TC-G 1008 facilitates epileptogenesis by acting selectively at the GPR39 receptor but non-selectively activates CREB in the hippocampus of pentylenetetrazole-kindled mice.

The pharmacological activation of the GPR39 receptor has been proposed as a novel strategy for treating seizures; however, this hypothesis has not been verified experimentally. TC-G 1008 is a small molecule agonist increasingly used to study GPR39 receptor function but has not been validated using gene knockout. Our aim was to assess whether TC-G 1008 produces anti-seizure/anti-epileptogenic effects in vivo and whether the effects are mediated by GPR39. To obtain this goal we utilized various animal models of seizures/epileptogenesis and GPR39 knockout mice model. Generally, TC-G 1008 exacerbated behavioral seizures. Furthermore, it increased the mean duration of local field potential recordings in response to pentylenetetrazole (PTZ) in zebrafish larvae. It facilitated the development of epileptogenesis in the PTZ-induced kindling model of epilepsy in mice. We demonstrated that TC-G 1008 aggravated PTZ-epileptogenesis by selectively acting at GPR39. However, a concomitant analysis of the downstream effects on the cyclic-AMP-response element binding protein in the hippocampus of GPR39 knockout mice suggested that the molecule also acts via other targets. Our data argue against GPR39 activation being a viable therapeutic strategy for treating epilepsy and suggest investigating whether TC-G 1008 is a selective agonist of the GPR39 receptor.

LC/ICP-MS AND COMPLEMENTARY TECHNIQUES IN BESPOKE AND NONTARGETED SPECIATION ANALYSIS OF ELEMENTS IN FOOD SAMPLES.

Chemical elements speciation analysis of food samples has been among the most important scientific topics over the last decades. Food samples are comprised of high variety of chemical compounds, from which many can interact with metals and metalloids, forming complex elemental species with various influence on the human body. It is particularly important not only to determine the amount of certain chemical element in food sample but also to identify the form in which given element occurs in given sample. Employment of bespoke and nontargeted speciation methods, with the use of liquid chromatography inductively coupled plasma mass spectrometry (LC/ICP-MS) and complementary techniques, provides more complete picture on the metals and metalloids speciation in food. This review discusses issues concerning speciation analysis of metals and metalloids in food samples with the use of LC/ICP-MS as a leading technique in elemental speciation nowadays and a complimentary technique intended for their identification. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.

In vitro gastrointestinal digestion and bioavailability of lithium from processed lithiated and nonlithiated white Agaricus bisporus mushrooms.

AIM: In order to avoid side effects of lithium doses in some patients, some commonly cultivated mushroom species including A. bisporus have been successfully lithiated, with the potential to provide more acceptable sources of Li. This study assessed the in vitro release (potential bioaccessibility) and possible intake of Li using the action of artificial gastrointestinal juices on lithiated and nonlithiated (control) button mushrooms (Agaricus bisporus) that were subjected to certain modes of culinary processing. METHODS: In the in vitro release study, mushrooms were processed using a number of routinely used domestic treatments including rehydrating dried mushrooms, blanching and blanching followed by pickling of fresh or frozen mushrooms. The in vitro digestion procedure used artificial gastrointestinal juices in a two-stage methodology that was adapted from 'The Bioaccessibility Research Group of Europe' method. The Li concentrations were determined using an inductively coupled argon plasma-dynamic reactive cell-mass spectrometer. RESULTS: Lithium was found to be more bioaccessible from caps of lithiated mushrooms compared with nonlithiated. Releases from the caps and stipes of blanched or blanched and then pickled mushrooms through gastric digestion ranged from 32 ± 2 to 50 ± 1% relative to the dried product and was lower for gastrointestinal digestion, which ranged from 16 ± 1 to 20 ± 1%. CONCLUSION: Losses of Li sustained through blanching or blanching followed by pickling of fresh mushrooms (41-87% wet weight) combined with limited accessibility during gastrointestinal release (16-55%) result in much lower bioavailability of the dose from lithiated products. A 300-g meal would provide <5% of the Li (6 mg) required for potential preventative treatments, such as reducing suicide rates and lowering dementia risk.

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 Versus Inorganic and Organic Species of As, Cr, and Sb in Flavored and Functional Drinking Waters: Analysis and Risk Assessment.

Packing material can release certain elements such as As, Cr, or Sb into its content and, thus, contaminate the drinking water. The effect of As, Cr, and Sb on human health depends highly on the chemical species in which these elements are introduced into the body. For the above reasons quantification and speciation of As, Cr, and Sb in flavored and functional drinking water samples is an important issue. Total, inorganic, and organic species of As, Cr, and Sb including As(III), As(V), Cr(VI), Sb(III), and Sb(V) were studied in flavored and functional drinking waters. Analyses of total As, Cr, and Sb were conducted using inductively coupled plasma mass spectrometry (ICP-MS) according to ISO 17294-2:2016. The speciation analysis of arsenic, chromium, and antimony in bottled flavored and functional drinking waters was conducted with the use of the elemental (HPLC/ICP dynamic reaction cell (DRC) MS) and molecular (electrospray ionization MS/MS) mass spectrometry. Concentrations of total As, Cr, and Sb (µg∙L-1) in waters studied were in the ranges 0.0922 ± 0.0067 to 8.37 ± 0.52, 0.0474 ± 0.0014 to 1.310 ± 0.045, and 0.0797 ± 0.0026 to 1.145 ± 0.019, respectively. Speciation analysis showed that, apart from the toxic ionic species, known and unknown organic species were present in test samples. The risk assessment results proved that there is no risk associated with consumption of these tested beverages in terms of the non-carcinogenic effect of total and inorganic or organic species of As, Cr, and Sb.

Insight into the Phytoremediation Capability of Brassica juncea (v. Malopolska): Metal Accumulation and Antioxidant Enzyme Activity.

Metal hyperaccumulating plants should have extremely efficient defense mechanisms, enabling growth and development in a polluted environment. Brassica species are known to display hyperaccumulation capability. Brassica juncea (Indiana mustard) v. Malopolska plants were exposed to trace elements, i.e., cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn), at a concentration of 50 µM and were then harvested after 96 h for analysis. We observed a high index of tolerance (IT), higher than 90%, for all B. juncea plants treated with the four metals, and we showed that Cd, Cu, Pb, and Zn accumulation was higher in the above-ground parts than in the roots. We estimated the metal effects on the generation of reactive oxygen species (ROS) and the levels of protein oxidation, as well as on the activity and gene expression of antioxidant enzymes, including superoxide dismutase (SOD), catalase (CAT), and ascorbate peroxidase (APX). The obtained results indicate that organo-specific ROS generation was higher in plants exposed to essential metal elements (i.e., Cu and Zn), compared with non-essential ones (i.e., Cd and Pb), in conjunction with SOD, CAT, and APX activity and expression at the level of encoding mRNAs and existing proteins. In addition to the potential usefulness of B. juncea in the phytoremediation process, the data provide important information concerning plant response to the presence of trace metals.

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.

Study on Speciation of As, Cr, and Sb in Bottled Flavored Drinking Water Samples Using Advanced Analytical Techniques IEC/SEC-HPLC/ICP-DRC-MS and ESI-MS/MS.

The main aim of the research was to develop a complementary analytical approach consisting of bespoke speciation analysis and non-targeted speciation analysis of As, Sb, and Cr in flavored bottled drinking water samples using HPLC/ICP-DRC-MS and ESI-MS/MS. The scope of two previously developed analytical procedures, (1) multielemental speciation procedure for AsIII, AsV, CrVI, SbIII, and SbV analysis and (2) arsenic speciation procedure for AsB, AsIII, DMA, MMA, and AsV quantification, was extended to the analysis of a new sample type in terms of bespoke speciation analysis. As for the non-targeted speciation, analysis size exclusion chromatography was used with ICP-MS and a complementary technique, ESI-MS/MS, was used for the organic species of As, Sb, and Cr screening. Full validation of procedures 1 and 2 was conducted. Procedure 1 and 2 were characterized with precision values in the range from 2.5% to 5.5% and from 3.6% to 7.2%, respectively. Obtained recoveries ranged from 97% to 106% and from 99% to 106% for procedures 1 and 2, respectively. Expanded uncertainties calculated for procedures 1 and 2 ranged from 6.1% to 9.4% and from 7.4% to 9.9%, respectively. The applicability of the proposed procedures was tested on bottled drinking water samples. Results for the real samples in procedure 1 were in the range from 0.286 ± 0.027 [µg L-1] to 0.414 ± 0.039 [µg L-1] for AsIII, from 0.900 ± 0.083 [µg L-1] to 3.26 ± 0.30 [µg L-1] for AsV, and from 0.201 ± 0.012 [µg L-1] to 0.524 ± 0.032 [µg L-1] for SbV. CrVI and SbIII were not detected in any sample. As for procedure 2, results were in the range from 0.0541 ± 0.0053 [µg L-1] to 0.554 ± 0.054 [µg L-1] for AsB. Results for AsIII and AsV obtained with procedure 2 were in good accordance with results obtained with procedure 1. DMA and MMA were not detected in any sample.

Mineral constituents of conserved white button mushrooms: similarities and differences

Background: Mushrooms are a food that is often considered as an important source of minerals and other nutrients for consumers. There is little data on the minerals in mushrooms processed culinary and on the impact of processing. Objective: The research was aimed at understanding the similarities and differences in the mineral composition (Hg, Li, Mg, Al, Co, Ni, Cu, As, Se, Rb, Sr, Ag, Cd, Cs, Sb, Tl, Pb, U, Ba, Cr, Zn, Mn and V) of white button mushrooms (Agaricus bisporus) processed in industrial conditions. Material and methods: Fungal materials came from six producers. The elements were determined by ICP-MS DRC and CV-AAS using validated methods and QA/QC protocol. The interdependencies of 18 elements and 10 batches of mushrooms examined were tested with the help of principal component analysis. Results: Some significant differences were found in the content and composition of minerals in marinated white button mushrooms depending on producer. Conserved white button mushrooms are poorer in major essential elements but also in toxic Hg, As, Ag, Cd, Sb, Tl or Pb which has been reported for unprocessed mushrooms. Conclusions: The relatively higher levels of Ag in some batches seem to be largely explained by the quality of the substrate used for mushrooms cultivation, while of Li, Rb, Cs, Cr, Al, U, V, As and Mn (in part also of Ba and Sr) largely by the quality of the marinade.

Metallic elements and metalloids in Boletus luridus, B. magnificus and B. tomentipes mushrooms from polymetallic soils from SW China.

Yunnan Province in China is known for its high biodiversity of mushrooms and a diverse geochemistry of soil bedrock and polymetallic soils, but our knowledge of mineral compositions of mushrooms from Yunnan is scarce. The metallic trace elements, Ag, Ba, Co, Cd, Cs, Cu, Cr, Hg, Li, Mn, Ni, Pb, Rb, Sr, V, Tl, U and Zn, and the metalloids, As and Sb, have been investigated using validated methods with a dynamic reactive cell by mass spectroscopy - inductive coupled plasma and cold vapour - atomic absorption spectroscopy on three popular species of Boletus mushrooms from Southwestern China. The trace mineral profiles in caps and stipes of B. luridus (24 individuals), B. magnificus (29 individuals) and B. tomentipes (38 individuals) have been evaluated. The interspecific differences in the content of several trace elements could be attributed to known differences in the geochemistry of soils in Yunnan, but for copper a difference was observed within species. The mean values of concentrations in composite samples of caps for B. luridus, B. magnificus and B. tomentipes from three to four locations were at the ranges (mgkg-1 dry biomass): Ag (1.3-3.7), As (0.79-53), Ba (4.0-12), Co (0.68-1.2), Cd (0.79-2.2), Cs (0.67-55), Cu (37-77), Cr (5.0-7.6), Hg (2.1-5.4), Li (0.15-0.61), Mn (13-28), Ni (0.86-4.6), Pb (0.59-1.8), Rb (90-120), Sb (0.014-0.088), Sr (0.63-1.6), V (1.4-2.2), Tl (0.017-0.054), U (0.029-0.065) and Zn (130-180). Caps of Boletus mushrooms were richer in Ag, Cu, Hg and Zn than stipes, while other elements were distributed roughly equally between both morphological parts. B. luridus, B. magnificus and B. tomentipes grew in certain sites in Yunnan contained Ag, As, Ba, Cr, Hg, Ni, Sr or V at elevated concentration. A specific geochemistry of the soils type (latosols, lateritic red earths, and red and yellow earths in the Circum-Pacific Mercuriferous Belt of Southwestern China) can explain occurrence of some minerals at greater or elevated amount in mushrooms in Yunnan, while number of available research and data on mineral composition of mushrooms due to geochemical anomalies of soil parent material is so far little.

Accumulation and distribution of metallic elements and metalloids in edible Amanita fulva mushrooms.

Baseline concentrations of Ag, Al, As, Ba, Ca, Cd, Co, Cu, Cr, Fe, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr, Tl, V, U and Zn were presented in Amanita fulva collected from unpolluted areas in Poland. There is no previous data published on the bio-element constituents of A. fulva. A very narrow range of values was determined by ICP-DRC-MS and ICP-AES for the trace elements Ag, Co, Cu, Cr, Ni, Rb, Sr, Tl and Zn in caps and of Ag, Co, Cu, Mn, Ni, Sr, U and Zn in stipes and also for the macro elements K, P, Na and Mg. The fruitbodies of A. fulva from the northern (Baltic Sea coastal forests) and southwestern (Lower Silesia forests) sites differed substantially in cadmium, lead and uranium, and those from the Lower Silesia region showed them in greater concentrations. This observation may imply that A. fulva under typical geochemical site conditions is able to regulate the accumulation of many of the elements mentioned in fruiting bodies.

Specific accumulation of cadmium and other trace elements in Sarcodon imbricatus using ICP-MS with a chemometric approach.

Fungi can effectively accumulate various metallic elements, metalloids and non-metals in fruiting bodies. This study provides information on the accumulation of Ag, As, Ba, Cd, Co, Cs, Cu, Cr, Li, Mn, Ni, Pb, Rb, Sr, V, Tl, U and Zn in the edible mushroom Sarcodon imbricatus (L.) P. Karst. using the technique of inductively coupled plasma - mass spectrometry with a dynamic reaction cell mode. Mushrooms were foraged from four regions in Poland. Baseline concentrations of minerals, expressed in mg kg-1 dry biomass (db), were in the composite samples of caps in the range: for Ag (0.27-0.29), As (1.0-1.9), Ba (0.31-0.45), Cd (4.5-6.3), Co (0.23-1.9), Cu (28-35), Cr (0.19-0.29), Cs (20-38), Li (0.013-0.020), Mn (5.9-8.8), Ni (0.81-1.4), Pb (0.94-1.6), Rb (490-700), Sr (0.14-0.19), Tl (0.058-0.11), U (0.002-0.002), V (0.044-0.054) and Zn (140-160). Concentration levels of Ag, As, Cd, Cs, Pb and Zn were higher in caps than in stipes of S. imbricatus, whereas for other elements the distribution between caps and stipes was nearly equal or for some differed depending on the location. Certainly, the content of toxic Cd in S. imbricatus was elevated (0.45-0.63 mg kg-1 in fresh caps) and therefore eating this mushroom could increase exposure to Cd. In addition, the content of toxic As in S. imbricatus was elevated.

Metal concentrations in hair of patients with various head and neck cancers as a diagnostic aid.

Head and neck cancers are one of the most frequent cancers worldwide. This paper attempts to evaluate disturbances of homeostasis of the necessary elements (calcium, magnesium, zinc, copper, iron, manganese) and changes in the levels of toxic metals (lead, cadmium, cobalt, chromium VI) in hair of patients with head and neck cancers, as well as people without a diagnosed neoplastic disease. In order to quantify the necessary elements and toxic metals, a method using ICP-MS and ICP-OES techniques had been developed and validated. The studies have shown that patients with head and neck cancer used to drink alcohol and smoked much more frequently than healthy individuals, both in the past and presently. Statistically significant differences in concentrations of average metal content in the group of patients with head and neck cancers compared to the control group were confirmed. Significant differences in metal content between the group of patients with head and neck cancers and healthy individuals were found which enabled distinguishing between the study groups. To this end, a more advanced statistical tool, i.e. chemometrics, was used. The conducted research analyses and the use of advanced statistical techniques confirm the benefits of using alternative material to distinguish the patients with head and neck cancers from the healthy individuals.

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.

Heavy metal contents in the sediments of astatic ponds: Influence of geomorphology, hydroperiod, water chemistry and vegetation.

The contents of heavy metals (Cd, Cr, Cu, Ni, Pb, Zn) were analysed in the bottom sediments of 30 small, astatic ponds located in the agricultural landscape of Western Poland. The samples were collected from 118 stations located in patches of four vegetation types. Relationships between the contents of particular elements and four groups of factors (geomorphology, hydroperiod, water quality and vegetation) were tested using Redundancy Analysis (RDA). The most important factors influencing the heavy metal contents were the maximum depth and area of the pond, its hydroperiod, water pH and conductivity values. In general, low quantities of heavy metals were recorded in the sediments of kettle-like ponds (small but located in deep depressions) and high in water bodies of the shore-bursting type (large but shallow). Moreover, quantities of particular elements were influenced by the structure of the vegetation covering the pond. Based on the results, we show which types of astatic ponds are most exposed to contamination and suggest some conservation practices that may reduce the influx of heavy metals.

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.

Are there different requirements for trace elements in eumelanin- and pheomelanin-based color production? A case study of two passerine species.

Melanin is the most common pigment in animal integuments including bird plumage. It has been shown that several trace elements may play roles in the production and signaling function of melanin-colored plumage. We investigated coloration and content of various metal elements in the rectrices of two insectivorous passerines, Common Redstarts (Phoenicurus phoenicurus) and Blackcaps (Sylvia atricapilla), which have eumelanin- and pheomelanin-based coloration, respectively. We hypothesized that 1) the two species would differ in concentrations of metals important in melanin synthesis (Ca, Fe, Cu, Zn), 2) differences in metal concentration levels would be related to feather coloration. Our study confirmed the first prediction and provides the first evidence that selected elements may play a greater role in pheomelanin than in eumelanin synthesis. Concentrations of three elements considered as important in melanin synthesis (Ca, Fe, Zn) were 52% to 93% higher in rusty colored Common Redstart feathers compared to the dark gray Blackcap feathers. However, element concentrations were not correlated with feather coloration or sex in either species. Our study suggests that, of the two melanin forms, pheomelanin synthesis may bear higher costs associated with the acquisition of specific elements or limited elements may create trade-offs between ornamentation and other physiological functions. Our findings warrant further investigations designed to better understand the roles of macro- and microelements in the synthesis of both forms of melanin.

Storm water contamination and its effect on the quality of urban surface waters.

We studied the effect of storm water drained by the sewerage system and discharged into a river and a small reservoir, on the example of five catchments located within the boundaries of the city of Poznan (Poland). These catchments differed both in terms of their surface area and land use (single- and multi-family housing, industrial areas). The aim of the analyses was to explain to what extent pollutants found in storm water runoff from the studied catchments affected the quality of surface waters and whether it threatened the aquatic organisms. Only some of the 14 studied variables and 22 chemical elements were important for the water quality of the river, i.e., pH, TSS, rain intensity, temperature, conductivity, dissolved oxygen, organic matter content, Al, Cu, Pb, Zn, Fe, Cd, Ni, Se, and Tl. The most serious threat to biota in the receiver came from the copper contamination of storm water runoff. Of all samples below the sewerage outflow, 74% exceeded the mean acute value for Daphnia species. Some of them exceeded safe concentrations for other aquatic organisms. Only the outlet from the industrial area with the highest impervious surface had a substantial influence on the water quality of the river. A reservoir situated in the river course had an important influence on the elimination of storm water pollution, despite the very short residence time of its water.