Consumption of freshwater fish: A variable but significant risk factor for PFOS exposure.

PFOS, PFOA, PFNA and PFHxS are the PFAS substances that currently contribute most to human exposure, and in 2020 the European Food Safety Authority (EFSA) presented a draft opinion on a tolerable intake of 8 ng/kg/week for the sum of these four substances (equaling 0.42 µg/kg if expressed as an annual dose). Diet is usually the dominating exposure pathway, and in particular the intake of PFOS has been shown to be strongly related to the consumption of fish and seafood. Those who eat freshwater fish may be especially at risk since freshwater and its biota typically display higher PFOS concentrations than marine systems. In this study, we estimated the range in PFOS intake among average Swedish "normal" and "high" consumers of freshwater fish. By average we mean persons of average weight who eat average-sized portions. The "normal consumers" were assumed to eat freshwater fish 3 times per year, and the "high consumers" once a week. Under these assumptions, the yearly tolerable intake for "normal" and "high" consumers is reached when the PFOS concentrations in fish equals 59 and 3.4 µg per kg fish meat. For this study, PFOS concentrations in the muscle tissue of edible-sized perch, pike and pikeperch were retrieved from three different Swedish datasets, covering both rural and urban regions and a total of 78 different inland waters. Mean PFOS concentrations in fish from these sites varied from 0.3 to 750 µg/kg. From the available data, the annual min-max dietary PFOS intake for male "normal consumers" was found to be in the range 0.0021-5.4 µg/kg/yr for the evaluated scenarios, with median values of 0.02-0.16 µg/kg/yr. For male "high consumers", the total intake range was estimated to be 0.04-93 µg/kg/yr, with median values being 0.27-1.6 µg/kg/yr. For women, the exposure estimates were slightly lower, about 79% of the exposure in men. Despite highly variable PFOS concentrations in fish from different sites, we conclude that the three most commonly consumed freshwater species in Sweden constitute an important source for the total annual intake even for people who eat this kind of fish only a few times per year. The analyses of PFOA, PFNA and PFHxS showed values which were all below detection limit, and their contribution to the total PFAS intake via freshwater fish consumption is negligible in comparison to PFOS.

Failure of generic risk assessment model framework to predict groundwater pollution risk at hundreds of metal contaminated sites: Implications for research needs.

Soil pollution constitutes one of the major threats to public health, where spreading to groundwater is one of several critical aspects. In most internationally adopted frameworks for routine risk assessments of contaminated land, generic models and soil guideline values are cornerstones. In order to protect the groundwater at contaminated sites, a common practice worldwide today is to depart from health risk-based limit concentrations for groundwater, and use generic soil-to-groundwater spreading models to back-calculate corresponding equilibrium levels (concentration limits) in soil, which must not be exceeded at the site. This study presents an extensive survey of how actual soil and groundwater concentrations, compiled for all high-priority contaminated sites in Sweden, relate to the national model for risk management of contaminated sites, with focus on As, Cu, Pb and Zn. Results show that soil metal concentrations, as well as total amounts, constitute a poor basis for assessing groundwater contamination status. The evaluated model was essentially incapable of predicting groundwater contamination (i.e. concentrations above limit values) based on soil data, and erred on the "unsafe side" in a significant number of cases, with modelled correlations not being conservative enough. Further, the risk of groundwater contamination was almost entirely independent of industry type. In essence, since neither soil contaminant loads nor industry type is conclusive, there is a need for a supportive framework for assessing metal spreading to groundwater accounting for site-specific, geochemical conditions.

Urban vegetable contamination - The role of adhering particles and their significance for human exposure.

While urban-grown vegetables could help combat future food insecurity, the elevated levels of toxic metals in urban soils need to be met with measures that minimise transfer to crops. This study firstly examines soil/dust particle inclusion in leafy vegetables and its contribution to vegetable metals (As, Ba, Cd, Co, Cr, Cu, Ni, Pb, Sb, and Zn), using vegetable, soil and dust data from an open-field urban farm in southeastern Sweden. Titanium concentrations were used to assess soil/dust adherence. Results showed that vegetables contained 0.05-1.3 wt% of adhering particles (AP) even after washing. With 0.5 % AP, an adult with an average intake of vegetables could ingest approximately 100 mg of particles per day, highlighting leafy vegetables as a major route for soil/dust ingestion. The presence of adhering particles also significantly contributed to the vegetable concentrations of As (9-20 %), Co (17-20 %), Pb (25-29 %), and Cr (33-34 %). Secondly, data from an indoor experiment was used to characterise root metal uptake from 20 urban soils from Sweden, Denmark, Spain, the UK, and the Czech Republic. Combining particle adherence and root uptake data, vegetable metal concentrations were calculated for the 20 urban soils to represent hypothetical field scenarios for these. Subsequently, average daily doses were assessed for vegetable consumers (adults and 3-6 year old children), distinguishing between doses from adhering particles and root uptake. Risks were evaluated from hazard quotients (HQs; average daily doses/tolerable intakes). Lead was found to pose the greatest risk, where particle ingestion often resulted in HQs > 1 across all assessed scenarios. In summary, since washing was shown to remove only a portion of adhering metal-laden soil/dust particles from leafy vegetation, farmers and urban planners need to consider that measures to limit particle deposition are equally important as cultivating in uncontaminated soil.

Future food contaminants: An assessment of the plant uptake of Technology-critical elements versus traditional metal contaminants.

Technology-critical elements (TCEs) include most rare earth elements (REEs), the platinum group elements (PGEs), and Ga, Ge, In, Nb, Ta, Te, and Tl. Despite increasing recognition of their prolific release into the environment, their soil to plant transfer remains largely unknown. This paper provides an approximation of the potential for plant uptake by calculating bioconcentration factors (BCFs), defined as the concentration in edible vegetable tissues relative to that in cultivation soil. Here data were obtained from an indoor cultivation experiment growing lettuce, chard, and carrot on 22 different European urban soils. Values of BCFs were determined from concentrations of TCEs in vegetable samples after digestion with concentrated HNO3, and from concentrations in soil determined after 1) Aqua Regia digestion and, 2) diluted (0.1 M) HNO3 leaching. For comparison, BCFs were also determined for 5 traditional metal contaminants (TMCs; As, Cd, Cu, Pb, and Zn). The main conclusions of the study were that: 1)BCF values for the REEs were consistently low in the studied vegetables;2)the BCFs for Ga and Nb were low as well;3) the BCFs for Tl were high relative to the other measured TCEs and the traditional metal contaminants; and 4) mean BCF values for the investigated TCEs were generally highest in chard and lowest in carrot. These findings provide initial evidence that there are likely to be real and present soil-plant transfer of TCEs, especially in the case of Tl. Improvements in analytical methods and detection limits will allow this to be further investigated in a wider variety of edible plants so that a risk profile may be developed.

Trace and major elements in food supplements of different origin: Implications for daily intake levels and health risks.

As the use of food supplements increases, voices are being raised questioning the safety of these products. As a contribution to understanding the trace and major elemental composition of food supplements and their potential health risks, this study presents concentrations of 71 elements in 138 supplements, categorised into synthetic products and three groups of products with natural ingredients. Concentrations were converted into average daily doses (ADDs) and compared to tolerable daily intakes (TDIs). For elements where we found significant ADDs relative to the TDI a comparison was also made to the normal dietary intake. Our main findings are that: 1) Most elements display highly variable concentrations in food supplements; more so than in normal foodstuff; 2) For ten of the analysed elements some products rendered ADDs > 50 % of the TDI. Half of the elements were essential (Fe, Mn, Se, Mo, Zn), and as such motivated in food supplements. The other half (As, Pb, Cd, Al, Ni) represent non-essential and highly toxic elements, where the occurrence in food supplements ought to be viewed as contamination. Although none of these toxic metals were declared on any product's table of content, several products gave high ADDs - in several cases even exceeding the TDIs; 3) The risk of reaching high ADDs for the toxic elements is strongly associated with products that contain marine ingredients (e.g. algae, mussels etc), and to some degree products of terrestrial plant-based origin. The health of consumers would benefit if food regulatory frameworks were updated to better address the risks of food supplements occasionally being contaminated with different toxic metals, for example by setting maximum permissible concentrations for a longer list of elements.

Metal solubility and transport at a contaminated landfill site - From the source zone into the groundwater.

Risks associated with metal contaminated sites are tightly linked to material leachability and contaminant mobility. In this study, metal solubility and transport were characterized within a glass waste landfill through i) lysimeter-collection of pore water and standardized batch leaching tests, ii) soil profiles extending from the landfill surface, through unsaturated soil underneath, and into the groundwater zone, and iii) groundwater samples upstream, at, and downstream of the landfill. The soil analyzes targeted both pseudo-total and geochemically active concentrations of contaminant metals (As, Cd, Pb, Sb) and basic soil geochemistry (pH, org. C, Fe, Mn). Water samples were analyzed for dissolved, colloid-bound and particulate metals, and speciation modelling of the aqueous phase was conducted. The results revealed a highly contaminated system, with mean metal concentrations in the waste zone between 90 and 250 times the regional background levels. Despite severe contamination of the waste zone and high geochemically active fractions (80-100%) of all contaminant metals as well as elevated concentrations in landfill pore water, the concentrations of Cd and Pb decrease abruptly at the transition between landfill and underlying natural soil and no indication of groundwater contamination was found. The efficient cation retention is likely due to the high pH. However, the sorption of As and Sb is weaker at such high pH, which explains their higher mobility from the pore water zone into groundwater. The field soil:solution partitioning (Kd) displayed a high spatial variability within the waste zone (the highest Kd variability was seen for Pb, ranging from 140 to 2,900,000 l kg-1), despite little variability in basic geochemical variables, which we suggest is due to waste material heterogeneity.

Assessing toxicity of metal contaminated soil from glassworks sites with a battery of biotests.

The present study addresses toxicological properties of metal contaminated soils, using glassworks sites in south-eastern Sweden as study objects. Soil from five selected glassworks sites as well as from nearby reference areas were analysed for total and water-soluble metal concentrations and general geochemical parameters. A battery of biotests was then applied to assess the toxicity of the glassworks soil environments: a test of phytotoxicity with garden cress (Lepidium sativum); the BioTox™ test for toxicity to bacteria using Vibrio fischeri; and analyses of abundancies and biomass of nematodes and enchytraeids. The glassworks- and reference areas were comparable with respect to pH and the content of organic matter and nutrients (C, N, P), but total metal concentrations (Pb, As, Ba, Cd and Zn) were significantly higher at the former sites. Higher metal concentrations in the water-soluble fraction were also observed, even though these concentrations were low compared to the total ones. Nevertheless, toxicity of the glassworks soils was not detected by the two ex situ tests; inhibition of light emission by V. fischeri could not be seen, nor was an effect seen on the growth of L. sativum. A decrease in enchytraeid and nematode abundance and biomass was, however, observed for the landfill soils as compared to reference soils, implying in situ toxicity to soil-inhabiting organisms. The confirmation of in situ bioavailability and negative effects motivates additional studies of the risk posed to humans of the glassworks villages.

The risk of overestimating the risk-metal leaching to groundwater near contaminated glass waste deposits and exposure via drinking water.

This study investigates metal contamination patterns and exposure to Sb, As, Ba, Cd and Pb via intake of drinking water in a region in southeastern Sweden where the production of artistic glass has resulted in a large number of contaminated sites. Despite high total concentrations of metals in soil and groundwater at the glassworks sites properties, all drinking water samples from households with private wells, located at a 30-640m distance from a glassworks site, were below drinking water criteria from the WHO for Sb, As, Ba and Cd. A few drinking water samples showed concentrations of Pb above the WHO guideline, but As was the only element found in concentrations that could result in human exposure near toxicological reference values. An efficient retention of metals in the natural soil close to the source areas, which results in a moderate impact on local drinking water, is implied. Firstly, by the lack of significant difference in metal concentrations when comparing households located upstream and downstream of the main waste deposits, and secondly, by the lack of correlation between the metal concentration in drinking water and distance to the nearest glassworks site. However, elevated Pb and Cd concentrations in drinking water around glassworks sites when compared to regional groundwater indicate that diffuse contamination of the soils found outside the glassworks properties, and not only the glass waste landfills, may have a significant impact on groundwater quality. We further demonstrate that different mobilization patterns apply to different metals. Regarding the need to use reliable data to assess drinking water contamination and human exposure, we finally show that the conservative modelling approaches that are frequently used in routine risk assessments may result in exposure estimates many times higher than those based on measured concentrations in the drinking water that is actually being used for consumption.

High metal reactivity and environmental risks at a site contaminated by glass waste.

This study addresses the reactivity and risks of metals (Ba, Cd, Co, Cr, Cu, Ni, Pb, Zn, As and Sb) at a Swedish site with large glass waste deposits. Old glassworks sites typically have high total metal concentrations, but as the metals are mainly bound within the glass waste and considered relatively inert, environmental investigations at these kinds of sites are limited. In this study, soil and landfill samples were subjected to a sequential chemical extraction procedure. Data from batch leaching tests and groundwater upstream and downstream of the waste deposits were also interpreted. The sequential extraction revealed that metals in <2 mm soil/waste samples were largely associated with geochemically active fractions, indicating that metals are released from pristine glass and subsequently largely retained in the surrounding soil and/or on secondary mineral coatings on fine glass particles. From the approximately 12,000 m(3) of coarse glass waste at the site, almost 4000 kg of Pb is estimated to have been lost through corrosion, which, however, corresponds to only a small portion of the total amount of Pb in the waste. Metal sorption within the waste deposits or in underlying soil layers is supported by fairly low metal concentrations in groundwater. However, elevated concentrations in downstream groundwater and in leachates of batch leaching tests were observed for several metals, indicating on-going leaching. Taken together, the high metal concentrations in geochemically active forms and the high amounts of as yet uncorroded metal-rich glass, indicate considerable risks to human health and the environment.

The neuromelanin of the human substantia nigra.

The pigment of the human substantia nigra was isolated after extraction of lipids and proteins with 2% sodium cholate in 30% ethanol followed by 2% sodium dodecyl sulfate in 10% glycerol. The pigment was hydrolysed with HI or degraded by treatment with KMNO4 and the samples were examined for compounds known to derive from pheomelanin (4-amino-3-hydroxyphenylalanine, AHP and 4-amino-3-hydroxyphenylethylamine, AHPEA), or from eumelanin (pyrrole-2,3,5-tricarboxylic acid, PTCA). The HI hydrolysis yielded AHPEA in large quantities, indicating cysteinyldopamine as the main source of the pheomelanin moiety of the neuromelanin, but also trace amounts of AHP, derived from cysteinyldopa oxidation products. Dopamine and small quantities of dopa were also obtained by HI hydrolysis of the neuromelanin. The yield of PTCA was low, but the amounts observed show that part of the neuromelanin is of the eumelanin type, a fact compatible with an occasional exhaustion of the glutathione-cysteine reduction system at the site of neuromelanin formation.

Conformation dependence of electronic structures of poly(ethylene oxide).

The electronic structure of pure poly(ethylene oxide) (PEO) for four different polymeric chain conformations has been studied by Hartree-Fock (HF) and density functional theory (DFT) through the analysis of their valence band photoelectron spectroscopy (VB-PES), X-ray emission spectroscopy (XES), and resonant inelastic X-ray scattering (RIXS). It is shown that the valence band of PEO presents specific conformation dependence, which can be used as a fingerprint of the polymeric structures. The calculated spectra have been compared with experimental results for PEO powder.

UVB irradiation induces melanocyte increase in both exposed and shielded human skin.

This study demonstrates for the first time in humans that UV light induces an increase of the melanocyte population in exposed skin as well as in shielded areas. Because an increased mitotic activity could promote tumor development, UV exposure might play a role in melanoma development not only in exposed but also in covered skin. In addition, it was found that subjects who initially had a small melanocyte population showed a larger increase in both exposed and covered skin compared to those with a high initial density. Individuals with a low density might therefore constitute a risk group for the development of malignant melanoma. These findings support the view that infrequent periods of intensive UV irradiation might be more harmful than regular exposure.

Urinary excretion of 5-S-cysteinyldopa in relation to skin type, UVB-induced erythema, and melanocyte proliferation in human skin.

5-S-Cysteinyldopa (5-S-CD) is found in all pigment-producing cells and is the major precursor of phaeomelanin. However, the melanocyte specificity of the compound has been questioned. In order to elucidate the origin of 5-S-CD, we have now systematically studied the relationship between the 5-S-CD excretion in urine and the size of the melanocyte organ, UV-induced melanocyte proliferation, skin type, and the erythemal reaction. The skin type had no influence on the basal excretion of 5-S-CD. There was no significant correlation between the basal 5-S-CD excretion and the size of the melanocyte organ; that is, the number of skin melanocytes and nevi. During the irradiation, subjects with skin type II developed a more pronounced erythema (p less than 0.01) and had a significantly higher 5-S-CD excretion than those with skin type III-IV (p less than 0.01). No correlation was found between 5-S-CD excretion and UV-induced melanocyte proliferation. The lack of correlation between the basal 5-S-CD excretion and skin type or number of melanocytes suggests that the basal 5-S-CD in urine is mainly of extra-melanocytic origin. Our findings favor the view that the increase in 5-S-CD excretion during UV irradiation is due to UV damage.

Regional distribution of common and dysplastic naevi in relation to melanoma site and sun exposure. A case-control study.

The frequency of melanoma (CMM), and of common and dysplastic naevi (CN and DN) in areas of skin chronically, intermittently and rarely exposed to UV light was investigated in 121 melanoma patients (30-50 years) and 310 controls. Both cases and controls had significantly more CN in intermittently exposed areas than in areas chronically or rarely exposed. The ratio of observed to expected number of CMM was also highest in intermittently exposed skin (1.3 compared to 0.8 in chronically exposed and 0.5 in rarely exposed areas). Thus, intermittent UV exposure seems to have the most potent 'naevogenic' as well as carcinogenic effect on melanocytes. Nineteen per cent of controls and 56% of cases had naevi fulfilling the clinical criteria for DN. The distribution pattern of DN was clearly different from that of CN and does not accord with the idea that UV light is a major aetiological factor for DN. The probability of CMM significantly increased with the degree of relative clustering of CN (p less than 0.05) and of DN (p less than 0.01). This co-variation of naevi and CMM over the body surface might be the result of the local insults to the melanocyte system caused by UV light and/or to the fact that naevi are precursor lesions of CMM.

Melanocytic naevi, melanoma and sun exposure.

The naevus profile was examined in 379 randomly selected Swedes (30-50 years) and in 121 melanoma patients in the same age-range selected from the Regional Cancer Register. The total body count of common naevi (CN) greater than or equal to 2 mm in the population was high (mean 67, range 1-300). Even so, the melanoma patients had almost twice as many CN as the controls (mean 113, range 13-347). The prevalence of clinical dysplastic naevi (DN) was 18% in the population and 56% in the patients. The corresponding figures for histologically diagnosed DN were 8% and 40% respectively. Subjects with dysplastic naevi had a significantly larger number of CN than those without DN. Subjects with a sun-sensitive skin, greater than or equal to 150 naevi and presence of DN had a 50 times higher melanoma risk than those without these characteristics. For identifying subjects at risk of developing cutaneous malignant melanoma (CMM), clinically diagnosed DN was as good a discriminator as histologically diagnosed DN. The numbers of naevi in different skin areas were tested for their power in predicting the total body naevus count. The strongest correlations were found between total counts and counts on the anterior surface of the thighs and the lateral aspect of the arms. Counts from either of these areas will provide a practical and satisfactory estimate of the total number of naevi. To study the possible link between sun exposure, naevus formation and melanoma development, the distribution of CN, DN and CMM over the body surface was studied in the 121 melanoma patients and in 310 consecutive controls. The number of naevi was four times as high in a sun-exposed area on the lower back compared with in an adjacent sun-protected area on the buttocks, indicating that sunlight plays a role in naevus development. Both CN and CMM were found to have a general distribution pattern over the body surface consistent with the idea that sun exposure is important for their formation. The number of CN and CMM per unit body surface area was significantly higher in intermittently sun-exposed than in rarely or chronically exposed skin. The distribution pattern of DN was quite different from that of CN, with few DN on the sun-exposed upper chest and face and many DN in protected areas such as the buttocks and lower abdomen, indicating that DN may develop independently of sun exposure.(ABSTRACT TRUNCATED AT 400 WORDS)

Electron correlation and charge transfer in superconducting superlattices.

We use x-ray spectroscopy to examine the electronic structure of high-temperature superconducting superlattices [(Ba0.9Nd0.10)CuO(2 + delta)]2/[CaCuO2]2. The O 2p density of states reveals the insulating character of the individual component layers and the metallic character of the superlattices. We report the first direct observation of Zhang-Rice singlets in artificial high-temperature superconducting heteroepitaxial structures. The experimental findings in the superlattices and its component layers offer evidence of charge transport from the so-called charge reservoir layer to the superconducting infinite layer. This suggests a strong link between superconductivity and both electron correlation and charge transfer within the superlattices.

Electronic structure of phospho-olivines Li(x)FePO4 (x = 0, 1) from soft-x-ray-absorption and -emission spectroscopies.

The electronic structure of the phospho-olivine Li(x)FePO4 was studied using soft-x-ray-absorption (XAS) and emission spectroscopies. Characteristic changes in the valence and conduction bands are observed upon delithation of LiFePO4 into FePO4. In LiFePO4, the Fe-3d states are localized with little overlap with the O-2p states. Delithiation of LiFePO4 gives stronger hybridization between Fe-3d states and O-2p states leading to delocalization of the O-2p states. The Fe L-edge absorption spectra yield "fingerprints" of the different valence states of Fe in LiFePO4 and FePO4. Resonant soft-x-ray-emission spectroscopy at the Fe L edge shows strong contributions from resonant inelastic soft x-ray scattering (RIXS), which is described using an ionic picture of the Fe-3d states. Together the Fe L-edge XAS and RIXS study reveals a bonding character of the Fe 3d-O2p orbitals in FePO4 in contrast to a nonbonding character in LiFePO4.

Atopic dermatitis and melanocytic naevi.

A study was performed to test the clinical impression that adults with severe atopic dermatitis (AD) have a low number of common naevi (CN). The number of CN > or = 2 mm was investigated in 51 Caucasian patients aged 20-63 years with severe AD since early childhood. The control group consisted of 379 randomly selected subjects, aged 30-50 years, investigated in an earlier study. Patients with AD had a significantly (P < 0.0001) lower total body count of CN (mean 9, median 5) compared with the control group (mean 67, median 53). It was also found that in the AD group there was a significant (P < 0.001) negative correlation between serum IgE and number of CN [r(s) = -0.50, 95% CI (-0.69; -0.24)]. The explanation for the low number of naevi that we have found in this highly selected subgroup of AD patients is not known. The atopic inflammation in the skin, genetics and treatment used for eczema are possible factors that may influence the formation of melanocytic naevi.

Regional distribution of melanocytic naevi in relation to sun exposure, and site-specific counts predicting total number of naevi.

The role of exposure to ultraviolet light in the formation of melanocytic naevi was analysed by investigating the regional naevus distribution in 310 subjects (30-50 years) from a Swedish census file. The lateral aspect of the arms and the back had the largest concentration of naevi. The mean naevus count per unit surface area was higher in intermittently exposed than in rarely exposed skin (p less than 0.001), while the lowest mean count was found in chronically exposed skin. These results support the idea that intermittent exposure to ultraviolet light has a "naevogenic" effect while chronic exposure might be protective. Dysplastic naevi had a distribution pattern quite different from common naevi. Considering the distribution pattern solely, dysplastic naevi seem to develop independently of exposure to ultraviolet light. The numbers of naevi in different skin areas were tested for their power in predicting the total body naevus count. The strongest correlations were found between total counts and counts on the anterior surface of the thighs and the lateral aspect of the arms. Counts from any of these areas will provide a practical and satisfactory estimate of the total number of naevi.

Melanocytic naevi in sun-exposed and protected skin in melanoma patients and controls.

The possible link between exposure to ultraviolet light and naevus development was studied in 121 melanoma patients and 310 controls by comparing the number of naevi in a sun-exposed area on the back with that in a sun-protected area on the buttocks. Both patients and controls had a four-fold increase in the number of naevi in the exposed compared with the protected area, p less than 0.001. The difference in naevus count between the exposed and the protected area was larger in patients than in controls, p less than 0.001. Subjects with dysplastic naevi, melanoma patients as well as controls, had a larger difference in the number of naevi between the two areas than subjects without dysplastic naevi, p less than 0.001. These results support the idea that sunlight plays an important role in naevus development and may explain why a high naevus count is a risk marker for malignant melanoma.