to characterize mineralogy at cored sites, in particular in both low- and high-carbonated samples, before the end of most cruises, thus enabling the quick modification of exploration strategies in light of new information as it becomes available in near-real time.

Limited special education and related services are available for children with autism spectrum disorder (ASD) in Macau, especially those who are educated in general education classrooms. No intervention study has been conducted on these children. This study was conducted to explore the relationship between a board game play intervention and board game play behaviors and social communication of children with ASD educated in general education classrooms in Macau. A repeated measures design was used and the results of this study showed the mean occurrence of unprompted board game play behaviors per session during intervention was not significantly different from that during pre- or post-intervention. The mean occurrence of social communication per session during intervention was significantly higher than that during pre- and post-intervention. These findings suggest a positive relationship existed between the board game intervention used in this study and social communication of children with ASD.

The Mesozoic gold deposits in the North China Craton (NCC) were hosted by the Precambrian basement and Mesozoic intrusions. Thus, most researchers consider that these gold deposits were genetically linked to the Mesozoic intrusions. However, we suggest that a metamorphic devolatilization model provides an alternative based on a combined Fe and in-situ S isotopes study on auriferous pyrites from the Baiyun gold deposit in the NCC. The Triassic Baiyun gold deposit contains the quartz vein and altered rock ores that were developed in the Paleoproterozoic metavolcanic-sedimentary rocks (the Liaohe Group). Our in-situ S isotopic analyses show that pyrites from the quartz vein ores are characterized by negative δ34S values (-10.7 ∼ -5.5‰), while those from the altered rock ores have two distinct groups of δ34S values, one being positive (+13.5 ∼ +16.2‰) and the other negative (-10.6 ∼ -3.0‰). We suggest that pyrite grains with positive δ34S values should be relicts from the host rocks, because they show comparable δ34S values with those from the host rocks schists (+3.3 ∼ +16.1‰). Thus, only the negative δ34S values of pyrites in ores (-10.7 ∼ -3.0‰) and the Fe isotopes of the quartz vein ores (δ56Fe = +0.30 ∼ +0.48‰) can represent the isotopic characteristics of ore-forming fluids at Baiyun. Our study shows that the sulfur were probably from the pyritic volcanic-sedimentary sequences of the Liaohe Group, rather than from magmas. The calculated δ56Fe values of the ore-forming fluids (-0.78 ∼ -0.37‰; pyrite-fluid isotope fractionation) could be modelled in a metamorphic devolatilization model with Fe-species (pyrite&magnetite) of the Liaohe Group as sources. Therefore, our combined S- and Fe- isotope data indicate that the metamorphic devolatilization of the Liaohe Group could account for the genesis of the Baiyun gold deposit.

Hydrothermal activity on mid-ocean ridges is an important mechanism for the delivery of Zn from the mantle to the surface environment. Zinc isotopic fractionation during hydrothermal activity is mainly controlled by the precipitation of Zn-bearing sulfide minerals, in which isotopically light Zn is preferentially retained in solid phases rather than in solution during mineral precipitation. Thus, seafloor hydrothermal activity is expected to supply isotopically heavy Zn to the ocean. Here, we studied sulfide-rich samples from the Duanqiao-1 hydrothermal field, located on the Southwest Indian Ridge. We report that, at the hand-specimen scale, late-stage conduit sulfide material has lower δ66Zn values (−0.05 ± 0.15 ‰; n = 19) than early-stage material (+0.13 ± 0.15 ‰; n = 10). These lower values correlate with enrichments in Pb, As, Cd, and Ag, and elevated δ34S values. We attribute the low δ66Zn values to the remobilization of earlier sub-seafloor Zn-rich mineralization. Based on endmember mass balance calculations, and an assumption of a fractionation factor (αZnS-Sol.) of about 0.9997 between sphalerite and its parent solution, the remobilized Zn was found consist of about 1/3 to 2/3 of the total Zn in the fluid that formed the conduit samples. Our study suggests that late-stage subsurface hydrothermal remobilization may release isotopically-light Zn to the ocean, and that this process may be common along mid-ocean ridges, thus increasing the size of the previously identified isotopically light Zn sink in the ocean.

Despite the levels of air pollution in Macao continuing to improve over recent years, there are still days with high-pollution episodes that cause great health concerns to the local community. Therefore, it is very important to accurately forecast air quality in Macao. Machine learning methods such as random forest (RF), gradient boosting (GB), support vector regression (SVR), and multiple linear regression (MLR) were applied to predict the levels of particulate matter (PM10 and PM2.5) concentrations in Macao. The forecast models were built and trained using the meteorological and air quality data from 2013 to 2018, and the air quality data from 2019 to 2021 were used for validation. Our results show that there is no significant difference between the performance of the four methods in predicting the air quality data for 2019 (before the COVID-19 pandemic) and 2021 (the new normal period). However, RF performed significantly better than the other methods for 2020 (amid the pandemic) with a higher coefficient of determination (R2) and lower RMSE, MAE, and BIAS. The reduced performance of the statistical MLR and other ML models was presumably due to the unprecedented low levels of PM10 and PM2.5 concentrations in 2020. Therefore, this study suggests that RF is the most reliable prediction method for pollutant concentrations, especially in the event of drastic air quality changes due to unexpected circumstances, such as a lockdown caused by a widespread infectious disease.

Air pollution in Macau has become a serious problem following the Pearl River Delta’s (PRD) rapid industrialization that began in the 1990s. With this in mind, Macau needs an air quality forecast system that accurately predicts pollutant concentration during the occurrence of pollution episodes to warn the public ahead of time. Five different state-of-the-art machine learning (ML) algorithms were applied to create predictive models to forecast PM2.5, PM10, and CO concentrations for the next 24 and 48 h, which included artificial neural networks (ANN), random forest (RF), extreme gradient boosting (XGBoost), support vector machine (SVM), and multiple linear regression (MLR), to determine the best ML algorithms for the respective pollutants and time scale. The diurnal measurements of air quality data in Macau from 2016 to 2021 were obtained for this work. The 2020 and 2021 datasets were used for model testing, while the four-year data before 2020 and 2021 were used to build and train the ML models. Results show that the ANN, RF, XGBoost, SVM, and MLR models were able to provide good performance in building up a 24-h forecast with a higher coefficient of determination (R2) and lower root mean square error (RMSE), mean absolute error (MAE), and biases (BIAS). Meanwhile, all the ML models in the 48-h forecasting performance were satisfactory enough to be accepted as a two-day continuous forecast even if the R2 value was lower than the 24-h forecast. The 48-h forecasting model could be further improved by proper feature selection based on the 24-h dataset, using the Shapley Additive Explanations (SHAP) value test and the adjusted R2 value of the 48-h forecasting model. In conclusion, the above five ML algorithms were able to successfully forecast the 24 and 48 h of pollutant concentration in Macau, with the RF and SVM models performing the best in the prediction of PM2.5 and PM10, and CO in both 24 and 48-h forecasts.

Employees work long hours in an environment where the ambient air quality is poor, directly affecting their work efficiency. The concentration of particulate matters (PM) produced by the interior renovation of shopping malls has not received particular attention in Macao. Therefore, this study will investigate the indoor air quality (IAQ), in particular of PM2.5, in large-scale shopping mall renovation projects. This study collected on-site PM data with low-cost portable monitoring equipment placed temporarily at specific locations to examine whether the current control measures are appropriate and propose some improvements. Prior to this study, there were no measures being implemented, and on-site monitoring to assess the levels of PM2.5 concentrations was non-existent. The results show the highest level of PM2.5 recorded in this study was 559.00 μg/m3. Moreover, this study may provide a reference for decision-makers, management, construction teams, design consultant teams, and renovation teams of large-scale projects. In addition, the monitoring of IAQ can ensure a comfortable environment for employees and customers. This study concluded that the levels of PM2.5 concentration have no correlation with the number of on-site workers, but rather were largely influenced by the processes being performed on-site.

Statistical methods such as multiple linear regression (MLR) and classification and regression tree (CART) analysis were used to build prediction models for the levels of pollutant concentrations in Macao using meteorological and air quality historical data to three periods: (i) from 2013 to 2016, (ii) from 2015 to 2018, and (iii) from 2013 to 2018. The variables retained by the models were identical for nitrogen dioxide (NO2), particulate matter (PM10), PM2.5, but not for ozone (O3) Air pollution data from 2019 was used for validation purposes. The model for the 2013 to 2018 period was the one that performed best in prediction of the next-day concentrations levels in 2019, with high coefficient of determination (R2), between predicted and observed daily average concentrations (between 0.78 and 0.89 for all pollutants), and low root mean square error (RMSE), mean absolute error (MAE), and biases (BIAS). To understand if the prediction model was robust to extreme variations in pollutants concentration, a test was performed under the circumstances of a high pollution episode for PM2.5 and O3 during 2019, and the low pollution episode during the period of implementation of the preventive measures for COVID-19 pandemic. Regarding the high pollution episode, the period of the Chinese National Holiday of 2019 was selected, in which high concentration levels were identified for PM2.5 and O3, with peaks of daily concentration exceeding 55 μg/m3 and 400 μg/m3, respectively. The 2013 to 2018 model successfully predicted this high pollution episode with high coefficients of determination (of 0.92 for PM2.5 and 0.82 for O3). The low pollution episode for PM2.5 and O3 was identified during the 2020 COVID-19 pandemic period, with a low record of daily concentration for PM2.5 levels at 2 μg/m3 and O3 levels at 50 μg/m3, respectively. The 2013 to 2018 model successfully predicted the low pollution episode for PM2.5 and O3 with a high coefficient of determination (0.86 and 0.84, respectively). Overall, the results demonstrate that the statistical forecast model is robust and able to correctly reproduce extreme air pollution events of both high and low concentration levels.

The levels of air pollution in Macao often exceeded the levels recommended by WHO. In order for the population to take precautionary measures and avoid further health risks under high pollutant exposure, it is important to develop a reliable air quality forecast. Statistical models based on multiple regression (MR) analysis were developed successfully for Macao to predict the next day concentrations of PM10, PM2.5, and NO2. All the developed models were statistically significantly valid with a 95% confidence level with high coefficients of determination (from 0.89 to 0.92) for all pollutants. The models utilized meteorological and air quality variables based on five years of historical data, from 2013 to 2017. The data from 2013 to 2016 were used to develop the statistical models and data from 2017 were used for validation purposes. A wide range of meteorological and air quality variables were identified, and only some were selected as significant dependent variables. Meteorological variables were selected from an extensive list of variables, including geopotential height, relative humidity, atmospheric stability, and air temperature at different vertical levels. Air quality variables translate the resilience of the recent past concentrations of each pollutant and usually are maximum and/or the average of latest 24-hour levels. The models were applied in forecasting the next day average daily concentrations for PM10, PM2.5, and NO2 for the air quality monitoring stations. The results are expected to be an operational air quality forecast for Macao.

Noise pollution is increasingly present in aquatic ecosystems, causing detrimental effects on growth, physiology and behaviour of organisms. However, limited information exists on how this stressor affects animals in early ontogeny, a critical period for development and establishment of phenotypic traits. We tested the effects of chronic noise exposure to increasing levels (130 and 150 dB re 1 μPa, continuous white noise) and different temporal regimes on larval zebrafish (Danio rerio), an important vertebrate model in ecotoxicology. The acoustic treatments did not affect general development or hatching but higher noise levels led to increased mortality. The cardiac rate, yolk sac consumption and cortisol levels increased significantly with increasing noise level at both 3 and 5 dpf (days post fertilization). Variation in noise temporal patterns (different random noise periods to simulate shipping activity) suggested that the time regime is more important than the total duration of noise exposure to down-regulate physiological stress. Moreover, 5 dpf larvae exposed to 150 dB continuous noise displayed increased dark avoidance in anxiety-related dark/light preference test and impaired spontaneous alternation behaviour. We provide first evidence of noise-induced physiological stress and behavioural disturbance in larval zebrafish, showing that both noise amplitude and timing negatively impact key developmental endpoints in early ontogeny.

Anthropogenic noise can be hazardous for the auditory system and wellbeing of animals, including humans. However, very limited information is known on how this global environmental pollutant affects auditory function and inner ear sensory receptors in early ontogeny. The zebrafish (Danio rerio) is a valuable model in hearing research, including investigations of developmental processes of the vertebrate inner ear. We tested the effects of chronic exposure to white noise in larval zebrafish on inner ear saccular sensitivity and morphology at 3 and 5 days post-fertilization (dpf), as well as on auditory-evoked swimming responses using the prepulse inhibition (PPI) paradigm at 5 dpf. Noise-exposed larvae showed a significant increase in microphonic potential thresholds at low frequencies, 100 and 200 Hz, while the PPI revealed a hypersensitization effect and a similar threshold shift at 200 Hz. Auditory sensitivity changes were accompanied by a decrease in saccular hair cell number and epithelium area. In aggregate, the results reveal noise-induced effects on inner ear structure–function in a larval fish paralleled by a decrease in auditory-evoked sensorimotor responses. More broadly, this study highlights the importance of investigating the impact of environmental noise on early development of sensory and behavioural responsiveness to acoustic stimuli.

Genotoxic effects of dicofol on the edible clam Meretrix meretrix were investigated through a mesocosm experiment. Individuals of M. meretrix, were exposed to environmental concentration (D1 = 50 ng/L) and supra-environmental concentration (D2 = 500 ng/L) of dicofol for 15 days, followed by the same depuration period. DNA damage (i.e., strand breaks and alkali-labile sites) was evaluated at day 1, 7 and 15, during uptake and depuration, using Comet assay (alkaline version) and nuclear abnormalities (NAs) as genotoxicity biomarkers. The protective effects of dicofol against DNA damage induced by ex vivo hydrogen peroxide (H2O2) exposure were also assessed. Comet assay results revealed no significant DNA damages under dicofol exposure, indicating 1) apparent lack of genotoxicity of dicofol to the tested conditions and/or 2) resistance of the animals due to optimal adaptation to stress conditions. Moreover, ex vivo H2O2 exposure showed an increase in the DNA damage in all the treatments without significant differences between them. However, considering only the DNA damage induced by H2O2 during uptake phase, D1 animals had significantly lower DNA damage than those from other treatments, revealing higher protection against a second stressor. NAs data showed a decrease in the % of cells with polymorphic, kidney shape, notched or lobbed nucleus, along the experiment. The combination of these results supports the idea that the clams used in the experiment were probably collected from a stressful environment (in this case Pearl River Delta region) which could have triggered some degree of adaptation to those environmental conditions, explaining the lack of DNA damages and highlighting the importance of organisms’ origin and the conditions that they were exposed during their lives.

Mangroves are a unique group of plants growing along tropical and sub-tropical coastlines, with the ability to remove several types of contaminants such as heavy metals and other persistent organic compounds in coastal waters. However, little attention has been given to the possible role of mangroves in the removal of organochlorinated pesticides (OCPs) from the environment. Used worldwide, these pesticides were banned in the late 80s, withal they can still be quantified in aquatic environments due to their high stability. Moreover, as persistent and lipophilic compounds, OCPs are known for their tendency to bioaccumulate and biomagnify through the food chain, affecting local ecosystems, and potentially human health. This work aimed to investigate the potential benefits of mangrove ecosystems as OCP phytoremediators. For this purpose, a total of seventy-three articles from non-mangrove and mangrove areas around the world were gathered, integrated and re-analysed as a whole. These data include information from four different matrices (water, sediment, benthic fauna and mangrove plants). A common trend of less pesticide contamination in mangrove areas was observed for all the selected matrices. As a complement, average concentrations were discussed considering International Directives, such as the European legislation 2013/39/EU for water policy and the Dutch List together with the International Sediment Quality Guideline, for sediments. Additionally, theoretical risk assessments were also included. Since information regarding OCPs in mangroves ecosystem is very scarce compared to non-mangrove areas, this review provides valuable insights regarding these environments, and the importance of preserving them as a relevant remediation unit.

The extraction of 21 insecticides and 5 metabolites was performed using an optimized and validated QuEChERS protocol that was further used for the quantification (GC–MS/MS) in several seafood matrices (crustaceans, bivalves, and fish-mudskippers). Seven species, acquired from Hong Kong and Macao wet markets (a region so far poorly monitored), were selected based on their commercial importance in the Indo-Pacific region, market abundance, and affordable price. Among them, mussels from Hong Kong, together with mudskippers from Macao, presented the highest insecticide concentrations (median values of 30.33 and 23.90 ng/g WW, respectively). Residual levels of fenobucarb, DDTs, HCHs, and heptachlors were above the established threshold (10 ng/g WW) for human consumption according to the European and Chinese legislations: for example, in fish-mudskippers, DDTs, fenobucarb, and heptachlors (5-, 20- and tenfold, respectively), and in bivalves, HCHs (fourfold) had higher levels than the threshold. Risk assessment revealed potential human health effects (e.g., neurotoxicity), especially through fish and bivalve consumption (non-carcinogenic risk; ΣHQLT > 1), and a potential concern of lifetime cancer risk development through the consumption of fish, bivalves, and crustaceans collected from these markets (carcinogenic risk; ΣTCR > 10–4). Since these results indicate polluted regions, where the seafood is collected/produced, a strict monitoring framework should be implemented in those areas to improve food quality and safety of seafood products.

The key challenge of Unsupervised Domain Adaptation (UDA) for analyzing time series data is to learn domain-invariant representations by capturing complex temporal dependencies. In addition, existing unsupervised domain adaptation methods for time series data are designed to align marginal distribution between source and target domains. However, existing UDA methods (e.g. R-DANN Purushotham et al. (2017), VRADA Purushotham et al. (2017), CoDATS Wilson et al. (2020)) neglect the conditional distribution discrepancy between two domains, leading to misclassification of the target domain. Therefore, to learn domain-invariant representations by capturing the temporal dependencies and to reduce the conditional distribution discrepancy between two domains, a novel Attentive Recurrent Adversarial Domain Adaptation with Top-k time series pseudo-labeling method called ARADA-TK is proposed in this paper. In the experiments, our proposed method was compared with the state-of-the-art UDA methods (R-DANN, VRADA and CoDATS). Experimental results on four benchmark datasets revealed that ARADA-TK achieves superior classification accuracy when it is compared to the competing methods.

Stock movement prediction is one of the most challenging problems in time series analysis due to the stochastic nature of financial markets. In recent years, a plethora of statistical methods and machine learning algorithms were proposed for stock movement prediction. Specifically, deep learning models are increasingly applied for the prediction of stock movement. The success of deep learning models relies on the assumption that massive training data are available. However, this assumption is impractical for stock movement prediction. In stock markets, a large number of stocks do not have enough historical data, especially for the companies which underwent initial public offering in recent years. In these situations, the accuracy of deep learning models to predict the stock movement could be affected. To address this problem, in this paper, we propose novel instance-based deep transfer learning models with attention mechanism. In the experiments, we compare our proposed methods with state-of-the-art prediction models. Experimental results on three public datasets reveal that our proposed methods significantly improve the performance of deep learning models when limited training data are available.

The recently explored inactive Tianzuo hydrothermal field, in the amagmatic segment of the ultraslow-spreading Southwest Indian Ridge (SWIR), is closely associated with detachment faults. In this site, sulfide minerals are hosted by serpentine-bearing ultramafic rocks and include high-temperature (isocubanite, sphalerite, and minor pyrrhotite) and low-temperature (pyrite I, marcasite, pyrite II, and covellite) phases. In this study, trace-element concentrations of isocubanite and pyrite II were used to elucidate mineralization processes in ultramafic rocks hosting sulfides. Results show that isocubanite is enriched in metals such as Cu, Co, Sn, Te, Zn, Se, Pb, Bi, Cd, Ag, In, and Mn, and pyrite II is enriched in Mo and Tl. The marked enrichment in Te, Cu, Co, and In in isocubanite (compared with Se, Zn, Ni, and Sn, respectively) is most likely due to the contribution of magmatic fluids from gabbroic intrusions beneath the hydrothermal field. The intrusion of gabbroic magmas would have enhanced serpentinization reactions and provided a relatively oxidizing environment through the dissolution of anhydrite precipitated previously in the reaction zone, within high temperature and low pH conditions. This might have facilitated the extraction of metals by initial hydrothermal fluids, leading to the general enrichment of most metals in isocubanite. Metals in pyrite II have compositions similar to those of isocubanite, except for strong depletion in magmatically derived Te, Cu, Co, and In. This means that serpentinization processes had a dominating role in pyrite II precipitation as well. The enrichment of pyrite II in Mo and Tl is also indicative of seawater contribution in its composition. The study concludes that serpentinization reactions contribute effectively both to high- and low-temperature sulfide mineralization at Tianzuo hydrothermal field, with gabbroic intrusions further promoting high-temperature sulfide mineralization, providing additional metals, fluids and heat. In contrast, low-temperature sulfide mineralization occurred during the cooling of gabbroic intrusions, with decreasing rates of serpentinization reactions and a significant influence of seawater.

Reaction of ultramafic rocks with seawater and subsequent serpentinization has been considered one of the most important factors controlling the formation of ultramafic-hosted seafloor massive sulfide (UM-SMS) deposits. However, the mineralization processes responsible for these deposits remain poorly understood, in particular because they are less abundant as compared with their basaltic counterparts. In this work, serpentinites with different alteration grades collected at the Tianzuo hydrothermal field (THF), Southwest Indian Ridge, were studied. Mineralogical and chemical analyses were performed in the secondary opaque minerals resulting from serpentinization to understand the role of this process during the formation of UM-SMS deposits. Our results show that these opaque minerals mainly consist of magnetite, hematite, pentlandite, and minor pyrite, suggestive of high but varying oxygen and sulfur fugacities. The hematite is characterized by an enrichment in Mg, Si, Ni, and Co as compared with magnetite. Pentlandite associated with hematite has elevated and consistent Ni contents as compared with that associated with magnetite. These results indicate that breakdown and decomposition of primary silicate and sulfide minerals during serpentinization has controlled the sources of ore-forming materials. Concentrations of Te are variable and show a positive correlation with Ni in pentlandite associated with magnetite or hematite, suggesting that gabbroic intrusions provided additional material to the hydrothermal system. Oxidation and sulfidation conditions are ideal for the formation of trisulfur ion S3− in THF, which can significantly improve the capability of hydrothermal fluids for leaching ore-forming metals from the wall rocks, promoting the formation of THF. In addition of reduced systems, hydrothermal fluids with high oxygen and sulfur fugacities triggered by extensive seawater infiltration can most likely also develop in ultramafic-hosted systems. These results suggest that the areas with well-developed fractures are promising candidates for further exploration of UM-SMS deposits along mid-oceanic ridges.