Arsenic accumulation in organs of the fresh water fish Tribolodon hakonensis.

The fish Tribolodon hakonensis lives in good health in Lake Usoriko, which has been acidified and naturally contaminated with arsenic by volcanic activities. We have determined the contents of various metals in various fish organs of T. hakonensis, collected at Lake Usoriko. We found that a large amount of arsenic was accumulated in the eye, especially in the choroid-retina part. The arsenic concentrations in the liver and kidneys were about 0.4 microgram/g (wet), whereas the muscle contained less arsenic. The arsenic accumulation in the skin was also observed, especially in the epaxial part. Zinc and arsenic contents in various fish organs correlated well.     

Transport of arsenolipids to the milk of a nursing mother after consuming salmon fish

ObjectiveWe address two questions relevant to infants’ exposure to potentially toxic arsenolipids, namely, are the arsenolipids naturally present in fish transported intact to a mother’s milk, and what is the efficiency of this transport.MethodsWe investigated the transport of arsenolipids and other arsenic species present in fish to mother’s milk by analyzing the milk of a single nursing mother at 15 sampling times over a 3-day period after she had consumed a meal of salmon. Total arsenic values were obtained by elemental mass spectrometry, and arsenic species were measured by HPLC coupled to both elemental and molecular mass spectrometry.ResultsTotal arsenic increased from background levels (0.1 μg As kg⁻¹) to a peak value of 1.72 μg As kg⁻¹ eight hours after the fish meal. The pattern for arsenolipids was similar to that of total arsenic, increasing from undetectable background levels (< 0.01 μg As kg⁻¹) to a peak after eight hours of 0.45 μg As kg⁻¹. Most of the remaining total arsenic in the milk was accounted for by arsenobetaine. The major arsenolipids in the salmon were arsenic hydrocarbons (AsHCs; 55 % of total arsenolipids), and these compounds were also the dominant arsenolipids in the milk where they contributed over 90 % of the total arsenolipids.ConclusionsOur study has shown that ca 2–3 % of arsenic hydrocarbons, natural constituents of fish, can be directly transferred unchanged to the milk of a nursing mother. In view of the potential neurotoxicity of AsHCs, the effects of these compounds on the brain developmental stage of infants need to be investigated.     

The removal of As(III) and As(V) from aqueous solutions by waste materials

The use of different waste materials such as Atlantic Cod fish scale, chicken fat, coconut fibre and charcoal in removing arsenic [As(III) and As(V)] from aqueous solutions was investigated. Initial experimental runs, conducted for both As(III) and As(V) with the aforementioned materials, demonstrated the potential of using Atlantic Cod fish scale in removing both species of arsenic from aqueous streams. Therefore, the biosorbent fish scale was selected for further investigations and various parameters such as residence time, adsorbent dose, initial concentration of adsorbate, grain size of the adsorbent and pH of the bulk phase were studied to establish optimum conditions. The maximum adsorption capacity was observed at pH value 4.0. The equilibrium adsorption data were interpreted by using both Freundlich and Langmuir models. Rapid small-scale column tests (RSSCT) were also performed to determine the breakthrough characteristics of the arsenic species with respect to packed biosorbent columns.     

Human Health Risk from Metals in Fish from Saudi Arabia: Consumption Patterns for Some Species Exceed Allowable Limits

Fish are a healthful source of protein, but contaminants in some fish pose a risk. While there are multiple risk assessments from Europe and North America, there are far fewer for other parts of the world. We examined the risks from mercury, arsenic, lead, and other metals in fish consumed by people in Jeddah area, Saudi Arabia, using site-specific data on consumption patterns and metal levels in fish. The U.S. Environmental Protection Agency's Hazard Quotient (HQ) and cumulative Hazard Index (HI) for non-cancer endpoints and Carcinogenic Index for cancer were used to determine the health risk based on fish consumption rates. Of the 13 fish species examined, HQ was greater than 1 (indicating elevated risk) in two species for arsenic, and seven species for methylmercury. The cumulative HI for all metals was above 1 for all but three species of fish at the mean consumption rates. Generally, fish species with HI above 1 for one sampling location, had HI above 1 for all sampling locations. The implications of these findings are discussed in the light of strategies for reducing risk from fish consumption while encouraging dietary intakes of fish with low mercury and arsenic levels.     

Importance of Arsenic Speciation in Populations Exposed to Arsenic in Drinking Water

Total arsenic in urine is often the principal means for assessing chronic exposure to arsenic-contaminated drinking water. This approach ignores many components of the human diet, especially fish and seafood that contain arsenic at significant concentrations. The toxicity differences between the inorganic forms and the dietary forms suggest both should be evaluated when attempting to assess risk from arsenic exposure. Urine biomonitoring for 53 participants was used to confirm reduction in arsenic exposure resulting from well water remediation removing inorganic arsenic from drinking water. Initially, only total arsenic urine assays were performed, but spikes in total arsenic urine concentrations were determined to be diet related and demonstrated the need for analytical methods that differentiate the arsenic species. A secondary analysis was added that quantified inorganic-related arsenic in urine and the dietary forms related to fish and seafood by subtraction from total arsenic. Significant differences were found between the inorganic arsenic component and the total arsenic measured in their urine. On average, approximately 76% of total arsenic in urine was attributed to fish and other organo-arsenic dietary sources, implying a potential significant overestimate of exposure, and demonstrating the need for differentiation of the inorganic-related arsenic from dietary arsenic.     

The presence of arsenobetaine in marine animals

Methanol soluble arsenic compounds were isolated from the muscle tissues of a crayfish, Jasus novaehollandiae, a prawn, Penaeus latisulcatus, a scallop, Pecten alba, a squid, Sepioteuthis australis and a fish, Sillaginodes punctatus. Arsenobetaine was found to be the major arsenic compound present in all muscle tissues. The prawn and scallop tissues also contained another organo arsenic compound that could be partially degraded to characterized methylated arsenic species.     

Resistance to oxidative stress in a freshwater fish Channa punctatus after exposure to inorganic arsenic

The biochemical toxicity of arsenic trioxide (As^III) in a freshwater edible fish Channa punctatus has been studied on exposures ranging from 7 to 90 d. The arsenic concentration increased exponentially in liver, kidney, gills, and muscles of fish up to 60 d of exposure to arsenic. However, arsenic concentration in these tissues declined at 90 d of exposure. This relationship between period of exposure and concentration of arsenic in selected tissues suggests an adaptive response of fish to arsenic. Furthermore, exposure to arsenic-induced lipid peroxidation in these organs increased initially at 7 d of exposure; however, it decreased up to 60 d of exposure but increased again at 90 d of treatment. Values of reduced glutathione (GSH) reflected the observations of lipid peroxidation. The role of GSH in this adaptive response has been discussed.     

Arsenic in the human food chain,biotransformation and toxicology – Review focusing on seafood arsenic

Fish and seafood are main contributors of arsenic (As) in the diet. The dominating arsenical is the organoarsenical arsenobetaine (AB), found particularly in finfish. Algae, blue mussels and other filter feeders contain less AB, but more arsenosugars and relatively more inorganic arsenic (iAs), whereas fatty fish contain more arsenolipids. Other compounds present in smaller amounts in seafood include trimethylarsine oxide (TMAO), trimethylarsoniopropionate (TMAP), dimethylarsenate (DMA), methylarsenate (MA) and sulfur-containing arsenicals. The toxic and carcinogenic arsenical iAs is biotransformed in humans and excreted in urine as the carcinogens dimethylarsinate (DMA) and methylarsonate (MA), producing reactive intermediates in the process. Less is known about the biotransformation of organoarsenicals, but new insight indicates that bioconversion of arsenosugars and arsenolipids in seafood results in urinary excretion of DMA, possibly also producing reactive trivalent arsenic intermediates. Recent findings also indicate that the pre-systematic metabolism by colon microbiota play an important role for human metabolism of arsenicals. Processing of seafood may also result in transformation of arsenicals.     

Arsenic in the water,sediment and fish in the Neretva River Delta,Croatia

The Neretva River Delta in Croatia is under constant threat of pollution from various sources along the river watercourse, such as the aluminium industry and bauxite mining, intensive agriculture and untreated sewage from towns. The area is also an important fishing ground and food source for the local residents, whereby the suitability of fish for human consumption is always in question. In this paper the presence of arsenic from six sources was analysed: in water, sediment and fish organs (kidneys, liver, muscles and gonads) of 11 fish species: Lepomis gibbosus, Carassius auratus gibelio, Cyprinus carpio, Anguilla anguilla, Ameiurus nebulosus, Mugil cephalus, Leuciscus svallize, Oncorhynchus mykiss, Salmo trutta, Tinca tinca and Scardinius plotiza. The research showed that arsenic concentrations varied significantly from one source to another in the water, sediment and organs of different fish species. Average concentrations in water and sediment were 18.1 μg L^?1 and 32.7 μg kg^?1, respectively. Average arsenic levels in the fish organs were 115.9, 105.8, 76.1 and 61.9 μg kg^?1 in muscles, kidneys, gonads and livers, respectively. These values are below legally permitted concentrations, although individuals with higher than average concentrations were recorded.     

Sub-lethal concentration of arsenic interferes with the proliferation of hepatocytes and induces in vivo apoptosis in Clarias batrachus L

We studied the hepatocellular alterations induced by sub-lethal concentrations (0.50 muM) of arsenic in Indian catfish Clarias batrachus L. Sub-lethal arsenic exposure altered serum aspartate aminotransferase and alkaline phosphatase levels and brought about significant changes in different serum biochemical parameters. Arsenic exposure reduced total hepatocyte protein content and suppressed the proliferation of hepatocytes in a time-dependent manner. Routine histological studies on liver documented arsenic-induced changes characterized by dilated sinusoids, formation of intracellular edema, megalocytosis, vacuolation and appearance of hepatic cells with distorted nuclei. Transmission electron microscopy of hepatocytes further revealed hyperplasia and hypertrophy of mitochondria, development of dilated rough endoplasmic reticulum and changes in peroxisome size with duration of arsenic exposure. Degeneration of mitochondrial cristae and condensation of chromatin was also evident in arsenic-exposed hepatocytes. A significant number of hepatocytes isolated from arsenic-exposed fish stained with annexin V and demonstrated DNA ladder characteristic of apoptosis. Single-cell gel electrophoresis of exposed hepatocytes also revealed the development of comets usually seen in apoptotic cells. Using specific inhibitors it was determined that the arsenic-induced apoptosis of hepatocytes was caspase-mediated, involving the caspase 3 pathway.     

Endothelial Function and Serum Concentration of Toxic Metals in Frequent Consumers of Fish

Background

Endothelial dysfunction is involved in the pathogenesis of atherosclerosis. Consumption of fish is associated with reduced cardiovascular risk, but there is paucity of data concerning its effect on endothelial function. Furthermore, investigation of the effects of fish consumption on health must take into account the ingestion of contaminants, including transition metals and some metalloids, which may have unfavorable effects on health, including those on the cardiovascular system. We investigated the association between fish consumption, endothelial function (flow mediated dilation of the brachial artery), and serum concentration of some toxic metals in apparently healthy people.

Methods

Twenty-nine high fish consumers (at least 3 portions a week) were compared with 25 low fish consumers (less than 1 portion a week). All participants were free of diabetes, cardiovascular or other systemic diseases. Serum metal (antimonium, arsenic, mercury, lead, cobalt, copper, zinc, selenium, strontium) concentrations were measured in subgroups of 24 high fish consumers and 19 low fish consumers.

Results

Both groups exhibited similar habitual dietary patterns, age and anthropometric characteristics. The high fish consumers had higher flow mediated dilation (9.7±1.8 vs. 7.3±1.9%; P<0.001), but also higher serum concentrations of mercury (5.87±2.69 vs. 1.65±1.10 mcg/L; P<0.001) and arsenic (6.04±3.25 vs. 2.30±1.58 mcg/L; P<0.001). The fasting plasma glucose concentrations were significantly correlated with both mercury (r = 0.39; P = 0.01) and arsenic concentrations (r = 0.55; P<0.001).

Conclusions

Habitual consumption of high amounts of fish is associated with better endothelial function despite higher serum concentrations of mercury and arsenic.     

Hepatobiliary and hematological effects of dietary disodium arsenate heptahydrate in juvenile rainbow trout (Oncorhynchus mykiss)

1. The impact of 8–12 weeks exposure to up to 55–60 μg arsenic/g diet as disodium arsenate (DSA) on the hepatobiliary and hematological systems of rainbow trout was assessed.2. Bile and washed gallbladder tissue arsenic residues in exposed fish were 2–4 times higher than in liver. Plasma arsenic concentration was slightly elevated following dietary DSA exposure.3. Chronic exposure to dietary DSA caused a mild to moderate responsive anemia.4. Lipid, but not protein, digestibility after 12 weeks of exposure showed an inverse relationship with severity of gallbladder inflammation in these fish.5. Changes in the hepatobiliary system appear to provide the most sensitive indicators of dietary DSA exposure in rainbow trout.     

Perturbations in the catfish immune responses by arsenic: organ and cell specific effects

The present study was an attempt to elucidate the effect of non-lethal arsenic (As) exposure (1/10 LC50) on different immunologically important organs and cells of a catfish. Clarias batrachus L. were exposed to arsenic trioxide for different time intervals, which resulted in significant, time-dependent changes in total head kidney and splenic leucocyte count (p<0.05) and reduction in the organosomatic indices (p<0.05) of these two important immunocompetent organs. Routine histological studies revealed arsenic induced changes in the cellular composition of head kidney and spleen. Arsenic also induced time-dependent and tissue-specific alterations in T and B cell functioning in catfish. When checked for its effects on macrophages, it was noted that arsenic interfered with bacterial phagocytosis. Furthermore, arsenic affected the general immune status of C. batrachus and rendered the fish immunocompromised and susceptible to pathogens.     

Effect of arsenic (AsIII) on glutathione-dependent enzymes in liver and kidney of the freshwater fish Channa punctatus

The possible role of glutathione-dependent enzymes in the liver and kidney of the freshwater fish Channa punctatus has been studied after exposure to arsenic trioxide for different durations. Activities of glutathione-S-transferases, glutathione peroxidase, glutathione reductase, and catalase decreased in the liver and kidney as a result of the initial increase in arsenic concentration in the liver and kidney. However, during longer exposures, a decline in arsenic concentration corresponded with improved enzyme activity. Because arsenic manifests its toxicity by inducing oxidative stress, the antioxidant enzymes, especially the glutathione-dependent enzymes, play a protective role in arsenic toxicity.     

Variation of Total and Speciated Arsenic in Commonly Consumed Fish and Seafood

This article compiles available data and presents an approach for predicting human intakes of inorganic arsenic (As_i), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) from marine, estuarine, and freshwater seafood when only total arsenic (As_tot) concentrations are reported. Twenty studies provided data on total arsenic (As_tot) and As_i. Mean As_i concentrations were approximately 10 to 20 ng/g wet weight (ww) in freshwater, anadromous, and marine fish, whereas crustaceans and molluscs had mean As_i concentrations of 40 to 50 ng/g ww. Thirteen studies provided data for MMA and DMA. MMA was seldom detected, whereas DMA averaged 10 ng/g ww in freshwater fish, and 45 to 95 ng/g ww in anadromous fish, marine fish, crustaceans, and molluscs. There was little correlation between As_tot concentrations and As_i concentrations; however, when only As_tot data are available to assess health risks from arsenic in seafood, these data could support conservative, upper end estimates of the percent of As_tot likely to be As_i. For marine and estuarine fish, and crustaceans and molluscs 2–3% of As_tot was As_i at the 75th percentile of the dataset. For freshwater fish As_i was 10% of As_tot at the 75th percentile. Due to the nonlinearity and low carcinogenic potency of DMA, the reported DMA concentrations should not contribute substantially to potential health risks from arsenic in seafood.     

Metagenomic study of red biofilms from Diamante Lake reveals ancient arsenic bioenergetics in haloarchaea

Arsenic metabolism is proposed to be an ancient mechanism in microbial life. Different bacteria and archaea use detoxification processes to grow under high arsenic concentration. Some of them are also able to use arsenic as a bioenergetic substrate in either anaerobic arsenate respiration or chemolithotrophic growth on arsenite. However, among the archaea, bioenergetic arsenic metabolism has only been found in the Crenarchaeota phylum. Here we report the discovery of haloarchaea (Euryarchaeota phylum) biofilms forming under the extreme environmental conditions such as high salinity, pH and arsenic concentration at 4589 m above sea level inside a volcano crater in Diamante Lake, Argentina. Metagenomic analyses revealed a surprisingly high abundance of genes used for arsenite oxidation (aioBA) and respiratory arsenate reduction (arrCBA) suggesting that these haloarchaea use arsenic compounds as bioenergetics substrates. We showed that several haloarchaea species, not only from this study, have all genes required for these bioenergetic processes. The phylogenetic analysis of aioA showed that haloarchaea sequences cluster in a novel and monophyletic group, suggesting that the origin of arsenic metabolism in haloarchaea is ancient. Our results also suggest that arsenite chemolithotrophy likely emerged within the archaeal lineage. Our results give a broad new perspective on the haloarchaea metabolism and shed light on the evolutionary history of arsenic bioenergetics.     

Arsenite medicinal use, metabolism, pharmacokinetics and monitoring in human hair

Acute promyelocytic leukaemia (APL) is a distinctive subtype of acute myeloid leukaemias. Even through this human disease can be treated by the intravenous administration of all-trans retinoic acid (ATRA), 25% of patients typically relapse after the first treatment. In this context, the intravenous administration of APL patients with an aqueous solution of arsenic trioxide has also been demonstrated to be successful despite the established mammalian toxicity of this arsenic compound. Accordingly, the administration of a therapeutic dose of arsenic trioxide has resulted in an improved patient survival in both relapsing as well newly diagnosed APL patients.We present here a mini-review of the medicinal use of arsenite, its mammalian metabolism (with an emphasis on biomethylation pathways), its elimination and pharmacokinetics and the novel application of hair analysis as a biomonitoring material. This mini-review also introduces our own results on the analysis of hair of patients receiving arsenic trioxide therapy.In this work, instead of quantifying arsenic content in bulk hair, we performed longitudinal analysis in order to use hair as a marker of arsenic exposure correlated to a time scale. Taking into account the hair growth rate, the longitudinal analysis of hair is demonstrated to provide a chronological record of the treatment of patients with arsenic trioxide. The small quantity of material to be analysed required the use of Synchrotron radiation based X-ray fluorescence (SXRF) spectroscopy. The hair arsenic content was well correlated with the clinical background of patients and reflected the intake of arsenic trioxide. In particular, the onset of arsenic trioxide therapy and interruptions during therapy were reflected by total arsenic content, which suggested rapid elimination.Another type of experiment, micro-XRF cartography on thin hair slices, allowed us to obtain distribution maps of arsenic, which demonstrated that arsenic is located at the periphery of hair. Micro-XANES spectra recorded at the periphery of hair, suggest that inorganic arsenic is incorporated in hair in its trivalent oxidation state, in agreement with previous results.     

Arsenolipids show different profiles in muscle tissues of four commercial fish species

Identification of arsenolipids in biological samples is today a challenge and in particular the need for speciation data for toxicological assessment. Fish is one of the major contributors of arsenic in diet. However, the majority of work in this area has only focused on the water soluble compounds. The aim of this study is to provide some data on total arsenic and in particular to gain insights into the types of arsenolipids in the muscle tissues of four commercial and commonly consumed fish species. Determination of total arsenic was carried out by ICP-MS following microwave-assisted acid digestion of the samples and the concentrations found for total arsenic in the muscles ranged from 4.8 to 6.0 μg/g d.w. Sequential extraction was carried out using hexane and MeOH/DCM followed by reversed phase HPLC-ICP-MS/ESI-MS analysis of the MeOH/DCM fraction. Eight arsenolipids including three arsenic fatty acids (AsFAs) and five arsenic hydrocarbons (AsHCs) were identified. The result showed that fish with higher arsenolipid (AsLp) content (brill and sardine) are dominated by AsHC, while those with the smaller proportion of AsLp (mackerel and red mullet) have predominately arsenic in the form of AsFA.     

Toxic metals in freshwater fish from the Zagreb area as indicators of environmental pollution

The aim of this investigation was to determine the levels of heavy metals and metalloids in freshwater fish from the Zagreb area. A total of 216 freshwater fish samples from 5 sites were examined: Sava river upstream from Zagreb, Sava river at Zagreb, Sava river downstream from Zagreb, Jarun Lake, and 5 "ecologic" fishponds from the Zagreb surroundings. The metals lead, cadmium, mercury and the metalloid arsenic were determined by the method of atomic absorption spectrometry. The mean pooled levels of lead, cadmium and arsenic in all fish samples were 112.3 +/- 95 micrograms/kg, 8.5 +/- 11 micrograms/kg and 23.5 +/- 36 micrograms/kg, and did not exceed the allowed levels of 1,000 mg/kg, 100 micrograms/kg and 200 micrograms/kg, respectively. In 4 fish samples, the levels of mercury exceeded the allowed limit of 500 micrograms/kg (509, 596, 605 and 788 micrograms/kg), however, the pooled mean level of mercury was 127.8 +/- 90 micrograms/kg. There was no major difference in the levels of heavy metals between the two fish families observed, although the levels of lead, cadmium and mercury were higher in the family Ictaluridae (144 vs. 107 micrograms/kg, 10.4 vs. 8.2 micrograms/kg, and 153 vs. 124 micrograms/kg, respectively), whereas the level of arsenic was higher in the family Cyprinidae (23.8 vs. 21.8 micrograms/kg). Although the Sava river at Zagreb is the main recipient of sewage and wastewater in the Republic of Croatia, the levels of heavy metals were within the allowed limits in all groups of freshwater fish samples, with the exception of 4 samples that contained moderately elevated levels of mercury. Study results suggest that only mercury could be considered a good indicator of environmental pollution, because higher levels of mercury were measured in the fish from the Sava river than in the fish from the Jarun Lake and fishponds from the Zagreb surroundings, considering both pooleded and fish family specified data.     

Arsenic in Seafood: Speciation Issues for Human Health Risk Assessment

Major sources of arsenic exposure for humans are foods, particularly aquatic organisms, which are called seafood in this report. Although seafood contains a variety of arsenicals, including inorganic arsenic, which is toxic and carcinogenic, and arsenobetaine, which is considered nontoxic, the arsenic content of seafood commonly is reported only as total arsenic. A goal of this literature survey is to determine if generalizable values can be derived for the percentage of total arsenic in seafood that is inorganic arsenic. Generalizable values for percent inorganic arsenic are needed for use as default values in U.S. human health risk assessments of seafood from arsenic-contaminated sites. Data from the worldwide literature indicate the percent of inorganic arsenic in marine/estuarine finfish does not exceed 7.3% and in shellfish can reach 25% in organisms from presumably uncontaminated areas, with few data available for freshwater organisms. However, percentages can be much higher in organisms from contaminated areas and in seaweed. U.S. site-specific data for marine/estuarine finfish and shellfish are similar to the worldwide data, and for freshwater finfish indicate that the average percent inorganic arsenic is generally < 10%, but ranges up to nearly 30%. Derivation of nationwide defaults for percent inorganic arsenic in fish, shellfish, and seaweed collected from arsenic-contaminated areas in the United States is not supported by the surveyed literature.