Chemometric evaluation of inorganic and organic parameters found in Rosaceae plants proposed as food supplements.

This study discusses the organic and inorganic composition of young inflorescence tissues of seven medical plants from the Prunus, Malus, and Chaenomeles families. These plants contain bioactive compounds with antioxidant and cytotoxic properties, and the study determined 29 elements, including essential and potentially harmful ones, established correlations with inorganic and organic compounds, as well as antioxidative and cytotoxic effects. The elemental patterns show that the plants contribute beneficial essential elements to the human diet. The levels of toxic elements in the plants are within safe limits set by the World Health Organization for medicinal herbs. The results confirmed genus- and species-specific uptake and accumulation. Positive correlations between d-block metals and alkaline earth metals in the inflorescences were found alongside statistically significant differences between analyte categories regarding macro-, micro- and trace elements and bioactive compounds. These correlations need to be considered when giving dietary recommendations or advice for uses as home-remedies.

Preliminary Study of Pepper Types Based on Multielement Content Combined with Chemometrics.

Different types of pepper (Piper nigrum L.) and cayenne pepper (Capsicum annuum L.) are widely used spices that exhibit therapeutic properties in addition to nutritional properties. In order to characterize these foods in further detail, the content of macro- (Ca, K, Mg, Na) and microelements (Ag, Al, As, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mn, Mo, Ni, Pb, Rb, Se, Sr, Te, Tl, V and Zn) of four pepper types was determined via inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted digestion using nitric acid and hydrogen peroxide. The obtained results were then evaluated using chemometric methods. The content of macroelements and microelements lies in the expected ranges for such spices but differs significantly between different types. The content of macro- and microelements is characteristic for pepper types originating from different plant species, but also based on further processing. Whilst green and black pepper are similar to each other, clearly diverse patterns are obtained for white pepper (different processing method) and cayenne pepper (different plant species).

Multielement Determination in Turmeric (Curcuma longa L.) Using Different Digestion Methods.

The antioxidant, anti-inflammatory and antiseptic properties of turmeric (Curcuma longa L.) derive from its rich nutritional composition making it interesting for medicinal uses, besides being used as spice in cooking. To complete the picture on the composition of turmeric, not only the organic compounds need to be known, but also the elemental composition covering essential and potentially toxic elements. The samples were digested in a microwave assisted digestion system using different reagent mixtures. The best digestion mixture was semi-concentrated nitric acid combined with hydrogen peroxide. After optimization of the sample preparation method, the contents of Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Se, Sr, Te, Tl, V and Zn in curcuma were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES), as well as by inductively coupled plasma mass spectrometry (ICP-MS). Even if the general composition found is in line with the scarce data in literature, clear differences can be seen between the analyzed samples, considering provenience, production procedures, and harvesting year as potential influencing factors. Whereas all samples contained less As and Pb than regulated by WHO, one limit exceeding was found for Cd.

Influence of Soil Salinity on Selected Element Contents in Different Brassica Species.

Climate changes in coastal regions cause increased soil salinity, a well-known type of environmental stress for a high number of agricultural crop species, including Brassicaceae, whose growth and development, and consequently the crop quality and yield, are affected by salinity stress. The aim of the present study is to investigate the effect of salt stress on micro- and macro-element homeostasis in different Brassica crops. Kale (Brassica oleracea var. acephala), white cabbage (B. oleracea var. capitata) and Chinese cabbage (B. rapa ssp. pekinensis) were grown hydroponically and treated with 200 mmol/L sodium chloride for 24 h to mimic short-term salt stress. The contents of Al, Ca, K, Mg, Na, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn were determined in the roots and leaves of the salt-treated plants and corresponding controls by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. While Al, Ca, K, Mg and Na were determined in the mg/g range, the contents of the other elements were found at the µg/g level. A statistical analysis of the obtained data showed that the applied salt treatment significantly influenced the single-element contents in different plant parts. The major elements Ca, K and Mg were mainly unaffected in the more-salt-tolerant kale and white cabbage under salinity stress, while K and Mg were significantly decreased in the more-sensitive Chinese cabbage. The levels of micro-elements were found to be species/variety specific. In general, potentially toxic elements were accumulated in the roots of salt-treated plants to a higher extent than in the corresponding controls.

Accumulation of Major, Minor and Trace Elements in Pine Needles (Pinus nigra) in Vienna (Austria).

Increasing heavy metal pollution in the environment and the fact that pine needles are good bio-monitors for air pollutants was the reason to investigate their accumulation in pine needles in Vienna (Austria). Pinus nigra is widespread over the city, thus allowing the study of different parameters influencing metal accumulation. The sampling sites were chosen based on traffic volume (low, medium, high). Fresh shoots were collected alongside one-year-old needles once per week from May to August 2015. The needle samples were washed and dried prior to acidic microwave-assisted digestion followed by quantitative determination using spectrometric methods. The investigation was focused on the following elements: Ag, Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Se, Sr, U, V, and Zn. The one-year-old needles mainly contained higher contents of elements than fresh shoots; in many cases, the values differed statistically significantly. By correlating needle elemental contents with the sampling site, statistically significant differences were registered for the majority of the investigated elements. These differences originate from the local traffic situation, soil elemental levels, translocation processes, and not traffic-related sources. No general trend of metal accumulation from spring to summer was registered.

Geographic Differences in Element Accumulation in Needles of Aleppo Pines (Pinus halepensis Mill.) Grown in Mediterranean Region.

Pine needles are widely used as bio-indicators due to their worldwide distribution and the ease of sample collection. In contrast to deciduous trees, conifers offer the possibility of monitoring long-term exposure through older needles. Pinus halepensis Miller is a pine species native to the Mediterranean region, which has been used for restoration activities in arid and semiarid areas leading to vast spatial expansion. Needles from pine trees collected in the southeastern to northwestern extension of Croatia's coastal area at twelve sampling sites were analysed for twenty-one metals and metalloids. Statistical evaluation of the obtained data revealed significant differences for Al, As, B, Ba, Ca, Cr, Fe, K, Mg, Mn, Na, Se, and Sr between the different regions. Needles from trees growing on islands did not show elevated levels of Mg and/or Na as a result of the sea spray influence. The differences in metal accumulation are supposed to be linked to the environmental conditions at the respective sampling site, since the species was the same everywhere. By comparing the elemental contents of the soil those of with needles, it can be clearly seen, that the root as well as the foliar uptake contribute to the final amount.

Mineral Composition of Elements in Walnuts and Walnut Oils.

Walnuts (Juglans nigra) are considered to be a functional food. In the present study, twenty one macro-, micro-, and trace elements (Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Se, Sr, and Zn) were selected to be determined in walnuts and walnut oils. The beneficial content of essential elements could be shown by the obtained results, the macro-elements Ca, K, Mg, and Na being present in nuts with 1062 mg/kg, 2771 mg/kg, 1426 mg/kg, and 42.3 mg/kg, respectively. Regarding micro- and trace elements, the following order (decreasing content) was found: Mn > Fe > Zn > B, Mo > Cu > Ni > Co > Al > Sr > Ba > Li > Pb > Se > Cr > As > Cd. Furthermore, the potentially toxic trace elements (As, Cd, Pb) determined were below the maximum allowed values in most of the investigated walnut samples. A comparison of oils and nuts revealed that the former contain lower concentrations of all elements analyzed except for Fe and Zn. This suggested the origin from contamination during oil processing. Fe influences the oil oxidation rate, thus its entry during production should be avoided.

Harmful Elements (Al, Cd, Cr, Ni, and Pb) in Wild Berries and Fruits Collected in Croatia.

Fruits and vegetables are considered a beneficial contribution to the human diet. Especially, berries contain a great deal of bioactive compounds, such as anthocyanins, organic acids, tannins, phenols, and antioxidants. Apart from organic substances, inorganic nutrients are also present in fruits. Some metals and metalloids are essential for humans, whilst others may exhibit harmful effects. Wild grown berries, collected in so-called unpolluted areas, are considered to be free of any potentially toxic ingredients. However, due to transmission processes pollutants can also reach remote areas and, furthermore, metal uptake from the soil via roots has to be taken into account. Thus, the presented study focused on the determination of Al, Cd, Cr, Ni, and Pb in lingonberries, blueberries, and rose hips collected in a non-polluted area in Croatia. Neither Cd nor Cr could be found in any sample. Ni levels were mainly up to 25 mg/kg, in a comparable range to the literature data. No health threat is to be expected by eating these fruits and berries regarding Cd, Cr, and Ni. Rose hips, however, contain Pb beyond the stipulated limit in fruits, and also Al is present at a high level (8 mg/g).

Influence of F1 hybridization on the metal uptake behaviour of pine trees (Pinus nigra x Pinus thunbergiana; Pinus thunbergiana x Pinus nigra).

Pine needles have been considered to be useful bio-indicators for air pollution. This phenomenon can be used for environmental studies for monitoring purposes. Additionally, this fact offers the possibility to study uptake and accumulation behaviour not only in different species, but also in hybrids obtained from common pine trees to inheritage processes. Therefore, needles of Pinus nigra Arnold and Pinus thunbergiana Franco as well as of their F1 hybrids were investigated for essential and non-essential metals, such as Al, B, Ba, Ca, Cd, Co, Cu, Cr, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sr, and Zn. The samples underwent acidic microwave-assisted digestion prior to analysis inductively coupled plasma atomic emission spectrometry (ICP-AES). Furthermore flavonoids were quantitatively determined to prove hybrid character. Regarding all determined analytes, increase and decrease of uptake in the needles of the hybrids were evaluated in comparison to the needles of the parent pine species to see which parent is the dominant one. In the hybrids higher amounts of Al, Cd, Mo, Ni, Mg, Mn, and Zn were found. Different behaviour was registered for flavonoids than for metals, due to different metabolic pathways.

Inorganic Macro- and Micronutrients in "Superberries" Black Chokeberries (Aronia melanocarpa) and Related Teas.

Black chokeberries (Aronia melanocarpa) are considered to be functional food containing high amounts of anthocyanins, phenols, antioxidants, vitamins and minerals. Whereas organic compounds are well studied, there is little research on the mineral composition of the chokeberries. Thus, the presented study is focused on the determination of Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Se, Sr and Zn in black chokeberry fruits and infusions to study the metals' extractability. The nutrients Ca, K and Mg are present in the fruits (dried matter) at g/kg level, whereas the other elements are present from µg/kg up to mg/kg level. The extraction yields of the metals from the infusion range from 4 (Al, Mn) up to 44% (Na). The toxic elements present do not pose any health risk when berries or infusions are consumed. Concluding, Aronia berries, as well as infusions derived from them, are a good dietary source of essential metals in addition to the organic compounds also contained.

Study of the Accumulation of Toxic and Essential Ultra-Trace Elements in Fruits of Sorbus domestica L.

In the present work, the accumulation of selected toxic and essential ultra-trace elements in fruits of service tree (Sorbus domestica L.) were determined depending on harvest time. Samples were collected from the same sampling area in two different years and within one year in September and October (maturity state). Harvesting the fruits in the same area excludes the influence of metals taken up via roots, thus the impact of airborne contamination by heavy metal translocation can be studied. All samples were dried and digested using an acidic microwave assisted digestion system prior to quantification by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS). The elements chosen were Arsenic and Cadmium as well as Lithium, Molybdenum, and Selenium. The Arsenic content rose with maturity in mesocarp. Cadmium found in the mesocarp was unaffected by ripeness. For Selenium and Molybdenum, no statistically significant effect of ripeness could be found on their content in mesocarp. Lithium could not be detected in the majority of fruit samples. Differences between the metal concentrations based on the year of harvest were found for Arsenic, Molybdenum, and Selenium, depending on precipitation. The drier the season, the more Arsenic was accumulated. For Molybdenum and Selenium, the opposite effect was observed.

Metal characterization of white hawthorn organs and infusions.

Hawthorn is one of the most commonly used European and North American phytopharmaceuticals. Because there is no information on metals in seeds, and only rare data for leaves and flowers, the aim of the present study was elemental analysis of the white hawthorn (Crataegus monogyna) by inductively coupled plasma emission spectrometry (ICP-AES) or inductively coupled plasma mass spectrometry (ICP-MS) after digestion in a microwave-assisted system. The limits of detection are below 2 µg/g for ICP-AES and 0.5 µg/g for ICP-MS. Hawthorn leaves and flowers contain essential elements at concentrations (mean values, RSD 2-8%) in mg/g of Ca, 1-4; K, 4-5; Mg, 1-2; and Na, <0.2); and at µg/g levels of Ba, 1-10; Co, <0.16; Cr, <1.4; Cu, 0.6-7; Fe, 1-37; Li, <0.5; Mn, 1-13; Mo, <0.17; Ni, <0.6; Sr, 0.2-2; and Zn, 1-31. Toxic elements were found in low quantities: As (<0.04), Cd (0.04-0.1), and Pb (0.1-2). Up to 10% of the metals is extracted into the infusions. The analyzed plant parts and infusions contain essential elements justifying its use as a medicinal plant, whereas the low quantities of harmful elements will not pose any risk to humans when consumed.

Elemental characterisation of the medical plant Alchemilla velebitica.

Alchemilla, commonly called "lady's mantle", is a genus of herbaceous perennial plants belonging to the family Rosaceae. The species Alchemilla velebitica is found only in Southern Europe, like in the Croatian National Park Northern Velebit. Its benefits, such as a astringent and emmenagogue activity as well as wound healing are correlated to the organic compounds found in the plant, but also certain trace elements are known to reduce skin lesions, such as zinc, selenium, copper, manganese, silicon and lithium. Thus the objective of the present study was the elemental characterization of leaves, blossoms and roots of A. velebitica. After acidic microwave assisted digestion the concentrations of selected essential and trace elements were determined by inductively coupled plasma--atomic emission spectrometry and inductively coupled plasma--mass spectrometry. Other minor elements, such as Al, B, Cu, Fe, Mn, Sr and Zn are also found in leaves, blossoms and roots with contents in µg/kg range. The preparation of decoctions and the extraction yields of the elements of interest are calculated.

Influence of soil composition on the major, minor and trace metal content of Velebit biomedical plants.

The use of medical herbs for the treatment of many human diseases is increasing nowadays due to their mild features and low side effects. Not only for their healing properties, but also for their nutritive value supplementation of diet with various herbs is recommended. Thus also their analysis is of rising importance. While total elemental compositions are published for many common herbs, the origin of toxic as well as beneficial elements is not yet well investigated. Thus different indigenous medicinal plants, namely Croatian spruce (Picea abies), savory (Satureja montana L.), mountain yarrow (Achillea clavennae), showy calamint (Calamintha grandiflora), micromeria (Micromeria croatica), yellow gentian (Gentiana lutea) and fir (Abies alba) together with soil samples were collected in the National Park Northern Velebit. The macro- and trace elements content, after microwave digestion, was determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and inductively coupled plasma mass spectroscopy (ICP-MS). The study focuses on the one hand on essential elements and on the other hand on non-essential elements which are considered as toxic for humans, covering in total Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr and Zn.

The determination of the extractability of selected elements from agricultural soil.

Concentrations of Ag, Al, Ba, Cd, Co, Cr, Cu, Fe, K, Mn, Na, Ni, Pb, Sr, and Zn-isolated by sequential extraction steps from apple orchard soil-were analyzed by inductively coupled plasma-atomic emission spectroscopy and compared to the total amount of metal in soil determined by XRF. The extractable amount of each metal was calculated by the extraction yields of the four steps. The LODs of the different elements in all extracts ware below 3 µg/L except for Ba (steps 1 and 2), Cu (step 1), Fe (all steps), K (steps 1-3), Mn (step 2), Na (steps 1-3), Ni (step 1), Pb (steps 1 and 4), and Zn (steps 1 and 2). The highest LOD (>10 µg/L) was found for Fe, K, and Na (step 1). The recovery of all metals after four sequential extraction steps was 90-112%. The repeatability (<1.1%), the intermediate precision (<5.3%), the day-to-day reproducibility (<6.2%), and the overall uncertainty of measurement (approximately 4-8.5%) for all analyzed metals supports the choice of the method used.

Removal of Cr, Mn, and Co from textile wastewater by horizontal rotating tubular bioreactor.

Environmental pollution by industrial wastewaters polluted with toxic heavy metals is of great concern. Various guidelines regulate the quality of water released from industrial plants and of surface waters. In wastewater treatment, bioreactors with microbial biofilms are widely used. A horizontal rotating tubular bioreactor (HRTB) is a combination of a thin layer and a biodisc reactor with an interior divided by O-ring shaped partition walls as carriers for microbial biomass. Using a biofilm of heavy metal resistant bacteria in combination with this special design provides various advantages for wastewater treatment proven in a pilot study. In the presented study, the applicability of HRTB for removing metals commonly present in textile wastewaters (chromium, manganese, cobalt) was investigated. Artificial wastewaters with a load of 125 mg/L of each metal underwent the bioreactor treatment. Different process parameters (inflow rate, rotation speed) were applied for optimizing the removal efficiency. Samples were drawn along the bioreactor length for monitoring the metal contents on site by UV-vis spectrometry. The metal uptake of the biomass was determined by ICP-MS after acidic microwave assisted digestion. The maximum removal rates obtained for chromium, manganese, and cobalt were: 100%, 94%, and 69%, respectively.

ICP-AES determination of minor- and major elements in apples after microwave assisted digestion.

The aim of this paper was to determine the content of minor and major elements in apples by inductively coupled plasma atomic emission spectrometry (ICP-AES). Prior to ICP-AES measurement, dried apples were digested in a microwave assisted digestion system. The differences in the measured element concentrations after application of open and closed microwave system as sample preparation procedures are discussed. In whole apples, flesh and peel Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr and Zn were analysed after optimisation and validating the analytical method using ICP-AES. The accuracy of the method determined by spiking experiments was very good (recoveries 88-115%) and the limits of detection of elements of interest were from 0.01 up to 14.7 µg g(-1). The reference ranges determined in all apple samples are 39-47 mg g(-1) for K, 9-14 mg g(-1) for Na, 3-7 mg g(-1) for Mg, 3-7 µg g(-1) for Zn, 0.7-2.8 µg g(-1) for Sr. The range of Mn in peel 4-6 µg g(-1) is higher compared to whole apple from 0.7 to 1.7 µg g(-1). Cd is found only in peel, in the concentration range of 0.4-1.1 µg g(-1).

Mathematical modeling of Fe(II), Cu(II), Ni(II) and Zn(II) removal in a horizontal rotating tubular bioreactor.

Industrial wastewaters polluted with toxic heavy metals are serious ecological and environmental problem. Therefore, in this study multi-heavy metals (Fe(2+), Cu(2+), Ni(2+) and Zn(2+)) removal process with mixed microbial culture was examined in the horizontal rotating tubular bioreactor (HRTB) by different combinations of process parameters. Hydrodynamic conditions and biomass sorption capacity have main impact on the removal efficiency of heavy metals: Fe(2+) 95.5-79.0%, Ni(2+) 92.7-54.8%, Cu(2+) 87.7-54.9% and Zn(2+) 81.8-38.1%, respectively. On the basis of experimental results, integral mathematical model of removal heavy metals in the HRTB was established. It combines hydrodynamics (mixing), mass transfer and kinetics to define bioprocess conduction in the HRTB. Mixing in the HRTB was described by structured cascade model and metal ion removal by two combined diffusion-adsorption models, respectively. For Langmuir model, average variances between experimental and simulated concentrations of metal ions were in the range of 1.22-10.99 × 10(-3) and for the Freundlich model 0.12-3.98 × 10(-3), respectively. On the basis of previous facts, it is clear that developed integral bioprocess model with Freundlich model is more efficient in the prediction of concentration of metal ions in the HRTB. Furthermore, the results obtained also pointed out that the established model is at the same time accurate and robust and therefore it has great potential for use in the scale-up procedure.

Determination of total chromium in tanned leather samples used in car industry.

Despite the high competition of synthetic fibers leather is nowadays still widely used for many applications. In order to ensure a sufficient stability of the skin matrix against many factors, such as microbial degradation, heat and sweat, a tanning process is indispensable. Using chromium (III) for this purpose offers a multitude of advantages, thus this way of tanning is widely applied. During the use of chromium tanned leather as clothing material as well as for decoration/covering purposes, chromium is extracted from the leather and may then cause nocuous effects to human skin, e.g. allergic reactions. Thus the knowledge of the total chromium content of leather samples expected to come into prolonged touch with human skin is very important. In car industry leather is used as cover for seats, steering wheel and gearshift lever The chromium contents often chromium tanned leather samples used in car industry were determined. First all samples were dried at 65 degrees C overnight and then cut in small pieces using a ceramic knife, weighed and analyzed by inductively coupled plasma--optical emission spectrometry (ICP-OES) after acidic microwave assisted digestion. The total chromium amounts found were in the range from 19 mg/g up to 32 mg/g. The extraction yield of chromium from leather samples in sweat is approximately 2-7%. Thus especially during long journeys in summer chromium can be extracted in amounts which may cause nocuous effects for example on the palm of the hands or on the back.

Determination of 28 selected elements in textiles by axially viewed inductively coupled plasma optical emission spectrometry.

A simple, robust and reliable analytical procedure for the determination of 28 selected elements, namely Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Hg, Mg, Mn, Mo, Na, Ni, Pb, Sc, Si, Se, Sn, Sm, Sr, Tl, V, and Zn in textile materials by inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave digestion of samples was optimized and validated in this work. The total amount of elements present in textile samples was determined after microwave digestion of materials in 7 mol/L nitric acid within the optimal working program: 5 min at 150°C (power 250 W), 15 min 180°C (300 W) and 20 min at the maximum temperature of 200°C (350 W). For the quality control reasons, which were ascertained by analysis of the certified cotton trace elements reference material IAEA-V9, the ICP-OES method was optimized through several parameters: by comparing Meinhard and Gemcone Low Flow nebulizers efficiency, ranging nebulizer gas flows from 0.6 to 1.0 L/min, ranging sample flows from 0.8 to 1.2 mL/min, testing RF power from 1200 to 1400 W, detecting data acquisition time (read time) from 0 to 527 s, ranging washing (delay) time from 0 to 408 s, as well as by checking the occurring interferences for the optimal line selection. Validation included determination of linearity, selectivity, accuracy, reproducibility, precision and limits of detection calculated for all 28 selected elements of interest. The developed analytical procedure was successfully applied on textile fibers (cotton, flax and hemp) as well as on standard knitted textile sample materials (cotton and wool).