An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters

• A hydrophilic resin (GCHM) was facile synthesis and characterized. • Average absolute recovery of GCHM (75.6%) performs better than Oasis^® HLB. • Detection limits of method (SPE-UPLC-MS/MS) ranged between 0.03 and 0.6 ng/L. • 22 PPCPs were determined in environmental waters ranging from 0.5 to 1590 ng/L. In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis^® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r²>0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.     

Potential toxic elements in stream sediments,soils and waters in an abandoned radium mine (central Portugal)

Environmental Geochemistry and Health - The Alto da Várzea radium mine (AV) exploited ore and U-bearing minerals, such as autunite and torbernite. The mine was exploited underground from 1911...     

Use of seaweeds for monitoring trace elements in coastal waters

Concentrations of a wide range of trace elements: arsenic, cadmium, cobalt, chromium, hafnium, nickel, thorium, uranium, zinc and the rare earth elements, cerium, europium, samarium, terbium and ytterbium were determined by instrumental neutron activation analysis in the brown alga,Fucus vesiculosus from Eckwarder Hörne, North Sea and from Rügen, Baltic Sea. Another brown alga,Sargassum filipendula from Sri Lanka, Indian ocean (representing an unpolluted control station) was similarly investigated. Cobalt, chromium and nickel concentrations were highest inF. vesiculosus from the North Sea while zinc was highest in samples from the Baltic Sea, reflecting high levels of these elements in coastal waters of the North and the Baltic sea. Cadmium, cobalt, nickel and zinc levels were lowest inS. filipendula from Sri Lanka, probably demonstrating lower levels of those elements in coastal waters. Concentration levels of hafnium, thorium, uranium, and the rare earth elements were highest inS. filipendula. Two years later in 1994,S. filipendula along withUlva sp. (green alga) was resampled from the same sampling site, and in addition to the above elements, six other trace elements (Ag, Ba, Br, Rb, Se and Sr) were determined.Sargassium filipendula showed a particular affinity for Ag, As, Br and Sr. For the other elements, marginal concentration differences were observed betweenS. filipendula andUlva sp., probably reflecting the regional background levels. Substantially higher concentrations of Hf, Th, U, and the rare earths were found again in the 1994Sargassum andUlva samples, reflecting the effect of a substrate rich in rare earth elements. The brown algae used in this study may be used to monitor trace elements in coastal waters.     

An exposure-risk assessment for potentially toxic elements in rice and bulgur

Rice and wheat are rich sources of essential elements. However, they may also accumulate potentially toxic elements (PTE). Bulgur, the popular alternative to rice in the eastern Mediterranean, is produced by processing wheat, during which PTE content may change. This study determined PTE concentrations in rice and bulgur collected from 50 participant households in the city of Izmir, Turkey, estimated ingestion exposure, and associated chronic-toxic and carcinogenic human health risks. Comparison of the determined concentrations to the available standard levels and the levels reported in the literature revealed that Cd, Co, and Pb in rice might be of concern. The estimated health risks of individual participants supported this result with exceedance of respective threshold or acceptable risk levels at the 95th percentile. Population risk estimates indicated that the proportion with higher than the threshold or acceptable risk is about 10, 24, and 12% for Cd, Co, and Pb in rice, respectively. Results of this study showed that health risks associated with PTE exposure through bulgur consumption are lower than those of rice, and below the threshold or acceptable risk levels.     

Distribution of toxic and essential elements in various chicken organs

An instrumental neutron activation technique was applied to determine toxic, essential and other elements in various chicken organs namely; liver, heart, gizzard, breast and leg. The range, arithmetic mean, geometric mean and median were computed which indicate normal distribution pattern for Hg, Se, Cl, Fe, Zn, Mn, Na, K and Cs in the five chicken organs. The concentration of Hg, Se, As, Fe, Zn and Mn in local chicken liver were also compared with the literature values. Dietary intake value for toxic and essential elements were also computed and compared with the recommended values.     

Potentially toxic elements in some fresh water bodies in Ethiopia

A total of thirty three water samples were collected from Tinishu Akaki River, Lake Awassa, and Lake Ziway, Ethiopia. Multi-element determination of trace elements (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Ag, Cd, Sn, Hg, and Pb) in water samples was carried out by inductively coupled plasma-mass spectrometry after acidification with 1% HNO₃. The concentration (in µg?L^?1) of the elements were in the range of 1.0–19, <0.42–83, 1.1–1580, <45–1760, <0.11–2.0, 0.43–13, 0.77–13, 6–300, <0.94–2.0, <0.3–1.5, <0.012–0.63, 0.13–4.8, <0.29, and 0.2–7.2 for V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Ag, Cd, Sn, Hg, and Pb, respectively. The concentrations of all the quantified elements, with the exception of Mn, were in the range of the permissible limits of the Ethiopian, European Community, and World Health Organization for both drinking water quality guidelines and irrigation water guidelines. The accuracy of the method was validated by analyzing trace elements in water standard reference material (SRM 1643e). The measured values of trace elements in the SRM agreed well with the certified values at the 95% confidence level.     

Spatial environmental risk evaluation of potential toxic elements in stream sediments

Potential toxic elements (PTE), in stream sediments, were used as contamination indicators for the definition of high-/low-grade spatial clusters in the Monfortinho area (Central Portugal). A set of 271 stream sediment samples was used for spatial modelling and further definition of rings of enrichment—high and low rings. A three-step multivariate statistical and geostatistical approach was used: (1) principal components analysis for PTE’s association evaluation and dimensionality reduction; (2) ordinary kriging as an unbiased interpolator for content inference and construction of a continuous representation of the considered attributes, at any arbitrary spatial location; (3) G clustering algorithm for the definition of high and low significance clusters. A moderate contamination in stream sediments is observed for almost all the considered PTE and a very high contamination for Ba, Cr and B. High contamination clusters are observed for Fe, Ni, Ba, Cu, B, Zn, V—northwest and southeast clusters—and for Cr—north and southwest clusters. The contamination degree index varies from moderate to high, which is mainly associated with the old mineralizations. The high computed rings often overlap the areas of abandoned Ba–Zn mineralization, as well as the sedimentary gold concentrations, along the Erges River banks. Tin and Cd spatial distribution may be related to former cassiterite exploitations in the survey area. Chromium is possibly connected with the schists. The definition of clusters with a PTE spatial enrichment will allow for the identification of contamination activities and therefore, the definition of adequate monitoring and mitigation actions.     

Essential and toxic elements in meat of wild and bred animals

Essential and toxic elements were determined by Energy Dispersive Polarized X-Rays Fluorescence Spectrometry (EDPXRF) in the meat of 145 wild and bred animals to provide the baseline data regarding meat of wild and bred animals consumed in central Italy. As far as K, Fe, Ni, Zn, and Cu are concerned, no significant differences resulted between young and adults and between males and females for farmed and wild animals. No marked differences were found between hunted and non-hunted animals groups. In all samples analyzed, Mn, Cr, and Mo were below the detection limit. As far as the non-essential or toxic elements are concerned, As, Cd, V, and Hg concentrations in muscle from wild and bred animals were low and always below the detection limits. Among the wild animals killed with lead (Pb) bullets, elevated Pb concentrations in tissues were detected. This finding may result in elevated Pb levels in meat ingested by humans.     

Comparison of methods used to calculate typical threshold values for potentially toxic elements in soil

The environmental quality of land can be assessed by calculating relevant threshold values, which differentiate between concentrations of elements resulting from geogenic and diffuse anthropogenic sources and concentrations generated by point sources of elements. A simple process allowing the calculation of these typical threshold values (TTVs) was applied across a region of highly complex geology (Northern Ireland) to six elements of interest; arsenic, chromium, copper, lead, nickel and vanadium. Three methods for identifying domains (areas where a readily identifiable factor can be shown to control the concentration of an element) were used: k-means cluster analysis, boxplots and empirical cumulative distribution functions (ECDF). The ECDF method was most efficient at determining areas of both elevated and reduced concentrations and was used to identify domains in this investigation. Two statistical methods for calculating normal background concentrations (NBCs) and upper limits of geochemical baseline variation (ULBLs), currently used in conjunction with legislative regimes in the UK and Finland respectively, were applied within each domain. The NBC methodology was constructed to run within a specific legislative framework, and its use on this soil geochemical data set was influenced by the presence of skewed distributions and outliers. In contrast, the ULBL methodology was found to calculate more appropriate TTVs that were generally more conservative than the NBCs. TTVs indicate what a “typical” concentration of an element would be within a defined geographical area and should be considered alongside the risk that each of the elements pose in these areas to determine potential risk to receptors.     

Concentrations of inorganic elements in bottled waters on the Swedish market

This study presents the concentrations of about 50 metals and ions in 33 different brands of bottled waters on the Swedish market. Ten of the brands showed calcium (Ca) concentrations ≤10 mg L⁻¹ and magnesium (Mg) levels <3 mg L⁻¹, implying very soft waters. Three of these waters had in addition low concentrations of sodium (Na; <7 mg L⁻¹), potassium (K; <3 mg L⁻¹) and bicarbonate (HCO₃ ≤31 mg L⁻¹). These brands were collected from barren districts. Nine of the brands were collected from limestone regions. They showed increased Ca-levels exceeding 50 mg L⁻¹ with a maximum of 289 mg L⁻¹. Corresponding Mg-levels were also raised in two brands exceeding 90 mg L⁻¹. Two soft and carbonated waters were supplemented with Na₂CO₃ and NaCl, resulting in high concentrations of Na (644 and 648 mg L⁻¹) and chloride (Cl; 204 and 219 mg L⁻¹). Such waters may make a substantial contribution to the daily intake of NaCl in high water consumers. The storage of carbonated drinking water in aluminum (Al) cans increased the Al-concentration to about 70 μg L⁻¹. Conclusion As there was a large variation in the material as regards concentrations of macro-elements such as Ca, Mg, Na, K and Cl. Supplementation with salts, e.g., Na₂CO₃, K₂ CO₃ and NaCl, can lead to increased concentrations of Na, K and Cl, as well as decreased ratios of Ca/Na and larger ratios of Na/K. Water with high concentrations of e.g., Ca and Mg, may make a substantial contribution to the daily intake of these elements in high water consumers. Al cans are less suited for storage of carbonated waters, as the lowered pH-values may dissolve Al. The levels of potentially toxic metals in the studied brands were generally low.     

About plant species potentially promising for phytoextraction of large amounts of toxic trace elements

There is no information yet about plant species capable of accumulating many different metals/metalloids. The plants feasible for phytoremediation aims must grow fast, have high biomass, deep roots, and should accumulate and tolerate a range of toxicants in their aerial parts. In our research, greenhouse and field experiments have been performed to investigate accumulation and tolerance of not well-studied trace elements such as Br, Eu, Sc, Th (and also U) in couch grass and wheat. We compared bioaccumulation abilities of the plants with those of some other plant species grown under the same conditions. Additionally, we tested the effects of inoculation of seeds with Cellulomonas bacteria on phytoextraction of the trace elements from contaminated soils. For determination of elements, we used neutron activation analysis and ICP-MS. It was found that couch grass and wheat can grow in heavily contaminated soils and accumulate different toxic trace elements to levels that exceed physiological requirements typical for most plant species. Infection of seeds with bacteria resulted in a significant increase in the uptake of various trace elements and their translocation to upper plant parts. The use of couch grass and/or wheat, either alone or in combination with microorganisms, is a promising way to phytoextract metals/metalloids from contaminated soils.

     

Urinary stones as a novel matrix for human biomonitoring of toxic and essential elements

Monitoring of body burden of toxic elements is usually based on analysis of concentration of particular elements in blood, urine and/or hair. Analysis of these matrices, however, predominantly reflects short- or medium-term exposure to trace elements or pollutants. In this work, urinary stones were investigated as a matrix for monitoring long-term exposure to toxic and essential elements. A total of 431 samples of urinary calculi were subjected to mineralogical and elemental analysis by infrared spectroscopy and inductively coupled plasma mass spectrometry. The effect of mineralogical composition of the stones and other parameters such as sex, age and geographical location on contents of trace and minor elements is presented. Our results demonstrate the applicability of such approach and confirm that the analysis of urinary calculi can be helpful in providing complementary information on human exposure to trace metals and their excretion. Analysis of whewellite stones (calcium oxalate monohydrate) with content of phosphorus <0.6 % has been proved to be a promising tool for biomonitoring of trace and minor elements.

     

Mobility of toxic elements in carbonate sediments from a mining area in Poland

The Boles?aw–Bukowno mining area in Poland is highly polluted by elements such as Zn, Pb, Cd and As. The reactivity and mobility of toxic elements such as Tl are poorly known. Here, we studied by sequential extraction the mobility of As, Cd, Co, Cr, Cu, Mn, Mo, Pb, Tl and Zn in sediments from two water reservoirs near Bukowno. Results show that available As, Co, Mn, Pb and Zn are found in carbonate minerals. Available Cd, Cu and Tl are found in sulphides and organic matter. The extractability of As, Cr, Mo and Tl was rather poor. By contrast, 85 % of total Cd, Pb and Zn was mobile. We discuss Tl and Mo association in carbonate sediments from ore deposits.     

Use of a physiologically based extraction test to estimate the human bioaccessibility of potentially toxic elements in urban soils from the city of Glasgow,UK

A simple, two-stage, physiologically based extraction has been applied to assess the human bioaccessibility of potentially toxic elements (PTE) in 20 urban soils from a major UK city. Chromium and iron bioaccessibilities were found to be markedly higher in the intestinal phase, whilst lead and zinc bioaccessibilities were higher in the stomach. Copper and manganese bioaccessibilities were generally similar under both extraction conditions. Principal component analysis was used to study relationships amongst bioaccessible element concentrations and land use. Distinctions could be observed between the distributions of the urban metals—copper, lead and zinc—and metals predominantly of geogenic origin, such as iron. There was no clear delineation between roadside soils and soils obtained from public parks. Bioaccessible analyte concentrations were found to be correlated with pseudototal (aqua regia soluble) analyte concentrations for all elements except iron. Results of the BCR sequential extraction did not, in general, provide a good indication of human bioaccessibility. Comparison of bioaccessible PTE concentrations with toxicological data indicated that lead is the element of greatest concern in these soils but that levels are unlikely to pose a health risk to children with average soil intake.     

基于改性石墨烯固相萃取-液相色谱法测定联苯菊酯

以石墨粉末为原料通过Hummers法逐步合成磁性胺基化石墨烯(Fe3O4-NH2-G),分别用扫描电镜和FTIR对其表面形貌和化学结构进行表征,并对Fe3O4-NH2-G用于实际样品中联苯菊酯的吸附性能进行了研究.以高效液相色谱为检测手段,对洗脱液和淋洗液的选择、萃取时间和洗脱时间、离子强度、溶液p H、吸附剂总量等相关参数进行优化.实验结果表明,用1%乙酸乙腈溶液做洗脱液,50%甲醇水溶液作为淋洗液,吸附时间洗脱时间都是20 min,溶液p H值为7,不加Na Cl时吸附效果最好.在293 K下改性石墨烯的平衡吸附量136 mg·g-1.实验表明最优条件下检出限达到1.7 ng·m L-1,线性范围为0.005—10μg·m L-1,方法对实际样品的加标回收率91.8%—101.6%,可应用于痕量联苯菊酯的测定.该实验研究表明Fe3O4-NH2-G对联苯菊酯有很好的吸附能力.     

Low levels of toxic elements in Dead Sea black mud and mud-derived cosmetic products

Natural muds used as or in cosmetics may expose consumers to toxic metals and elements via absorption through the skin, inhalation of the dried product, or ingestion (by children). Despite the extensive therapeutic and cosmetic use of the Dead Sea muds, there apparently has been no assessment of the levels of such toxic elements as Pb, As, or Cd in the mud and mud-based products. Inductively coupled plasma mass spectrometry analysis of eight toxic elements in samples collected from three black mud deposits (Lisan Marl, Pleistocene age) on the eastern shore of the Dead Sea in Jordan revealed no special enrichment of toxic elements in the mud. A similar analysis of 16 different commercial Dead Sea mud cosmetics, including packaged mud, likewise revealed no toxic elements at elevated levels of concern. From a toxic element standpoint, the Dead Sea black muds and derivative products appear to be safe for the consumer. Whatever the therapeutic benefits of the mud, our comparison of the elemental fingerprints of the consumer products with those of the field samples revealed one disturbing aspect: Dead Sea black mud should not be a significant component of such items as hand creams, body lotions, shampoo, and moisturizer.     

Enrichment of potentially toxic elements in areas underlain by black shales and slates in Korea

The Okchon black shale in Korea provides an important example of natural geological materials containing toxic elements; the Chung-Joo, Duk-Pyung, Geum-Kwan, I-Won and Chu-Bu areas are underlain by these black shales and slates of the Guryongsan Formation. This formation is part of the Okchon Group which is found in the central part of Korea. Geochemical surveys were undertaken in these five study areas in the Okchon Zone in order to examine the level of enrichment and dispersion patterns of potentially toxic elements in rocks and soils. After appropriate preparation, samples were analysed by instrumental neutron activation analysis and inductively coupled plasma atomic emission spectrometry for a range of elements. Arsenic, Cu, Mo, V, U and Zn are highly enriched in the Okchon black shales and their mean concentrations are significantly higher than those in black slates. These elements are closely associated with one another from a geochemical viewpoint and may be enriched simultaneously. Mean concentrations of As, Mo and U in soils derived from black shales occurring in the Duk-Pyung and Chu-Bu areas are higher than the permissible level suggested by Kloke (1979), and the enrichment index decreases in the order of Duk- Pyung > Chu-Bu > Chung-Joo > Geum-Kwan = I-Won areas. Uranium-bearing minerals such as uraninite and brannerite have been identified in black shales from the Chung-Joo area by electron probe micro-analysis. Uraninite grains are closely associated with monazite and pyrite with a grain size ranging from 2m to 10m whereas brannerite grains occur as a euhedral form 50m in diameter.     

Assessment of potentially toxic elements in Swiss chard and sediments of Akaki River,Ethiopia

For the determination of 15 potentially toxic elements (V, Cr, Fe, Mn, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sn, Hg, and Pb) in plant and sediment samples of the Akaki River, Ethiopia, inductively coupled plasma–mass spectrometry, inductively coupled plasma–optical emission spectrometry, and a RA-915+ mercury analyzer were applied. Sediment and plant samples were mineralized using a closed-vessel microwave-assisted digestion system. The elemental concentrations varied considerably in plant and sediment samples. The minimum concentration was observed for known toxic elements (As, Hg, and Cd) while the highest concentration was observed for the elements of relatively low toxicity Zn, Mn, and Fe. The concentration of Cr, Fe, Pb, Zn, and As in Swiss chard surpassed the maximum permissible levels at specific sites. At some of the sites, the sediment quality guidelines are surpassed for Cu, Zn, and Pb.     

液液提取-固相萃取-LC-MS/MS测定人体尿液中有机磷系阻燃剂及其二酯类代谢物

本研究基于液液提取和固相萃取技术建立了检测人体尿液中有机磷系阻燃剂(OPFRs)及其二酯类代谢产物(diesters)的前处理方法,采用液相色谱串联三重四极杆质谱(LC-MS/MS)进行定性定量分析.根据OPFRs与diesters理化性质的差异,尿液酶解后采用甲基叔丁基醚(MTBE)与二氯甲烷:正己烷(4∶1,V/V)混合液提取,有机相经Florisil固相萃取柱净化,乙酸乙酯洗脱后,测定OPFRs含量;水相过Strata-X-AW柱萃取,5%三乙胺/乙腈(V/V)洗脱后,测定diesters含量.在优化的实验条件下,OPFRs和diesters在相应浓度范围内呈良好线性关系,相关系数r介于0.9978—0.9997之间;尿液样品中OPFRs加标回收率平均值在72.4%—125%之间,RSD为0.62%—4.40%;6种diesters平均加标回收率为79.7%—126%,RSD介于2.20%—9.75%之间.本方法所需样品量少且能对OPFRs和diesters同时进行检测,方法的平行性好、结果可靠.使用该方法对15例尿液样品中的OPFRs与diesters含量进行分析发现,尿液中OPFRs检出率较低,7种OPFRs检出率均小于50%;6种diesters中仅双(丁氧乙基)磷酸酯(BBOEP)未在任何样品检出,其余5种diesters检出率介于33.3%—93.3%之间,其中磷酸二苯酯(DPHP)和双(1,3-二氯-2-丙基)磷酸酯(BDCIPP)检出率分别达93.3%和86.7%,是检出最高的两种化合物.     

Phytoremediation of potentially toxic elements using constructed wetlands in coastal areas with a mining influence

Environmental Geochemistry and Health - This paper proposes the use of wetlands as a phytoremediation strategy for areas of mining and maritime influence in the southeast of Spain. Potentially...