Quantifying the functional disparity in pigment spot-background egg colour ICP-OES-based eggshell ionome at two extremes of avian embryonic development.

It is known that a developing avian embryo resorbs micronutrients (calcium and other chemical elements) from the inner layer of the eggshell, inducing thinning and overall changes in the shell's chemical composition. However, an aspect yet to be explored relates to the local changes in the multi-elemental composition (ionome) of the pigment spot and adjacent background colour regions of eggshells resulting from avian embryogenesis (with respect to two extremes of embryonic growth: the maternal level at the moment of egg laying, and after the completion of embryonic growth). To address this problem, we used inductively-coupled plasma optical emission spectrometry (ICP-OES) to establish the elemental profiles of microsamples from the cryptic eggs of Capercaillie Tetrao urogallus and Black Grouse Tetrao tetrix, representing the background colour and pigment spot regions of the shell. We then related these to the developmental stage of the eggs (non-embryonated eggs vs. post-hatched eggshells) and their origin (wild vs. captive hens). Our results show an apparent local disparity between the pigment spot and background colour regions in the distribution of chemical elements: most elements tended to be at higher levels in the speckled regions of the shell, these differences becoming less pronounced in post-hatched eggshells. The trends of changes following embryonic eggshell etching between the pigment spot and background colour shell regions were conflicting and varied between the two species. We hypothesized that one potential working explanation for these interspecific differences could be based on the variable composition of elements (mostly of Ca and Mg), which are the result of the varying thickness of the individual shell layers, especially as the relative difference in shell thickness in the pigment spots and background colour regions was less in Black Grouse eggs. Overall, this investigation strongly suggests that egg maculation plays a functional role in the physiological deactivation of trace elements by incorporating them into the less calcified external shell layer but without participating in micronutrient resorption. Our major critical conclusion is that all research involving the chemical analysis of eggshells requires standardized eggshell sampling procedures in order to unify their colouration and embryonic status.

Colour-assisted variation in elytral ICP-OES-based ionomics in an aposematic beetle.

Very little is known about how the elemental composition (ionome) of an insect cuticle varies as a result of different colouration. Using inductively-coupled plasma optical emission spectrometry (ICP-OES), we established ionomic profiles in microsamples of two adjacent regions of an insect cuticle with a contrasting colour pattern, namely, the black and orange regions of the elytra of the aposematic burying beetle Nicrophorus vespillo. The analysis revealed 53 elements (ranging in atomic weight from Na to Bi) occurring above the detection limit. The frequency of detectability of individual elements varied strongly, and only ten elements (Ba, Cu, Fe, K, Mg, Mn, P, Rb, Sb and Zn) were present in concentrations exceeding the detection limit in all the samples. The sum of concentrations of all elements in the orange regions of the elytra was 9% lower than in the black ones. The opposite distribution was displayed by the rare earth elements (REEs), the sum of which was 17% lower in the black elytral regions than in the orange ones. The concentrations of six elements were significantly higher in the black than in the orange regions: Al (by 97%), Cu (41%), Mn (14%), Na (46%), Se (97%) and W (47%). The concentrations of essential elements measured in both the black and orange regions exhibited very considerable variance: Ca (σ2 = 1834; 1882, respectively), K (145; 82) P (97; 76), Na (84; 53), Mg (24; 26) and Ba (9; 13). This, in part, could be attributed to individual differences, e.g. those resulting from the consumption of animal carcasses of different quality/chemical composition, but interference between elements and the consequent lowering of measurement quality are also possible. We highlight the fact that deeper insight into the basic relationship between insect colouration and variation in elemental composition requires micro-sampling of the homogeneous layers of an exoskeleton.

Supporting dataset and methods for body sizes and concentrations of chemical elements measured in elytra and abdomens of Stag Beetles Lucanus cervus.

The dataset presented in this data paper supports "Breaking down insect stoichiometry into chitin-based and internal elemental traits: Patterns and correlates of continent-wide intraspecific variation in the largest European saproxylic beetle" (Orlowski et al. 2020). Here we present the supplementary data and description of methods on the following: (1) mass of elytra and abdomens across 28 local Stag Beetle Lucanus cervus populations in Europe. (2) Population origin and coverage of six major land-cover types, including transport infrastructure, measured in three radii (500 m, 1000 m and 5000 m) around the sampling sites of these populations. (3) The relationship between the mass and concentrations of elements measured in abdomens and elytra in 28 Stag Beetle populations and major land-cover types around the sampling sites.

Breaking down insect stoichiometry into chitin-based and internal elemental traits: Patterns and correlates of continent-wide intraspecific variation in the largest European saproxylic beetle.

Stoichiometric, trophic and ecotoxicological data have traditionally been acquired from patterns of variation in elemental traits of whole invertebrate bodies, whereas the critical issue of the extracellular origin of some portion of elements, such as those present in ingested food and internal organs, has been ignored. Here we investigated an unexplored, yet crucial, question relating to whether, and to what degree, metals from two major body fractions: exoskeleton (elytra) and internal (body organs with gut material present in abdomens), are correlated with each other in wild populations of the largest European saproxylic insect, the Stag Beetle Lucanus cervus, and how metals from these two fractions vary with insect size and local habitat conditions. We examined the continent-wide variation in the concentrations of 12 chemical elements (Ca, Mg, K, Na, Mn, Fe, Zn, Cu, As, Cd, Pb and Ni) measured in the elytra and abdomen of specimens from 28 populations inhabiting an urban-woodland habitat gradient across the species' entire distributional range from Spain to Russia. Across populations, elemental concentrations (except Ni and Pb) were 2-13 times higher in abdominal samples than in elytra, and the magnitude of these differences was related to both insect size and local habitat conditions. Smaller individuals from both woodland and urban habitat tended to have higher concentrations of trace elements (Zn, As, Cd, Pb and Ni). The concentration of only six elements (Mg, K, Na, Mn, Cd and Ni) was correlated in the elytra and abdomen at the individual and population levels, implying a limitation to the broader applicability of elytra as a surrogate for internal elemental pools. We highlight that in non-feeding adult saproxylic beetles, minerals, acquired during the larval stage, may be concentrated in the large quantities of residual body fat.

Supporting dataset for elemental traits of plant-invertebrate food web components of oilseed rape fields.

This dataset is provided in support of the paper "Edge effect imprint on elemental traits of plant-invertebrate food web components of oilseed rape fields" (Orlowski et al., 2019). Supplementary data are given on the following: (1) the full taxonomic list of invertebrates (n = 12 916) classified into food guilds and functional groups, which were sampled in 34 oilseed rape fields in SW Poland in spring 2015; (2) concentrations of 12 chemical elements measured in invertebrates; (3) the relationships between abundance and percentage (%) in the community of major invertebrate groups, and habitat variables; (4) the statistical tests comparing the concentrations of chemical elements between the different groupings of organisms; (5) the relationships between the elemental traits of oilseed rape plant samples and major functional invertebrate groupings or main taxonomic insect groups, and the habitat variables of oilseed rape fields.

Edge effect imprint on elemental traits of plant-invertebrate food web components of oilseed rape fields.

Of fundamental importance for the functioning of a community is the flow of energy and elements through its components. However, the question of how (if at all) the edge effect of habitats can drive elemental traits of organisms has hitherto been largely neglected issue in ecosystem ecology at the community level. We quantified the abundance of invertebrates and measured the elemental composition (K, Na, Ca, Mg, Cu, Zn, Fe, Mn, As, Cd, Co and Pb) of 15 different organisms within the plant-invertebrate food web (plant - oilseed rape pests/herbivores - pollinators = wild bees - saprovores - predators - parasitoids) sampled in 34 fields of a key bioenergy crop that is an exceptionally strong biodiversity driver, the oilseed rape. Then these were related to the individual field edge habitat features (including typically anthropogenic ones like dirt and tarred roads) measured within a 100 m radius around the invertebrate sampling sites. Our study showed that elemental traits of the plant-invertebrate food web components in oilseed rape crops varied owing to the habitat specificity determined at the relatively small spatial scale of an individual field, and that the elemental traits of these organisms differed from both an inter- and an intra-guild perspective. The major mechanistic explanation for most of these relationships seems to derive from the secondary gut content effect. Determining one single state for the homeostatic/stoichiometric regulation of chemical elements in invertebrates based on the application of whole-body metal concentrations is in principle impossible, because of the unknown noise caused by the inclusion of extracellular portions of metals in the analysis. It is thus imperative to develop consistent principles for assessing elemental traits of organisms that are based on highly sensitive and high-throughput analytical methods for the ionomic profiling of microsamples at the organ, tissue, cellular or even sub-cellular levels.

Supporting dataset and methods for egg sizes, eggshell thicknesses and metal concentrations measured in the shells and contents of eggs of Capercaillies Tetrao urogallus.

The dataset presented in this data paper supports "Eggshell resorption, and embryonic mobilization and accumulation of calcium and metals in eggs of wild and captive Capercaillies Tetrao urogallus" (Orlowski et al., 2019) [1]. Here we present the supplementary data on the following: (1) egg sizes, regional eggshell thicknesses (at the equator, sharp pole and blunt pole) as well as the concentrations of two major micronutrients (Ca and Mg) and eight trace elements (Cr, Cu, Mn, Fe, Co, Cd, Pb and Zn), measured in the shells and contents of eggs of captive-bred and wild Capercaillies. (2) How the proportions of elements sequestered into eggshells become depleted during embryogenesis expressed as the %change of concentrations of various elements measured in the shells and contents of eggs at different stages of embryonic advancement (early dead embryos, late dead embryos and hatched eggs). (3) The relationships between the age of dead embryos and three regional eggshell thicknesses and concentrations of different elements measured in the shells and contents of these eggs.

Eggshell resorption, and embryonic mobilization and accumulation of calcium and metals in eggs of wild and captive Capercaillies Tetrao urogallus.

Although it is fairly well known that eggshells are the major source of Ca and other micronutrients for developing avian embryos, potential anatomical and/or ecological correlates explaining the variation in embryo-induced depletion of micronutrients from eggshells remain to be addressed. Using unhatched eggs at various developmental stages and post-hatched eggshells of wild and captive-bred birds of a large precocial species, the Capercaillie Tetrao urogallus, we explored two major questions. (i) Do egg size, regional eggshell thickness as well as levels of two major micronutrients (Ca and Mg) and eight trace elements (Cr, Cu, Mn, Fe, Co, Cd, Pb and Zn) measured in egg shells and contents vary with embryonic age within and between wild and captive-bred bird eggs? (ii) How the proportions of eggshell elements become depleted during the entire process of embryogenesis? The eggshells of wild Capercaillies were thinner at the equator and the sharp pole, and contained more Mg and Ca, while in their contents there was more Cu, Cd and Pb compared with captive birds. All ten metal concentrations measured in the egg contents increased (from 15% to 285% more) with the age of embryos. The concentrations of six elements measured in eggshells (Cu, Mn, Fe, Co, Cd and Zn) decreased consistently (from 15 to 70% less) during embryogenesis. This suggests the presence of these elements in the innermost decalcified shell layer and their further mobilization into the embryos/egg contents. Our results strongly imply that most trace elements present in the egg contents/developing embryos are mobilized from the eggshells. We highlight the fact that knowledge of the magnitude of embryogenesis-related functional changes in the physical (such as shell thickness) and chemical traits of the eggs and eggshells of oviparous vertebrates is fundamental for drawing correct inferences regarding the response of an individual to variable environmental conditions.

Linking land cover satellite data with dietary variation and reproductive output in an opportunistic forager: Arable land use can boost an ontogenetic trophic bottleneck in the White Stork Ciconia ciconia.

Determining how the progressive loss of resources due to agricultural intensification and habitat degradation affect individual fitness and population persistence is a matter of urgency. Here we explored three major questions in order to extend knowledge of the relationship between reproduction rate, diet and energy intake in White Storks Ciconia ciconia based both on our own analysis of pellets and landscape properties sampled in 52 nests in south-western Poland, and published literature data. (1) How many individual prey items are needed to meet the daily energy requirements of nestlings over the brood rearing period? (2) How do the dietary patterns vary under different habitat conditions and what is the spatial scale responsible for these relationships? (3) Is reproductive output related to variations in landscape traits, and is diet variability related to intraspecific competition resulting from colonial breeding? In our estimation, the energy requirements of nestlings during the brood rearing period showed that the most profitable invertebrate prey items were Orthoptera and earthworms. Owing to the nestlings' gape-size constraint (precluding consumption of vertebrate prey items of the size of Common Voles), these most likely comprise the staple diet enabling survival during the first 20 days of life. The total energy content across all the pellets was a simple function (a negative correlation) of %arable land within a distance of 5 km around the nests. White Storks from nests of high-productivity pairs (with 3-4 fledglings and less %arable around) consumed equal %biomasses of invertebrate and vertebrate prey, while invertebrates prevailed in the diet of the low-productivity pairs. Our results suggest that a two-level ontogenetic trophic bottleneck may explain the low productivity of White Stork pairs in simplified landscapes with predominant arable land use. As a result of this, parent birds are unable to satisfy the growing energy demands of nestlings (1) by gathering a sufficient volume of abundant small-sized prey (early nestlings) and (2) by delivering energetically more profitable vertebrate prey at the time of the diet switch.

Data exploration on diet, and composition, energy value and functional division of prey items ingested by White Storks Ciconia ciconia in south-western Poland: Dietary variation due to land cover, reproductive output and colonial breeding.

The dataset presented in this data paper supports "Linking land cover satellite data with dietary variation and reproductive output in an opportunistic forager: Arable land use can boost an ontogenetic trophic bottleneck in the White Stork Ciconia ciconia" (Orlowski et al. 2019) [1]. Analysis of data on diet and prey composition based on an investigation of 165 pellets of White Storks Ciconia ciconia sampled from 52 nests showed that their diet was based primarily on 'eurytopic prey' (embracing taxa from grassland and a variety of non-cropped habitats), the biomass contribution of which in the diet was disproportionately (3-4-fold) higher than the percentage of available corresponding habitats. Similarly, prey items from water/wetland sites prevailed over the availability of corresponding habitats. The opposite pattern characterized prey taxa from arable habitats and forests, the contribution of which was lower than the availability of the corresponding habitats. The total energy content per pellet (calculated by summing the energy content of all individual prey items across one specific prey group) was the most strongly correlated with the biomass of Orthoptera, thereafter with that of mammals, other vertebrates, earthworms and other invertebrates, but not with the biomass of Coleoptera. White Storks from nests of low productivity pairs (i.e. with 1-2 fledglings) consumed a significantly (up to two-fold) higher biomass of Coleoptera, Orthoptera and all invertebrates, which also translated into a higher total biomass and a higher total energy content compared to the diet of high-productivity pairs (i.e. with 3-4 fledglings). Our data, in particular those relating to energy content in a variety of invertebrate taxa, and their body mass and functional division in terms of habitat preferences should be useful for other researchers to calculate energy budgets of predatory animals living in agricultural landscapes in Europe.

Effect of spatial resolution of soil data on predictions of eggshell trace element levels in the Rook Corvus frugilegus.

Although a considerable research effort has gone into studying the dietary pathways of metals to the bodies of laying female birds and their eggs in recent years, no detailed investigations have yet been carried out relating the properties of the biogeochemical environment at large spatial scales to eggshell trace element levels in typical soil-invertebrate feeding birds under natural conditions. We used data from a large-scale nationwide monitoring survey of soil quality in Poland (3724 sampling points from the 43 792 available) to predict levels of five trace elements (copper [Cu], cadmium [Cd], nickel [Ni], zinc [Zn] and lead [Pb]) in Rook Corvus frugilegus eggshells from 42 breeding colonies. Our major aim was to test whether differences exist in the explanatory power of soil data (acidity, content of elements and organic matter, and particle size) used as a correlate of concentrations of eggshell trace elements among four different distances (5, 10, 15 and 20 km) around rookeries. Over all four distances around the rookeries only the concentrations of Cu and Cd in eggshells were positively correlated with those in soil, while eggshell Pb was correlated with the soil Pb level at the two longest distances (15 and 20 km) around the rookeries. The physical properties of soil (primarily the increase in pH) adversely affected eggshell Cd and Pb concentrations. The patterns and factors governing metal bioaccumulation in soil invertebrates and eggshells appear to be coincident, which strongly suggests a general similarity in the biochemical pathways of elements at different levels of the food web. The increasing acidification of arable soil as a result of excessive fertilisation and over-nitrification can enhance the bioavailability of toxic elements to laying females and their eggs.

Embryonic eggshell thickness erosion: A literature survey re-assessing embryo-induced eggshell thinning in birds.

Although eggshell thinning has been described mainly in the context of environmental pollution, it can also be the effect of reproductive changes induced by a developing embryo. On the basis of a literature survey of 25 bird species (26 published papers) we reviewed data on embryo-induced eggshell thinning (EET) in three groups of birds: precocials, semi-precocials and altricials. The average EET at the equator of the eggs was 6.4% (median = 4.7%). Our review did not confirm a general prediction of elevated EET at the egg equator in precocial species: altricial birds exhibited the highest EET (average = 12.0%), followed by precocials (7.6%) and semi-precocials (4.2%). We make certain critical recommendations based on the results of this study. Studies aiming to assess variation in eggshell thickness should examine intrinsic factors affecting shell properties of avian eggs, like thickness, which are the result of anatomical or reproductive changes.

Effect of Brood Age on Nestling Diet and Prey Composition in a Hedgerow Specialist Bird, the Barred Warbler Sylvia nisoria.

The composition and quality of food provided to nestling birds influence their growth and development and offers key insight into the ecological requirements of birds. One bird species whose feeding ecology is poorly understood is the Barred Warbler (Sylvia nisoria), which utilizes semi-natural shrubby vegetation in agroecosystems. Because Barred Warbler nestlings vary greatly in body mass we hypothesised that diet and prey properties (size, diversity, taxonomic composition, and chitin content and resulting body hardness and digestibility) would differ as the nestlings aged. We quantified the diet based on faecal analysis, sampling faecal sacs from the nestlings pooled into three age classes: 2-3 days old, 4-6 d old, and 7-9 d old. Nestlings were provided a wide diversity of food and a strong relationship existed between food characteristics and nestling age. The youngest nestlings (2-3 d old) had the lowest values of each dietary characteristic (diversity, number and total biomass of prey, and individual prey weight), that were significantly lower than the oldest nestlings (7-9 d old). Nestlings aged 4-6 d exhibited intermediate dietary characteristics. Differences in dietary composition of the six major food types showed marked differences between the individual broods and age categories. Percentages of the number and biomass of soft-bodied prey were highest in the diet of 2-3 d and 4-6 d old nestlings, and decreased with increasing age, whereas the opposite trend was observed in the percentage of intermediately and heavily chitinised prey. Parent Barred Warblers probably preferentially select soft-bodied prey for the youngest nestlings, and satisfy the greater energy demands of the older ones by providing them with a greater variety of prey containing more chitin, as well as plant food. The provisioning of less-readily digestible prey to older nestlings suggests that as the quality of food decreases the quantity increases, implying that the youngest nestlings may be physiologically limited as regards their ability to digest more heavily chitinised prey.

Variable contribution of functional prey groups in diets reveals inter- and intraspecific differences in faecal concentrations of essential and non-essential elements in three sympatric avian aerial insectivores: a re-assessment of usefulness of bird faeces in metal biomonitoring.

Aerial insectivores through their insect diet can contribute to biotransfer of elements across habitats. We investigate the relationship between dietary composition as expressed by the contributions of six functional invertebrate prey groups (primarily of agriculturally subsidised invertebrates characteristic of agricultural areas in temperate regions of Europe) and concentrations of essential (Na, K, Ca, Mg, Fe, Cu, Zn, Mn, Co) and non-essential (As, Cd, Pb) elements of environmental concern in the faeces of nestlings of three species of avian aerial insectivores - Common Swift Apus apus, Barn Swallow Hirundo rustica and House Martin Delichon urbicum - which breed sympatrically and use apparently similar resources of flying insect prey. There were significant differences between the species for 7 of the 12 elements (Ca, Zn, Cu, Co, As, Pb, Cd); these differences were attributable to the variable dietary composition, even though the concentrations of the elements varied enormously between the faecal samples from the individual species. Partial correlation analysis between the biomass (expressed in mg dry weight) of the six functional prey groups and faecal concentrations of elements showed the highest number of significant relationships for toxic metals (As, Pb and Cd). The results of the General Regression Model explaining faecal element concentrations revealed the different explanatory power of the effects of PCA (of six functional prey groups) dietary scores. A significant fit of GRM was obtained for 7 elements (Na, Mg, Fe, Mn, As, Pb, Cd) for Barn Swallows, 2 elements (Cu, As) for House Martins and 1 element (Mn) for Common Swifts. Overall, the results confirmed our predictions that the biomass of consumed coprophilous taxa and insects from crop habitats was positively correlated with the faecal concentrations of toxic elements. Unexpectedly, however, the faecal samples (primarily those of Common Swifts) that contained many oil-seed rape insect pests had lower Ca, Pb and Cd levels and a higher As level. Our study implies that the cross-boundary transfer of contaminants, primarily non-essential elements, by aerially foraging birds through the considerable accumulation of their faeces has potential consequences for the local biogeochemical cycle and environmental quality.

Functional invertebrate prey groups reflect dietary responses to phenology and farming activity and pest control services in three sympatric species of aerially foraging insectivorous birds.

Farming activity severely impacts the invertebrate food resources of farmland birds, with direct mortality to populations of above-ground arthropods thorough mechanical damage during crop harvests. In this study we assessed the effects of phenological periods, including the timing of harvest, on the composition and biomass of prey consumed by three species of aerial insectivorous birds. Common Swifts Apus apus, Barn Swallows Hirundo rustica and House Martins Delichon urbica breed sympatrically and most of their diet is obtained from agricultural sources of invertebrate prey, especially from oil-seed rape crops. We categorized invertebrate prey into six functional groups, including oil-seed rape pests; pests of other arable crops; other crop-provisioned taxa; coprophilous taxa; and taxa living in non-crop and mixed crop/non-crop habitats. Seasonality impacted functional groups differently, but the general direction of change (increase/decrease) of all groups was consistent as indexed by prey composition of the three aerial insectivores studied here. After the oil-seed rape crop harvest (mid July), all three species exhibited a dietary shift from oil-seed rape insect pests to other aerial invertebrate prey groups. However, Common Switfts also consumed a relative large quantity of oil-seed rape insect pests in the late summer (August), suggesting that they could reduce pest insect emigration beyond the host plant/crop. Since these aerially foraging insectivorous birds operate in specific conditions and feed on specific pest resources unavailable to foliage/ground foraging avian predators, our results suggest that in some crops like oil-seed rape cultivations, the potential integration of the insectivory of aerial foraging birds into pest management schemes might provide economic benefits. We advise further research into the origin of airborne insects and the role of aerial insectivores as agents of the biological control of crop insect pests, especially the determination of depredation rates and the cascading effects of insectivory on crop damage and yield.

Residues of chromium, nickel, cadmium and lead in Rook Corvus frugilegus eggshells from urban and rural areas of Poland.

We examined the concentrations of chromium (Cr), nickel (Ni), cadmium (Cd) and lead (Pb) in Rook Corvus frugilegus eggshells from 43 rookeries situated in rural and urban areas of western (=intensive agriculture) and eastern (=extensive agriculture) Poland. We found small ranges in the overall level of Cr (the difference between the extreme values was 1.8-fold; range of concentrations=5.21-9.40 Cr ppm), Ni (3.5-fold; 1.15-4.07 Ni ppm), and Cd (2.6-fold; 0.34-0.91 Cd ppm), whereas concentrations of Pb varied markedly, i.e. 6.7-fold between extreme values (1.71-11.53 Pb ppm). Eggshell levels of these four elements did not differ between rural rookeries from western and eastern Poland, but eggshells from rookeries in large/industrial cities had significantly higher concentrations of Cr, Ni and Pb than those from small towns and villages. Our study suggests that female Rooks exhibited an apparent variation in the intensity of trace metal bioaccumulation in their eggshells, that rapid site-dependent bioaccumulation of Cu, Cr, Ni and Pb occurs as a result of the pollution gradient (rural

Trace-element interactions in Rook Corvus frugilegus eggshells along an urbanisation gradient.

Concentrations of seven trace elements [arsenic (As), chromium (Cr), nickel (Ni), lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd)] in the eggshells of Rooks Corvus frugilegus, a focal bird species of Eurasian agricultural environments, are increased above background levels and exceed levels of toxicological concern. The concentrations of Cr, Ni, Pb, Cu, and Zn are greater in eggshells from urban rookeries (large cities) compared with rural areas (small towns and villages) suggesting an urbanisation gradient effect among eggs laid by females. In the present study, the investigators assessed whether the pattern of relationships among the seven trace elements in eggshells change along an urbanisation/pollution gradient. Surprisingly, we found that eggshells with the greatest contaminant burden, i.e., from urban rookeries, showed far fewer significant relationships (n = 4) than eggshells from villages (n = 10), small towns (n = 6), or rural areas (n = 8). In most cases, the relationships were positive. As was an exception: Its concentration was negatively correlated with Ni and Cd levels in eggshells from small town rookeries (where As levels were the highest), whereas eggshells from villages (with a lower As level) showed positive relationships between As and Cd. Our findings suggest that at low to intermediate levels, interactions between the trace elements in Rook eggshells are of a synergistic character and appear to operate as parallel coaccumulation. A habitat-specific excess of some elements (primarily Cr, Ni, Cu, As) suggests their more competitively selective sequestration.

Essential and nonessential elements in nestling rooks Corvus frugilegus from eastern Poland with a special emphasis on their high cadmium contamination.

Concentration of minerals (sodium, potassium, calcium [Ca], magnesium, iron [Fe], copper, zinc [Zn], manganese [Mn], and cobalt) as well as toxic metals (cadmium [Cd], lead [Pb]) were determined in five tissues (liver, lung, kidney, muscle, and bone) of nestling rooks (Corvus frugilegus; 1 to 13 days old) found dead in seven breeding colonies in eastern Poland. Cd concentration in all analyzed tissues was in the narrow range of 17.0-17.2 mg/kg dry weight (dw) Cd, which in the light of the literature data indicates acute contamination by this toxic metal. Similarly, we found increased levels of Pb, which in all tissues ranged between 5.0 and 6.2 mg/kg dw. Results of multivariate general linear model (GLM) testing of the effect of three variables (tissue type, colony, and nestling age) on tissue concentrations of various metals showed significance for Fe, Cu, Zn, and Mn. Only concentrations of Ca, Fe, and Zn differed significantly between the analyzed tissues. GLM analysis did not show any statistically significant differences in tissue levels of minerals and both toxic metals among examined rookeries, which indicates the widespread presence of nonpoint Cd and Pb pollution linked to agricultural activity and similar levels of these inorganic contaminants on crop fields (feeding grounds) around breeding colonies. We concluded that high levels of both toxic metals, Cd and Pb, probably resulting from the diet of nestling rooks, are based mainly on a diet of ground-dwelling beetles gathered on crop fields.

Mechanically interlocked and switchable molecules at surfaces.

Mechanically interlocked molecules are of considerable interest from data storage, molecular scale or sensory device perspectives. Though the solution phase characterisation of these compounds has been extensively explored, progress towards real world application will, in many cases, necessitate a detailed understanding of their interfacing with supportive, optically transparent or electroactive surfaces. This feature article summarises the developments made in surface assembly and characterisation including recent progress in exploiting templating methods to interlock molecular systems on surfaces.

Reorganization energies of ferrocene-peptide monolayers.

To deepen understanding of the electron transfer through a peptide backbone, we have investigated a series of noncyclic and cyclic ferrocene-peptide (Fc-peptide) cystamine conjugates immobilized on the gold microelectrode. Interaction of the ferrocenium group with BF4-, ClO4-, and PF6- as counterions was explored and the electron-transfer rates and reorganization energies were determined by variable temperature cyclic voltammetry. The highest reorganization energy was observed for the BF4- counterion, which has the weakest ability to associate with the ferrocenium cation. In addition, the more rigid cyclic Fc-peptide conjugates have a smaller reorganization energy ranging from 0.3 to 0.5 eV compared to less rigid noncyclic Fc-peptide cystamine conjugates which have higher reorganization energies in the range of 0.5-1.0 eV, which suggests that the dynamic properties of the conjugate play a role in mediating electron transfer in these systems.