Direct Mercury Analysis Research Articles

Health-risk assessment of mercury in main market-sold foods in the Pingliang region of Gansu province, China, from 2013 to 2021

In the present study, we analyzed mercury concentrations in 742 samples across five main food categories from 2013 to 2021 using direct mercury analysis (DMA) to understand mercury pollution in major market-sold foods in the Pingliang region of Gansu Province and assess the health risks of mercury dietary exposure in adults. Health risks of adult dietary exposure were assessed through deterministic evaluation. Total mercury content ranged from non-detectable (ND) to 0.13 mg/kg, with a detection rate of 90.70% (673/742), the highest detection rates being in fresh edible mushrooms and nuts. The overall exceedance rate was 0.13% (1/742), with one sample of fresh edible mushrooms exceeding the regulatory limit for total mercury content. Additionally, we incorporated the average mercury content and consumption levels of meat and seafood from regions geographically close to Pingliang, as reported in the Fifth National Total Diet Study, to calculate the Estimated Daily Intake (EDI) by a deterministic evaluation. For adult males, the exposure was 0.120 μg/(kg BW), while for adult females, it was 0.141 μg/(kg BW). Both values are significantly lower than the provisional tolerable weekly intake (PTWI) of 4 μg/(kg BW) established by JECFA in 2010, indicating that the total mercury concentration from food intake does not pose a significant health risk to the residents of the Pingliang area. These findings offer valuable scientific data to inform food safety regulations in the region and can serve as a benchmark for future mercury pollution risk assessments in other locations.

Trace metal transfer to passerines inhabiting wastewater treatment wetlands

Wastewater treatment wetlands are cost-effective strategies for remediating trace metals in industrial effluent. However, biogeochemical exchange between wastewater treatment wetlands and adjacent environments provides opportunities for trace metals to cycle in surrounding ecosystems. The transfer of trace metals to wildlife inhabiting treatment wetlands must be considered when evaluating wetland success. Using passerine birds as bioindicators, we conducted a multi-tissue analysis to investigate the mobilization of zinc, copper, and lead derived from wastewater to terrestrial wildlife in treatment wetlands and surrounding habitat. In addition, we evaluate the strength of relationships between metal concentrations in non-lethal (blood and feathers) and lethal (muscle and liver) sample types for estimation of toxicity risk. From July 2020 to August 2021, 177 passerines of seven species were captured at two wetlands constructed to treat industrial wastewater and two reference wetlands in the coastal plain of South Carolina. Feather, blood, liver, and muscle samples from each bird were analyzed for fourteen metals using inductively coupled plasma mass spectrometry and direct mercury analysis. Passerines inhabiting wastewater treatment wetlands accumulated higher concentrations of zinc in liver, copper in blood, and lead in feathers than passerines in reference wetlands, but neither blood nor feather concentrations were correlated with internal tissue concentrations. Of all the detected metals, only mercury in the blood showed a strong predictive relationship with mercury in internal tissues. This study indicates that trace metals derived from wastewater are bioavailable and exported to terrestrial wildlife and that passerine biomonitoring is a valuable tool for assessing metal transfer from treatment wetlands. Regular blood sampling can reveal proximate trace metal exposure but cannot predict internal body burdens for most metals.

Human health risk assessment of mercury in highly consumed fish in Salvador, Brazil

This work reports assessing risks to human health resulting from mercury levels in sardines (Sardinella brasiliensis), which have been highly consumed by the low-income population from Salvador, Brazil. Mercury was determined using the Direct Mercury Analysis (DMA) in fifty-one commercially acquired samples in seventeen neighborhoods. The mercury content on a wet basis ranged from 0.023 to 0.083 μg g−1 for an average value of 0.039 μg g−1. The estimated weekly intake (EWI), target hazard quotient (THQ), and maximum safe consuming quantity (MSCQ) were used in the toxicological assessment, and all these indices denoted that this food does not pose any risks to the human health of the population that consumes it. The development of this work was very significant because most sardines sold in Salvador originate from Todos os Santos Bay, which has a history of mercury contamination.

Evaluating methods for determining mercury concentrations in ancient marine fish and mammal bones as an approach to assessing millennial-scale fluctuations in marine ecosystems

Millennial-scale datasets of heavy metals in biota are difficult to obtain but are important for determining patterns and underlying drivers of toxicant concentrations. This is particularly important to better discriminate contemporary natural and anthropogenic sources. Globally mercury is a contaminant of concern. Post-industrial increases in mercury in arctic biota have been documented and monitoring of Steller sea lions (Eumetopias jubatus) in the Aleutian Islands, Alaska, has revealed a high proportion of pups with fur mercury concentrations above thresholds of concern in some regions. As bone is a tissue that is well preserved in archeological middens, it may prove useful for developing long-term mercury data sets under appropriate conditions. The goal of this study was to evaluate methodologies for measuring mercury concentration in Steller sea lion bone using a direct mercury analyzer, considering sample preparation methods and variability among bone tissue types (e.g., compact versus spongy bone). Finally, we directly compare sensitivity and precision of two different direct mercury analyzer models. Based on the methods presented here, direct mercury analysis using the Nippon MA-3000 can quantify small (ppb) quantities of Hg accurately and precisely in 20 to 60mg of bone with minimal specimen processing. The described method is efficient, relatively inexpensive, and requires minimal bone, conserving rare and valuable specimens. Hydrogen peroxide cleaning and collagen extraction were not required, and may be detrimental for optimal Hg quantification in bone. Further, while homogenization of distinct compact and spongy bone did not impact concentration determination, variance of technical replicates was lower improving quantitation precision. Most importantly, significant differences between compact and spongy bone exist within some individual specimen; however, the difference is not consistent and may indicate differential Hg exposure windows influenced by turnover rate of bone types. We conclude bone provides a natural archive for mercury ecosystem dynamics over millennial time scales in regions where appropriate samples are available. Compact bone has lower and less variable [THg] simplifying analysis and interpretation of data; however, the more dynamic concentrations observed in spongy bone should not be dismissed as invaluable due to their variability in [THg]. Comparisons of [THg] between bone type within individual may provide insight into more acute changes in mercury exposure within an individual’s lifetime.

Risk Assessment and Determination of Arsenic and Heavy Metals in Fishery Products in Korea.

The purpose of this study is to quantify several heavy metals (Pb, Cd, Hg, Me-Hg, and metalloid arsenic) contained in Korean fishery products (seven categories, 1186 samples) and assess their health risk. Heavy metals quantification was conducted using inductively coupled plasma mass spectrometry (ICP-MS) and a direct mercury analysis (DMA). The good linearity (R2 > 0.999), limits of detection (1.0-3.2 µg/kg), limits of quantification (3.1-9.6 µg/kg), accuracy (88.14-113.80%), and precision (0.07-6.02%) of the five heavy metals were obtained, and these results meet the criteria recommended by the AOAC. The average heavy metal concentrations of fishery products were in the following order: As > Cd > Pb > Hg > Me-Hg for sea algae, crustaceans, mollusks, and echinoderms, As > Hg > Me-Hg > Pb > Cd for freshwater fish and marine fish, and As > Pb > Cd > Hg > Me-Hg for tunicates. Heavy metal concentrations were lower than MFDS, EU, CODEX, and CFDA standards. In addition, the exposure, non-carcinogenic, and carcinogenic evaluation results, considering the intake of aquatic products for Koreans, were very low. It was concluded that this study will provide basic data for food safety and risk assessment.

Natural and anthropogenic radionuclides concentration with heavy metals analysis of the sediments collected around Novaya Zemlya

The Dispersal profile of the radioisotopes (226Ra, 232Th, 235U, 40K, 137Cs) along with potentially toxic elements (Cd, Co, Cr, Cu, Ni, Pb, V, Zn, and Hg) in the sediments around the Novaya Zemlya was determined. The task was fulfilled with the aid of HPGe gamma spectrometry, inductively coupled plasma optical emission spectroscopy, DMA-80 Direct Mercury Analysis System, X-ray diffraction and statistical tools. At most of the locations, the radionuclides activity was higher than the world average activity concentration for the respective nuclei, 40K being the most abundant. From all the potentially toxic elements detected, Cr and Ni were usually observed on higher levels compared to their background values, indicating the probability of the detrimental biological effects. Thus, the present situation at the studied area might be a threat to the neighboring marine life.

Elemental profiles of swine tissues as descriptors for the traceability of value-added Italian heavy pig production chains

The increasing demand for reliable traceability tools in the meat supply chain has prompted the exploration of innovative approaches that meet stringent quality standards. In this work, 57 elements were quantified by inductively coupled plasma mass spectrometry and direct mercury analysis in 80 muscle and 80 liver samples of Italian heavy pigs to investigate the potential of new tools based on multi-elemental profiles in supporting value-added meat supply chains. Samples from three groups of animals belonging to the protected designation of origin (PDO) Parma Ham circuit (conventionally raised; raised with genetically modified organism (GMO)-free feeds; raised with GMO-free feeds plus the supplementation of omega-3 polyunsaturated fatty acids (n-3 PUFA)) and a fourth group of samples from animals not compliant with the PDO Parma Ham production process were analyzed. Hierarchical cluster analysis allowed for the identification of three macro-clusters of liver or muscle samples, highlighting some inhomogeneities among the target groups. Following SIMCA analysis, better classification models were obtained by using liver elemental profiles (95% correct classification rate), with the highest classification accuracy observed for GMO-free livers (100%). The elements contributing the most to the separation of livers by class membership were La, Ce, and Pb for conventional, Li, Cr, Fe, As, and Sr for GMO-free + n-3 PUFA, and Lu for non-PDO samples. Given these findings, the analysis of the elemental profiles of pig tissues can be regarded as a promising method to confirm the declared pig meat label attributes, deter potential complex fraud, and support meat traceability systems.

Determination and evaluation of the ecological risk of mercury in different granulometric fractions of sediments from a public supply river in Brazil

This work reports the quantification of total mercury in sediments collected in periods with and without rain from the Joanes River, Bahia, Brazil. Determinations were made using Direct Mercury Analysis (DMA), the accuracy of which was confirmed with two certified reference materials. The highest total mercury concentrations were found at the sampling point close to commercial areas and large residential condominiums. On the other hand, the lowest levels were found in the site close to a mangrove region. The geoaccumulation index was applied to the total mercury results, evidencing low contamination in the region studied. The contamination factor showed that of the seven stations investigated, four samples collected in the rainy season showed moderate contamination. The results of the ecological risk assessment were utterly consistent with the contamination factor data. This study showed that the smaller sediment particles concentrate more mercury, corroborating what has been predicted by the adsorption processes.

A simple method for direct mercury analysis in dried blood spots (DBS) samples for human biomonitoring studies

Human exposure to mercury can have serious health effects, especially in vulnerable groups such as children and fetuses. The use of dried blood spot (DBS) samples to collect capillary blood greatly facilitates sample collection and fieldwork, being a less invasive alternative to blood collection by venipuncture, needing a small volume of sample, and does not require specialized medical staff. Moreover, DBS sampling reduces logistical and financial barriers related to transport and storage of blood samples. We propose here a novel method to analyze total mercury in DBS samples in a Direct Mercury Analyzer (DMA) that allow the control of the volume of the DBS samples. This method has shown good results in terms of precision (<6% error), accuracy (<10% coefficient of variation) and recovery (75–106%). The applicability of the method in human biomonitoring (HBM) was demonstrated in a pilot study involving 41 adults aged 18–65. Mercury concentrations of DBS samples from capillary blood collected by finger prick (real DBS samples) were determined in the DMA and compared with those determined in whole blood (venous blood) by ICP-MS, the method usually used in HBM. The sampling procedure was also validated by comparison of real DBS samples and DBS generated artificially in the laboratory by depositing venous samples in cellulose cards (laboratory DBS). There were no statistically significant differences in the results obtained using both methodologies (DMA: Geometric Mean (confidence interval 95%) = 3.87 (3.12–4.79) µg/L; ICP-MS: Geometric Mean (confidence interval 95%) = 3.46 (2.80–4.27) µg/L). The proposed method is an excellent alternative to be applied in clinical settings as screening methodology for assessing mercury exposure in vulnerable groups, such us pregnant woman, babies and children.

Mercury biomonitoring in German adults using volumetric absorptive microsampling

Mercury (Hg) is a global pollutant and a danger to human health. Human biomonitoring of Hg using a dried blood matrix instead of venous blood sampling for exposure assessment is of growing interest. This study aims to develop, validate, and evaluate the application of volumetric absorptive microsampling (VAMS) for Hg biomonitoring in humans. Sampling, drying, and storage conditions were evaluated during method development. Storage in pre-cleaned glass vials after drying for 2 h in a desiccator ensured analyte stability for at least 4 weeks. Sixty-eight paired capillary VAMS and venous blood samples from volunteers in Munich, Germany, were used for method validation. Hg levels in VAMS and venous blood samples were determined by direct mercury analysis. The limits of detection and quantitation for VAMS were 0.18 and 0.61 µg/l, respectively. However, sensitivity could be improved by using two microsamples for analysis instead of one. Hg levels in VAMS samples correlated very well with Hg levels in venous blood samples (R2 = 0.958). Furthermore, VAMS showed a high accuracy (median recovery: 117%) and precision (median relative standard deviation: 8.7%), especially for Hg concentrations above 1.0 µg/l. In fact, accuracy and precision of VAMS improved with increasing Hg concentrations. In conclusion, VAMS in combination with direct mercury analysis is an accurate and viable alternative for human biomonitoring of Hg.Graphical abstract

RETRACTED ARTICLE: Elemental Analysis of Crustaceans by Inductively Coupled Plasma–Mass Spectrometry and Direct Mercury Analysis

We, the Editor, the Authors, and Publisher, have retracted the following article: Nargis Jamila, In Ming Hwang, Yu Min Park, Ga Hyun Lee, Ji Yeon Choi, Naeem Khan, Min Ja Cho, Kyung Su Park & Kyong Su Kim “Elemental Analysis of Crustaceans by Inductively Coupled Plasma—Mass Spectrometry and Direct Mercury Analysis.” Analytical Letters (2017), https://dx.doi.org/10.1080/00032719.2017.1296851 The authors have requested the retraction of their article due to variations in the concentration of the arsenic identified at the data analysis stage, which affected the reported results of the paper and conclusion. Upon realizing this error, the authors brought the issue to the journal Editor and Publisher immediately. There are no concerns regarding research or publishing conduct and the authors have had already resubmitted an updated paper, which has been accepted and published as https://dx.doi.org/10.1080/00032719.2021.1895188 We have been informed in our decision-making by our policy on publishing ethics and integrity and the COPE guidelines on retractions. The retracted article will remain online to maintain the scholarly record, but it will be digitally watermarked on each page as RETRACTED.

Statement of Retraction

This article refers to:RETRACTED ARTICLE: Elemental Analysis of Crustaceans by Inductively Coupled Plasma–Mass Spectrometry and Direct Mercury Analysis

Implementation of mercury biomonitoring in German adults using dried blood spot sampling in combination with direct mercury analysis

Venous blood is a preferred matrix for the determination of total mercury (Hg) in human biomonitoring but has some drawbacks such as the requirement for an uninterrupted cold chain for transport and storage and the need of medical personnel for sample collection. Therefore, we tested and implemented a simpler and less expensive method for measuring Hg in human blood using dried blood spots (DBS). For method development, we investigated the influence of different storage conditions (temperature, storage vessel, time) on DBS samples. For method validation, we compared DBS and venous blood and investigated whether DBS sampling is suitable for measuring Hg in the general population in countries with low Hg exposure such as Germany. Based on our results, we found that pre-cleaned glass tubes were most suitable for storage of DBS samples, as this allowed the samples to remain stable for at least 4 weeks even at high temperatures (40 °C). When comparing venous blood and DBS, a very good correlation (r = 0.95, p < 0.01, Spearman-Rho) and high precision of DBS (mean relative standard deviation 8.2% vs. 7.2% in venous blood samples) were observed. Comparing the recoveries of both matrices in different concentration ranges, the variation of the recoveries decreases with increasing Hg concentration. The mean recoveries also decreased with increasing Hg concentration. Overall, we found comparable results for DBS and venous blood using direct Hg analysis. Furthermore, we demonstrated that DBS are suitable for Hg biomonitoring in the general population in Germany and improved the storage conditions for the DBS.

Essential and toxic elements in sardines and tuna on the Colombian market

ABSTRACT The presence of metals in canned fish has been associated with adverse effects on human health. The aim of this study was to evaluate risk-based fish consumption limits based on the concentrations of eight essential elements and four elements of toxicological concern in sardines and tuna brands commercially available in the Latin American canned goods market. One brand of canned sardines and six of canned tuna were collected and evaluated by ICP-MS and direct mercury analysis. The Hg content was much higher than that previously observed in scientific literature. According to the calculated hazard quotients, all brands may present some risk in terms of this element, especially brand F in which levels up to 3.1 µg/g were measured. Sardine samples surpassed the maximum limits of Mn and As. Stricter quality control in retail chains and industries should be implemented in order to guarantee safe levels in fishery products.

Classification of transformed anchovy products based on the use of element patterns and decision trees to assess traceability and country of origin labelling

Quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) and direct mercury analysis were used to determine the elemental composition of 180 transformed (salt-ripened) anchovies from three different fishing areas before and after packaging. To this purpose, four decision trees-based algorithms, corresponding to C5.0, classification and regression trees (CART), chi-squareautomatic interaction detection (CHAID), and quick unbiased efficient statistical tree (QUEST) were applied to the elemental datasets to find the most accurate data mining procedure to achieve the ultimate goal of fish origin prediction. Classification rules generated by the trained CHAID model optimally identified unlabelled testing bulk anchovies (93.9% F-score) by using just 6 out of 52 elements (As, K, P, Cd, Li, and Sr). The finished packaged product was better modelled by the QUEST algorithm which recognised the origin of anchovies with F-score of 97.7%, considering the information carried out by 5 elements (B, As, K. Cd, and Pd). Results obtained suggested that the traceability system in the fishery sector may be supported by simplified machine learning techniques applied to a limited but effective number of inorganic predictors of origin.

Multi-element signature of cuttlefish and its potential for the discrimination of different geographical provenances and traceability

The measurement and analysis of fifty-two elements by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) and direct mercury analysis were applied to origin discrimination of Italian traditional cuttlefish (Chioggia, Venice lagoon) from Mediterranean and Atlantic samples. A total 68 specimens were analyzed in triplicates to generate 204 mass spectra profiles which were statistically processed by different chemometric techniques. Loading weights from principal component analysis as input for linear discriminant analysis (LW-LDA), stepwise-LDA (S-LDA) and variable influence of projection-partial least square discriminant analysis (VIP-PLS-DA) were used to classify samples while retaining the lowest possible number of key variables. VIP-PLS-DA was found to be the best variable selection-discriminant tool combo since the selected Na–Co–B–K–Cd–V–U–Rb–Ni–Ba–Cu–As–Sr–Mn–Mo–Li–Ca–Mg–Se–Bi–Cs–P–Y elemental pattern allowed the samples to be classified with 100% sensitivity, specificity and accuracy.

Elemental Analysis of Crustaceans by Inductively Coupled Plasma–Mass Spectrometry (ICP-MS) and Direct Mercury Analysis

This study determined the concentrations of toxic metals including As, Cd, Hg and Pb in commonly consumed crustaceans collected from South Korea. The samples were prepared by wet digestion using HNO3 and H2O2 by microwave assisted combustion. For As, Cd, and Pb, inductively coupled plasma–mass spectrometry (ICP-MS) was used. Hg content was determined using gold amalgation direct mercury analysis (DMA). The analytical techniques were validated by determining the correlation coefficients, limits of detection and quantification, coefficients of variance, spiking, and accuracy by analysis of an oyster tissue certified reference material (NIST CRM-1566b). The distribution of toxic metals was determined in whole, muscles, and digestive tracts of crustaceans. Furthermore, to provide information on consumer safety, risk assessment in terms of estimated dietary daily/weekly intake, target hazard quotient, and hazard index values was performed. The concentration (mg/kg) was in decreasing order of As (2.17–6.05) > Cd (0.154–4.57) > Pb (0.033–0.128) > Hg (0.011–0.086). The estimated dietary daily/weekly intake, target hazard quotient, and hazard indices were compared with the standards established by United States Environmental Protection Agency, and Joint Food and Agriculture Organization/World Health Organization Expert Committee on Food Additives and were below the threshold values. The analyzed crustaceans are not expected cause threats to consumers upon normal consumption.

Reaction of Cyanide with Hg0-Contaminated Gold Mining Tailings Produces Soluble Mercuric Cyanide Complexes.

Elemental mercury (Hg0) contamination in artisanal and small-scale gold mining (ASGM) communities is widespread, and Hg0-contaminated tailings are often reprocessed with cyanide (-CN) to extract residual gold remaining after amalgamation. Hg0 reacts with -CN under aerobic conditions to produce Hg(CN)42- and other Hg(CN)nn-2 complexes. The production of solvated Hg(CN)nn-2 complexes increases upon agitation in the presence of synthetic and authentic Hg0-contaminated tailings that aid in dispersing the Hg0, increasing its reactive surface area. Adult rats were exposed to various concentrations of Hg(CN)2, and accumulation in organs and tissues was quantified using direct mercury analysis. The primary site of Hg(CN)2 accumulation was the kidney, although accumulation was also detected in the liver, spleen, and blood. Little accumulation was observed in the brain, suggesting that Hg(CN)2 complexes do not cross the blood-brain barrier. Renal tissue was particularly sensitive to the effects of Hg(CN)2, with pathological changes observed at low concentrations. Hg(CN)2 complexes are handled by mammalian systems in a manner similar to other inorganic species of Hg, yet appear to be more toxic to organ systems. The findings from this study are the first to show that Hg(CN)2 complexes are highly stable complexes that can lead to cellular injury and death in mammalian organ systems.

Phosphorus, chemical base and other renewables from wastewater with three 168-L microbial electrolysis cells and other unit operations

Phosphate rock is a depleting resource and wastewater a sustainable long-term alternative for phosphorous mining. In modern wastewater treatment phosphate is concentrated 7500 times from wastewater into sludge as iron phosphate (FeP). Recently developed bioelectrochemical reactors enabled phosphate recovery from sewage sludge containing FeP. The integrated bioelectric process was found of much broader utility than initially elaborated. It refines all principle components of wastewater. The implementation is confronted to a number of challenges. Three pilot microbial electrolysis cells (MECs) of 168 L each were constructed and installed in different municipal wastewater treatment plants (WWTPs). The scale-up MECs generated renewable chemical base and co-extracted abundant species such as Na+, K+, Ca2+, Mg2+ and NH4+ from wastewater. The chemical base remobilized phosphate quantitatively from iron phosphates contained in digested sewage sludge. Phosphate extracts contained ammonia and upon magnesium (Mg2+) addition struvite crystalized. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) on heavy metals, Direct Mercury Analysis (DMA), Liquid Chromatography Mass Spectroscopy (LC-MS/MS) on organic micropollutants, metagenomics sequencing, Scanning Electron Microscopy (SEM-EDS), and X-Ray Diffraction (XRD) indicated that a highly pure struvite-fertilizer was produced. Microbial electricity co-generation was verified by electrochemical characterisation and microbiome analysis using 16S rRNA V4-V5 methodology. Geobacter, Dechloromonas, Desulfobulbus and cyanobacteria were the principal electrogens found. All in all, renewable chemical base as well as phosphate were obtained in high quantities and other renewables became accessible such as the critical material magnesium and other compounds of importance like ammonia, potassium, calcium, solid P-free sludge useful as biofuel and purified water. In general, the process recycles important compounds from waste, in a close to traceless manner while purifying wastewater.

Determination of mercury solvation during cyanidation of artisanal & small-scale gold mining tailings via inductively coupled plasma optical emission spectroscopy in comparison to direct mercury analysis

ABSTRACT A procedure employing inductively coupled plasma optical emission spectrometry (ICP-OES) for the determination of solubilised Hg during the modelled cyanidation of Hg0-contaminated tailings from artisanal and small-scale gold mining sites was developed. Verification of Hg concentrations were achieved by comparing results using a Direct Mercury Analyser (DMA-80). The standards and the aqueous samples containing dissolved mercury were introduced into the ICP-OES directly after the addition of AuCl3 and HCl to each solution. Results indicated no retention of dissolved solids, and hence preservation of Hg within the solutions was achieved. The limit of detection for the ICP-OES was determined to be 0.005 μg/L, and the average relative standard deviation was better than 1.1% at levels of 2.0 mg/L Hg, calculated from the peaks obtained. The addition of NaCN significantly increased the concentration of dissolved Hg and confirms that Hg0 is oxidised and then solubilised in the presence of cyanide.