Toxic metals in human milk in relation to tobacco smoke exposure.

Several reports confirm the deleterious effects of tobacco smoking and exposure to second-hand smoke (SHS) resulting in changes in the composition of breast milk. The aim of our study was to compare the levels of selected essential, as well as, toxic metals found in colostrum (collected at day 1 ± 2 post-birth) and mature milk (1 month ± 7 days post-birth) of nonsmoking women (n = 52) compared to those found in women who smoke tobacco (n = 51) and women exposed to second-hand smoke during pregnancy and lactation (n = 47). Women's non-smoking or smoking status was determined by their responses to a questionnaire, including questions about others who may smoke in the home environment, and confirmed by measurement of cotinine in the blood serum by high performance liquid chromatography with diode array detector (HPLC-DAD). Inductively coupled plasma mass spectrometry (ICP-MS) and flame atomic absorption spectroscopy (F-AAS) techniques were used to determine the metal concentrations in colostrum and mature milk previously digested by a microwave mineralizer. We confirmed that exposure to tobacco smoke increases concentrations of heavy metals (cadmium and lead) in colostrum and mature milk. These increased concentrations of heavy metals may disturb the action of bioactive substances necessary for the optimal growth and development of newborns and infants. These findings support the need for increased concern and information to lactating women about preventing their exposure to cigarette smoking and SHS due to the adverse effects of tobacco smoke on breast milk with added risks to their infants.

Lithiation of Agaricus bisporus mushrooms using compost fortified with LiOH: Effect of fortification levels on Li uptake and co-accumulation of other trace elements.

This study investigated the lithiation of white Agaricus bisporus (common button) mushrooms using compost fortified with LiOH solutions at concentrations from 1 to 500 mg kg-1 compost dw. Apart from the highest level of fortification, the median Li concentrations in the cultivated mushrooms were elevated from 0.74 to 21 mg kg-1 dw (corresponding to compost fortification from 1.0 to 100 mg LiOH, kg-1 dw), relative to control mushrooms at 0.031 mg kg-1 dw. The bio-concentration potential for Li uptake in fruiting bodies was found to decrease at higher levels of fortification e.g. 50 - 100 mg kg-1 dw, and at the highest level - 500 mg kg-1, the mycelium failed to produce mushrooms. The fortification of the compost with LiOH appears to have had little, if any, effect on the co-accumulation of other elements such as Ag, Al, As, Ba, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Pb, Rb, Sr, Tl, U, V and Zn in the fruiting bodies, which generally occurred at the lower range of the results reported in the literature for cultivated A. bisporus. Thus compost fortification with LiOH provides an effective means of lithiating A. bisporus for potential pro-therapeutic use.

Total Arsenic and Arsenic Species Determination in Freshwater Fish by ICP-DRC-MS and HPLC/ICP-DRC-MS Techniques.

Analytical methods for the determination of total arsenic (TAs) and arsenic species (arsenite-As(III), arsenate-As(V), monomethylarsenic acid-MMA, dimethylarsenic acid-DMA and arsenobetaine-AsB) in freshwater fish samples were developed. Inductively coupled plasma mass spectrometry with dynamic reaction cell (ICP-DRC-MS) and high-performance liquid chromatography hyphenated to ICP-DRC-MS were used for TAs and arsenic species determination, respectively. The DRC with oxygen as a reaction gas was used. Sample preparation, digestion, and extraction were optimized. Microwave assisted digestion and extraction provided good recovery and extraction efficiency. Arsenic species were fully separated in 8 min using 10 mmol L-1 of ammonium dihydrogen phosphate and 10 mmol L-1 of ammonium nitrate. Overlapping of AsB and As(III) of arsenic species in the presence of a high concentration of AsB and trace amounts of As(III) were studied. Detailed validation of analytical procedures proved the reliability of analytical measurements. Both procedures were characterized by short-term and long-term precision: 2.2% (TAs) up to 4.2% (AsB), and 3.6% (TAs) up to 7.2% (DMA), respectively. Limits of detection (LD) were in the range from 0.056 µg L-1 for TAs to 0.15 µg L-1 for As(V). Obtained recoveries were in the range of 85%⁻116%. Developed methods were applied to freshwater fish samples analysis.

Chemometric approach to evaluate element distribution in muscle, liver and fish bone of roach (Rutilus rutilus), silver bream (Blicca bjoerkna) and crucian carp (Carassius carassius) from Swarzedzkie Lake (Poland) using ICP-MS and FIAS-CVAAS techniques.

The content of elements in fish tissues and organs from Swarzedzkie Lake was investigated in order to evaluate the possible risk associated with their consumption by animals as well as humans. Samples of muscle, liver and fish bone of three fish species; roach (Rutilus rutilus), silver bream (Blicca bjoerkna) and crucian carp (Carassius carassius) were collected from seine catches undertaken as part of the biomanipulation of Swarzedzkie Lake. Element concentration (Al, As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Zn) was determined by inductively coupled plasma mass spectrometry (ICP-MS), with the exception of Hg where the flow injection analysis system cold vapour atomic absorption spectrometry (FIAS-CVAAS) was applied. The study indicated a large variation in the occurrence of the investigated elements in different parts of the fish body. The highest content of Al and Zn was stated in all fish organs for each fish species. The majority of the applied statistical and chemometric methods (e.g., PCA, CA) refer to roach since we had a large number of data for this species. The obtained results were assessed in terms of their accuracy and precision using certified reference material of Fish Muscle ERM BB422.

Determination of total arsenic and arsenic species in drinking water, surface water, wastewater, and snow from Wielkopolska, Kujawy-Pomerania, and Lower Silesia provinces, Poland.

Arsenic is a ubiquitous element which may be found in surface water, groundwater, and drinking water. In higher concentrations, this element is considered genotoxic and carcinogenic; thus, its level must be strictly controlled. We investigated the concentration of total arsenic and arsenic species: As(III), As(V), MMA, DMA, and AsB in drinking water, surface water, wastewater, and snow collected from the provinces of Wielkopolska, Kujawy-Pomerania, and Lower Silesia (Poland). The total arsenic was analyzed by inductively coupled plasma mass spectrometry (ICP-MS), and arsenic species were analyzed with use of high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Obtained results revealed that maximum total arsenic concentration determined in drinking water samples was equal to 1.01 µg L(-1). The highest concentration of total arsenic in surface water, equal to 3778 µg L(-1) was determined in Trujaca Stream situated in the area affected by geogenic arsenic contamination. Total arsenic concentration in wastewater samples was comparable to those determined in drinking water samples. However, significantly higher arsenic concentration, equal to 83.1 ± 5.9 µg L(-1), was found in a snow sample collected in Legnica. As(V) was present in all of the investigated samples, and in most of them, it was the sole species observed. However, in snow sample collected in Legnica, more than 97 % of the determined concentration, amounting to 81 ± 11 µg L(-1), was in the form of As(III), the most toxic arsenic species.

Arsenic speciation in water by high-performance liquid chromatography/inductively coupled plasma mass spectrometry-method validation and uncertainty estimation.

RATIONALE: In order to obtain reliable analytical results for the separation and determination of arsenic species by high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICP-MS), the analytical procedure must be fully validated and the measurement uncertainty of the analytical result should be estimated. METHODS: The total arsenic concentration of the samples was determined by ICP-MS. Separation of the arsenic species, AsB, As(III), DMA, MMA and As(V), was accomplished by liquid chromatography, which was hyphenated to inductively coupled plasma mass spectrometry, used for detection purposes. Automated handling of these systems was achieved with Chromera software. RESULTS: The separation capability between the analytical signals of arsenic species, AsB-As(III), As(III)-DMA, DMA-MMA and MMA-As(V), was 1.3, 1.1, 5.1 and 4.6, respectively. The limit of detection (LOD) values ranged from 0.070 µg L(-1) for DMA to 0.13 µg L(-1) for MMA. The expanded uncertainty U [%] values for coverage factor k = 2 estimated for AsB, As(III), DMA, MMA and As(V) were 12 %, 13 %, 5.6 %, 9.6 % and 8.6 %, respectively. CONCLUSIONS: This study reports, for the first time, building the uncertainty budgets for five arsenic species and estimation of the expanded uncertainty (for k = 2). The qualitative and quantitative parameters determined in the validation process indicate that the presented analytical procedure can be applied for the determination of AsB, As(III), DMA, MMA and As(V) in water.

Can arsenic do anything good? Arsenic nanodrugs in the fight against cancer - last decade review.

Arsenic has been an element of great interest among scientists for many years as it is a widespread metalloid in our ecosystem. Arsenic is mostly recognized with negative connotations due to its toxicity. Surely, most of us know that a long time ago, arsenic trioxide was used in medicine to treat, mainly, skin diseases. However, not everyone knows about its very wide and promising use in the treatment of cancer. Initially, in the seventies, it was used to treat leukemia, but new technological possibilities and the development of nanotechnology have made it possible to use arsenic trioxide for the treatment of solid tumours. The most toxic arsenic compound - arsenic trioxide - as the basis of anticancer drugs in which they function as a component of nanoparticles is used in the fight against various types of cancer. This review aims to present the current solutions in various cancer treatment using arsenic compounds with different binding motifs and methods of preparation to create targeted nanoparticles, nanodiamonds, nanohybrids, nanodrugs, or nanovehicles.

Lithiation of white button mushrooms (Agaricus bisporus) using lithium-fortified substrate: effect of fortification levels on Li uptake and on other trace elements.

High doses of lithium salts are used for the treatment or prevention of episodes of mania in bipolar disorder, but the medication is rapidly excreted and also shows side effects. Li may also be beneficial in people with mood disorders. Nutritionally, popular foods such as wild and cultivated mushrooms have low Li contents. This study evaluated the Li enrichment of white Agaricus bisporus mushrooms using Li2CO3 solutions to fortify the commercial growing substrate at various concentrations from 1.0 to 500 mg kg-1 dry weight (dw). Fortification of up to 100 mg kg-1 dw resulted in a significant (p < 0.01) dose-dependent increase in the accumulation of Li in mushroom, but the highest fortification level was found to be detrimental to fruitification. The median values of Li in fortified mushrooms corresponded to the fortification levels, increasing from 0.49 to 17 mg kg-1 dw relative to the background concentration of 0.056 mg kg-1 dw (control substrate contained 0.10 mg kg-1 dw). The potential for Li uptake in fruiting bodies was found to decrease at higher levels of fortification, with saturation occurring at 100 mg kg-1. Resulting lithiated mushrooms were up to 300-fold richer in Li content than specimens grown on control substrate. The fortification showed some effects on the uptake of other trace minerals, but concentrations of co-accumulated Ag, Al, As, Ba, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Pb, Rb, Sr, Tl, U, V and Zn were similar or lower than values reported in the literature for commercial A. bisporus. These lithiated mushrooms could be considered as a pro-medicinal alternative to treatments that use Li salts.

Enhancing the lithium content of white button mushrooms Agaricus bisporus using LiNO3 fortified compost: effects on the uptake of Li and other trace elements.

Attempts to bio-enrich fungal biomass with an essential trace elements to produce dietary supplements have some tradition and an example is selenium. Lithium salts have medical applications, but safer forms are sought after, and lithiated foods and food supplements may be an alternative. This study evaluated the lithiation of white Agaricus bisporus mushrooms using commercial compost fortified with LiNO3 and investigated the effects on co-accumulation of trace elements. The fortifications at levels of 1.0, 5.0, 10, 50 and 100 mg·kg-1 dw, resulted in corresponding median increases in mushroom Li concentrations of 0.74, 5.0, 7.4, 19 and 21 mg kg-1 dw, respectively, relative to 0.031 mg kg-1 dw in control mushrooms. The bio-concentration potential for Li uptake decreased at higher levels of fortification, with saturation occurring at 100 mg·kg-1, and the level of 500 mg kg-1 mycelium failed to produce mushrooms. The compost fortification resulted in up to several hundred-fold enrichment of mushrooms compared to those grown on control compost, underlining their potential therapeutic use. At higher fortification levels, some effects were seen on the co-accumulation of other elements, such as Ag (stems), As, Cd, Cr, Cs, Cu, Hg (stems), Mn, Rb, Sr, U (stems) and Zn; 0.05 < p < 0.10), but no effects were seen for Ag (caps), Al, Ba, Co, Hg (caps) Ni, Tl, U (caps), and V (p > 0.05).

Estimation of the lake water pollution by determination of 18 elements using ICP-MS method and their statistical analysis.

Eighteen elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Sr and Zn) were determined in water taken from Malta Lake. All the analyses were made using the inductively coupled plasma mass spectrometry method (ICP-MS). In our investigations we focused on the variability of the element content in water from a number of sampling stations and over different seasons. The obtained results were submitted to statistical analysis. First, the results were interpreted using the analysis of variance test (ANOVA). This has revealed differences in concentration for the majority of elements with regard to seasons. Then, cluster analysis (CA) and factor analysis (FA) were applied to explore similarities between sampling stations. Neither of these have demonstrated any grouping. Finally, factor analysis and principal component analysis (PCA), applied to show the grouping of elements, revealed how different sampling stations are related to each other.

Test of the relationships between the content of heavy metals in sewage sludge and source of their pollution by chemometric methods.

The content of various metals (Cd, Cr, Cu, Ni, Pb and Zn) in sewage sludge was analysed by ICP-OES technique. The study was performed on 14 samples from the Wielkopolska region and 4 from the neighbouring provinces. The results were used to perform chemometric analysis. Two chemometric methods were used to test the relationships between the content of heavy metals in sewage sludge and the sources of their pollution. The application of cluster analysis displayed important information about the identification of similar locations of sewage sludge sampling stations. This chemometric method showed that all the monitoring locations are grouped into three main clusters. Separated clusters present similarities between locations of the sewage treatment plants, which have the same kind of industrial plants in their catchment area. Principal component analysis enabled interpretation of the complex relationships between determined elements. Application of principal component analysis to the whole data set helped to distinguish only two sewage sludge stations (Ostrow Wlkp. and Poznan-Kozieglowy) that could be interpreted, each in different principal component thereby suggesting that element's concentration differ considerably. The interpretation of relationships between the rest of the stations was possible by performing PCA for the second time, but on the reduced data set (two above-mentioned stations were excluded). It distinguished two groups: (1) Gniezno, Srem, Kalisz, Inowroclaw and Sroda Wlkp, and (2) Gostyn, Gniezno and Kalisz, which differ with regard to element's concentration.

Arsenic speciation in mushrooms using dimensional chromatography coupled to ICP-MS detector.

This study concerns total arsenic (TAs) and arsenic species determination in three species of mushrooms collected in Yunnan, China. The purpose of this study was to check concentration level of arsenic in Boletus edulis, Tricholoma matsutake and Suillellus luridus, estimate arsenic bioaccessibility and find out which arsenic species occur in mushrooms to assess if they may pose a threat to human health. An analytical methodology based on ion chromatography (IC) hyphenated to inductively coupled plasma mass spectrometry (ICP-MS) with dynamic reaction cell (DRC) and size exclusion chromatography (SEC) with UV-Vis detection and ICP-DRC-MS detection. Ultrasound assisted extraction (UAE), microwave assisted extraction (MAE) and enzymatic assisted extraction (EAE) were applied. Quantification of As species in extracts was performed by IC/ICP-DRC-MS in the first dimension. Slightly better extraction efficiencies were obtained for MAE (from 75% to 90%) then for UAE. EAE was used for estimation of bioaccessibility by application of a modified BARGE bioaccessibility method (UBM) for in vitro studies. Bioaccessibility values were in the ranges of 73%-102%, 74%-115% and 18%-87% for step 1 (S1), for step 2 (S2) and for step 3 (S3) of EAE, respectively. Extracts obtained after EAE were subjected to SEC-UV-Vis/ICP-DRC-MS analysis as the second dimension. The main signal was obtained in the area of a molecular mass of ∼5 kDa for all mushroom extracts. Monitoring of an 50SO+ ion confirmed that this signal comes from As-protein. In sample of Boletus edulis additional signal occurred which is classified as unknown As-compound. Both signals require identification with another analytical technique.

Accurate quantification of total chromium and its speciation form Cr(VI) in water by ICP-DRC-IDMS and HPLC/ICP-DRC-IDMS.

Two analytical procedures have been developed for the determination of total chromium (TCr) and its highly toxic species, i.e. Cr(VI) in water samples using the following methods: inductively coupled plasma dynamic reaction cell isotope dilution mass spectrometry (ICP-DRC-IDMS) and high performance liquid chromatography inductively coupled plasma dynamic reaction cell isotope dilution mass spectrometry (HPLC/ICP-DRC-IDMS). Spectral interferences, predominantly occurring in chromium determination, were removed using a dynamic reaction cell (DRC). The presented procedures facilitate the quantification of trace amounts - below 1 µg L(-1) of TCr and individual Cr species - in various water matrices including drinking water and still bottled water with different mineral composition. Special attention has been paid to the adequate preparation of isotopically enriched (53)Cr(VI) standard solution in order to avoid artifacts in chromium speciation. Both procedures were fully validated as well as establishing the traceability and estimation of the uncertainty of measurement were carried out. Application of all of the above mentioned elements and of the isotope dilution technique, which provides the highest quality of metrological traceability, allowed to obtain reliable and high quality results of chromium determination in water samples. Additionally, the comparison of two methods: HPLC/ICP-DRC-MS and HPLC/ICP-DRC-IDMS for Cr(VI) determination, was submitted basing on the validation parameters. As a result, the lower values for these parameters were obtained using the second method.

New procedure for multielemental speciation analysis of five toxic species: As(III), As(V), Cr(VI), Sb(III) and Sb(V) in drinking water samples by advanced hyphenated technique HPLC/ICP-DRC-MS.

Analytical procedure dedicated for multielemental determination of toxic species: As(III), As(V), Cr(VI), Sb(III) and Sb(V) in drinking water samples using high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-DRC-MS) technique was developed. Optimization of the detection and separation conditions was conducted. Dynamic reaction cell (DRC) with oxygen as a reaction gas was involved in the experiments. Obtained analytical signals for species separation were symmetrical, as studied by anion-exchange chromatography. Applied mobile phase consisted of 3 mM of EDTANa2 and 36 mM of ammonium nitrate. Full separation of species in the form of the following forms: H3AsO3, H2AsO4(-), SbO2(-), Sb(OH)6(-), CrO4(2-) was achieved in 15 min with use of gradient elution program. Detailed validation of analytical procedure proved the reliability of analytical measurements. The procedure was characterized by high precision in the range from 1.7% to 2.4%. Detection limits (LD) were 0.067 µg L(-1), 0.068 µg L(-1), 0.098 µg L(-1), 0.083 µg L(-1) and 0.038 µg L(-1) for As(III), As(V), Cr(VI), Sb(III) and Sb(V), respectively. Obtained recoveries confirmed the lack of interferences' influence on analytical signals as their values were in the range of 91%-110%. The applicability of the proposed procedure was tested on drinking water samples characterized by mineralization up to 650 mg L(-1).

Study on multielemental speciation analysis of Cr(VI), As(III) and As(V) in water by advanced hyphenated technique HPLC/ICP-DRC-MS. Fast and reliable procedures.

Analytical procedures for multielemental speciation analysis of arsenite - As(III), arsenate - As(V) and hexavalent chromium - Cr(VI) in water using high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-DRC-MS) hyphenated technique have been developed. A dynamic reaction cell (DRC) for spectral interferences elimination has been involved in the experiment. Application of oxygen and ammonia as reaction gases in the DRC under various conditions has been verified. Optimization of the following chromatographic conditions: mobile phase composition, concentration of particular components, mobile phase pH and flow rate, injection volume and column temperature, has been conducted. Species separation has been carried out on anion-exchange chromatographic column using isocratic elution with: 22 mM (NH4)2HPO4, 25 mM NH4NO3 (for procedure A) and 22 mM (NH4)2HPO4, 65 mM NH4NO3 (for procedure B) as mobile phases. Detection limits (LD) for procedure A were 0.16 µg L(-1), 0.090 µg L(-1), 0.073 µg L(-1), and for procedure B were 0.14 µg L(-1), 0.062 µg L(-1), 0.15 µg L(-1) for As(III), As(V) and Cr(VI), respectively. Linearity was tested at two concentration ranges of: (0.5-10.0) µg L(-1) for procedure A and (5-50) µg L(-1) for procedure B, and showed correlation coefficients for each of the analytes to be above 0.999. Repeatability values obtained for spiked real water samples were in the range of (4.2-7.6)% and (2.0-2.4)% for procedure A and B respectively. Accuracy was calculated based on the analysis of spiked real water samples at three concentration levels. Obtained recoveries were from 94% to 102%.

Chromium and its speciation in water samples by HPLC/ICP-MS--technique establishing metrological traceability: a review since 2000.

Chromium holds a special position among living organisms because depending on its species it can be either essential or toxic. Cr(VI) even at very low concentrations is harmful and carcinogenic, while Cr(III) is a necessary microelement for cellular metabolism. Therefore, a simple analysis of Cr concentration in collected samples will not be able to distinguish these differences effectively: for a proper chemical analysis we need to perform a reliable detection and quantification of Cr species. Separation and detection of chromium can be accomplished with high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS) in a one-step. Our review assembles articles published since 2000 regarding chromium speciation in water samples with the use of HPLC/ICP-MS. It addresses the following issues: chromium chemistry, the possibilities of dealing with interferences, metrological aspects, analytical performance and speciated isotope dilution mass spectrometry (SIDMS) which is a definitive measurement method. The authors would like to advocate this hyphenated advanced technique as well as the metrological approach in speciation analysis of chromium.

Rhizoremediation of diesel-contaminated soil with two rapeseed varieties and petroleum degraders reveals different responses of the plant defense mechanisms.

Plant-assisted bioremediation (rhizoremediation) stands out as a potential tool to inactivate or completely remove xenobiotics from the polluted environment. Therefore, it is of key importance to find an adequate combination of plant species and microorganisms that together enhance the clean-up process. To understand the response of plants upon bioaugmentation, the antioxidative and detoxification system was analyzed in high and low erucic acid rapeseed varieties (HEAR and LEAR, respectively), after 8 weeks of their treatment with petroleum degraders and 6000 mg diesel oil/kg dry soil. The oxidative stress was enhanced in LEAR being exposed to sole diesel oil, in comparison with HEAR. However, when LEAR plants were additionally inoculated with bacteria, suppression of total catalase (CAT) and ascorbate peroxidase (APX) activity were observed. Interestingly, glutathione transferase (GST) activity was found in these plants at a much higher level than in HEAR, which correlated with a more efficient diesel removal performed by LEAR in the polluted soil and upon bioaugmentation. A distinct profile of polycyclic aromatic hydrocarbons (PAH) was detected in leaves of these plants. Neither LEAR nor HEAR experienced any changes in the photosynthetic capacity upon diesel pollution and presence of petroleum degraders, which supports the usefulness of rhizoremediation with rapeseed.

Arsenic and its speciation in water samples by high performance liquid chromatography inductively coupled plasma mass spectrometry--last decade review.

Arsenic composes a danger for human health all over the world as it is responsible for water resources contamination. The toxicity of arsenic depends on its chemical form. However, occurrence of particular arsenic species is dependent on processes occurring in water. Nowadays, more arsenic species is detected and analyzed in different kind of water (mineral, tap, waste), mainly owing to great possibilities resulting from coupling high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS). This review mainly describes arsenic speciation analysis by HPLC-ICP-MS technique on the basis of articles that have been published since 2000. Arsenic chemistry, occurrence in different kind of water, total arsenic determination with interferences elimination and its validation and analytical performance are also reviewed.