In vitro and in vivo approaches for the measurement of oral bioavailability of lead (Pb) in contaminated soils: a review

We reviewed the published evidence of lead (Pb) contamination of urban soils, soil Pb risk to children through hand-to-mouth activity, reduction of soil Pb bioavailability due to soil amendments, and methods to assess bioaccessibility which correlate with bioavailability of soil Pb. Feeding tests have shown that urban soils may have much lower Pb bioavailability than previously assumed. Hence bioavailability of soil Pb is the important measure for protection of public health, not total soil Pb. Chemical extraction tests (Pb bioaccessibility) have been developed which are well correlated with the results of bioavailability tests; application of these tests can save money and time compared with feeding tests. Recent findings have revealed that fractional bioaccessibility (bioaccessible compared to total) of Pb in urban soils is only 5-10% of total soil Pb, far lower than the 60% as bioavailable as food-Pb presumed by U.S.-EPA (30% absolute bioavailability used in IEUBK model).     

Bioaccessibility of polychlorinated biphenyls in workplace dust and its implication for risk assessment

Human exposure to bioaccessible PCBs via indoor dust is limited around the world. In the present study, the workplace dust sample from commercial office, hospital, secondary school, shopping mall, electronic factory and manufacturing plant were collected from Hong Kong for PCBs analyses. Total PCBs concentrations ranged from 46.8 to 249 ng g⁻¹, with a median of 107 ng g⁻¹. Manufacturing plant showed the highest concentration among all of sampling sites. PCB 77 was found as the dominant congeners. The bioaccessibility of PCBs in small intestinal juice ranging from 8.3% to 26.0% was significantly higher than that in gastric condition, ranging from 4.8% to 12.4%. In addition, significant negative correlations (p < 0.05) were observed between K_OW and bioaccessibility for all workplace dust samples. Risk assessment indicated that the averaged daily dose of dioxin-like PCBs via non-dietary intake of workplace dust, considering the bioaccessibility of PCBs, were much lower than the TDI of dioxins (2.3 pg WHO-TEQ kg bw⁻¹ d⁻¹) established by Joint FAO/WHO Expert Committee on Food Additives.     

Organohalogen exposure in a Eurasian Eagle owl (Bubo bubo) population from Southeastern Spain: temporal-spatial trends and risk assessment

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and organochlorine insecticides (OCs) were analysed in 58 Eurasian Eagle owl (Bubo bubo) unhatched eggs collected between 2004 and 2009 in Southeastern Spain. Levels of p,p′-DDE were found to be higher than in eggs laid by other European owls in the same decade, probably due to the greater agricultural activity in our study area. Compared to other European raptors, exposure to PCBs can be considered intermediate, but low to PBDEs. Land use differences and prey availability were the rationale to divide the study area in two subareas in further assessments. Temporal trends of HCB, p,p′-DDE, β-HCH, PCBs and PBDEs were significantly different in each subarea, generally increasing over time in the Southern but decreasing or remaining stable in the Northern. On the contrary, levels of cyclodienes tended to decrease in both subareas. Dietary shifts with a greater amount of birds are suggested as a cause for increasing organochlorine loads in raptors. This may explain the increasing trend in the Southern territories. However, due to the proximity of most of these nests to Cartagena, an important industrial city, increasing environmental pollution cannot be ruled out. Although average levels of the compounds analysed are below threshold levels, 17% of the samples exceeded 400 pg g⁻¹ ww (wet weight), the LOAEC for Total TEQs. Moreover, a negative correlation between TEQ concentrations and the metabolizable fraction of PCBs (F_prob = 0.0018) was found when TEQs values were above 10 pg g⁻¹ ww. This could be indicative of hepatic enzymes induction in the birds exposed at higher concentrations, which are mainly breeding in the Southern subarea. These females could be suffering from Ah-receptor-related toxic effects, some of which have been related to altered bird reproduction. Finally, a significant negative correlation between p,p′-DDE levels and eggshell thickness (r = −0.469, p < 0.001) was observed, with about 17% of eggshell thinning for eggs with p,p′-DDE levels above 100 μg g ⁻¹ lw. The persistence of this degree of thinning over a period of time has been related to population declines in other raptor species.     

Changes in arsenic fractionation, bioaccessibility and speciation in organo-arsenical pesticide amended soils as a function of soil aging

Although organoarsenical pesticides are being phased out, sites with high concentrations of organic arsenical residues still exist due to the long-term application of these pesticides. The biotic and abiotic speciation of dimethylarsinic acid (DMA) can result in the formation of inorganic arsenic (As) species. Oxidation state, retention, and thereby persistence, varies according to temporal changes, influencing the availability and toxicity of contaminants. The current greenhouse study aimed at evaluating temporal changes in the oxidation state of As, geochemical partitioning, and bioaccessibility. Four soils with varying physiochemical properties were contaminated with DMA at two concentrations (675 and 1500 mg kg⁻¹ of As). Rice plants were grown for a 6 months period, following which, the soils were allowed to age. The operationally defined forms of As and its bioaccessibility was analyzed at 0, 6 months, 1 year, and 3 years. Changes in oxidation state of As were evaluated immediately after spiking and after 3 years of soil-pesticide equilibration. Results show that geochemical partitioning of As was affected significantly (P < 0.05) by soil type, loading rates, and equilibration time. Arsenic was bound mainly to the poorly-crystalline Fe/Al-oxyhydroxides in the soil. However, these interactions did not affect As bioaccessibility, presumably due to the dissolution of the bound fractions of As in the acidic stomach. While 74-94% of the total bioaccessible As was transformed to As(V), 4-19% was transformed to the more toxic As(III). This study indicates that although aging affected the geochemical partitioning of As in the soil, bioaccesibility was controlled by the gastric pH.     

Surfactant-induced mobilisation of trace metals from estuarine sediment: implications for contaminant bioaccessibility and remediation

The mobilisation of metals (Al, Fe, Cd, Cu, Mn, Ni, Pb, Sn, Zn) from contaminated estuarine sediment has been examined using commercially available surfactants. Metal release by the anionic surfactant, sodium dodecyl sulphate (SDS), increased with increasing amphiphile concentration up to and above its critical micelle concentration (CMC). Metal mobilisation by the bile acid salt, sodium taurocholate, and the nonionic surfactant, Triton X-100, however, did not vary with amphiphile concentration. SDS was the most efficient surfactant in mobilising metals from the sample, and Cd, Cu and Ni were released to the greatest extents (12-18% of total metal at [SDS] > CMC). Metal mobilisation appeared to proceed via complexation with anionic amphiphiles and denudation of hydrophobic host phases. Surfactants may play an important role in the solubilisation of metals in the digestive environment of deposit-feeding animals and, potentially, in the remediation of metal-contaminated soil and sediment.     

Fractionation and speciation of arsenic in three tea gardens soil profiles and distribution of As in different parts of tea plant (Camellia sinensis L.)

The distribution pattern and fractionation of arsenic (As) in three soil profiles from tea (Camellia sinensis L.) gardens located in Karbi-Anglong (KA), Cachar (CA) and Karimganj (KG) districts in the state of Assam, India, were investigated depth-wise (0-10, 10-30, 30-60 and 60-100 cm). DTPA-extractable As was primarily restricted to surface horizons. Arsenic speciation study showed the presence of higher As(V) concentrations in the upper horizon and its gradual decrease with the increase in soil depths, following a decrease of Eh. As fractionation by sequential extraction in all the soil profiles showed that arsenic concentrations in the three most labile fractions (i.e., water-soluble, exchangeable and carbonate-bound fractions) were generally low. Most arsenic in soils was nominally associated with the organic and Fe-Mn oxide fractions, being extractable in oxidizing or reducing conditions. DTPA-extractable As (assumed to represent plant-available As) was found to be strongly correlated to the labile pool of As (i.e. the sum of the first three fractions). The statistical comparison of means (two-sample t-test) showed the presence of significant differences between the concentrations of As(III) and As(V) for different soil locations, depths and fractions. The risk assessment code (RAC) was found to be below the pollution level for all soils. The measurement of arsenic uptake by different parts of tea plants corroborated the hypothesis that roots act as a buffer and hold back contamination from the aerial parts.     

Arsenic stability and mobilization in soil at an amenity grassland overlying chemical waste (St. Helens, UK)

A 6.6 ha grassland, established on a former chemical waste site adjacent to a residential area, contains arsenic (As) in surface soil at concentrations 200 times higher than UK Soil Guideline Values. The site is not recognized as statutory contaminated land, partly on the assumption that mobility of the metalloid presents a negligible threat to human health, groundwater and ecological receptors. Evidence for this is evaluated, based on studies of the effect of organic (green waste compost) and inorganic (iron oxides, lime and phosphate) amendments on As fractionation, mobility, plant uptake and earthworm communities. Arsenic mobility in soil was low but significantly related to dissolved organic matter and phosphate, with immobilization associated with iron oxides. Plant uptake was low and there was little apparent impact on earthworms. The existing vegetation cover reduces re-entrainment of dust-blown particulates and pathways of As exposure via this route. Minimizing risks to receptors requires avoidance of soil exposure, and no compost or phosphate application.     

Levels and speciation of arsenic in the atmosphere in Beijing, China

Arsenic levels and speciation in the total suspended particles (TSPs) were quantitatively determined by high performance liquid chromatography on-line coupled with hydride generation atomic fluorescence spectrometry in Beijing, China from February 2009 to March 2011. The high TSP levels fluctuated between 0.07 and 0.79 mg m⁻³, with a mean level of 0.32 ± 0.17 mg m⁻³. The total arsenic concentrations ranged from 0.03 to 0.31 μg m⁻³ (mean: 0.13 ± 0.06 μg m⁻³) in Beijing‘s air. The concentrations of As(III) and As(V) ranged from 0.73 to 20 ng m⁻³ (mean: 4.7 ± 3.6 ng m⁻³) and from 14 to 2.5 × 10² ng m⁻³ (mean: 67 ± 35 ng m⁻³), respectively. As levels and speciation demonstrated relative higher levels in spring and autumn and lower values in summer and winter. As(V) accounted for 81-99% of the extractable species in the TSP samples which showed that As(V) was the major fraction of the extractable As. Organoarsenic species, monomethylarsonate (MMA) and dimethylarsinate (DMA) were not found in all samples. Higher values of enrichment factors demonstrated that arsenic in TSP mainly come from anthropogenic sources. High As and its species levels in air and respiratory exposure (0.30-0.84 μg d⁻¹) attributed to higher excess cancer risk ((4.2 ± 2.0) × 10⁻⁴) for people in Beijing.     

Distribution, availability, and sources of trace metals in different particle size fractions of urban soils in Hong Kong: Implications for assessing the risk to human health

The concentration and loading distribution of trace metals (Cu, Zn, Pb, Co, Ni, Cr, and Mn) and major elements (Al, Ca, Fe, and Mg) in different particle size fractions (2000-280, 280-100, 100-50, 50-10, 10-2, and <2 μm) of surface soils from highly urbanized areas in Hong Kong were studied. The enrichment of Pb, Cu, and Zn in the urban soils was strongly influenced by anthropogenic activities, and Pb accumulated in fine particles was mainly derived from past vehicular emissions as shown by Pb isotopic signatures. Trace metals primarily accumulated in clay, fine silt, and very fine sand fractions, and might pose potential health risks via the inhalation of resuspended soil particles in the air (PM₁₀ or PM_2.5), and ingestion of adhered soils through the hand-to-mouth pathway. The mobility, bioavailability, and human bioaccessibility of Pb and Zn in bulk soils correlated significantly with metal concentrations in fine silt and/or very fine sand fractions.     

An approach for arsenic in a contaminated soil: Speciation, fractionation, extraction and effluent decontamination

The fractionation and speciation of As in a contaminated soil were investigated, and a remediation strategy was tested. Regarding speciation, we found that As(V) prevails over As(III) whereas more than 40% of total arsenic is in organic form. The fractionation of As was investigated with two sequential extraction methods: a low mobility was found. Then we tested the possibility of using phosphoric acid to extract As from the soil and cleaning the washing effluents by sorption onto montmorillonite. The efficiency of the extraction and of the adsorption onto the clay were also investigated for Cr, Cu, Fe, Mn, Ni, Pb and Zn, whose total concentrations and fractionation in the soil are reported here. The extraction percentages for As and metals ranged from 30 to 65%; the residual proportions in the soil are presumably in very unreactive forms. Montmorillonite showed a good uptake capacity towards the investigated pollutants.     

Distribution, source and risk assessment of polychlorinated biphenyls (PCBs) in urban soils of Beijing, China

The concentration of PCBs in urban soils of Beijing across six land types including business districts (BD), cultural and educational areas (CE), classical gardens (CG), public green (PG), residential areas (RA), and roadsides (RD) was investigated. The total concentrations of PCBs ranged from below method detection limit (M.D.L.) to 37.11 × 10⁻³ mg kg⁻¹ dry weight (mean: 11.70 × 10⁻³ mg kg⁻¹; median: 13.28 × 10⁻³ mg kg⁻¹), which was at a medium level compared with other cities around the world. In general, the levels of PCBs decreased from the center of Beijing city to the suburb, suggesting the increasing PCBs concentrations with the age of the urban area. For different types of land use, the highest level of PCBs was observed in CG soils which have the oldest age, and the homologue profiles were similar, which were predominated by lowly chlorinated congeners including di-, tri- and tetra-CBs. Principal component analysis indicated that local sources such as Aroclor 1016, 1242, and 1248 were important sources in addition to long-range transport of PCBs all over the world. Although the toxic equivalency (TEQ) concentrations of dioxin-like PCBs in all soil samples of Beijing were higher than those in other urban areas of China, they met the Canadian soil quality standard.     

Residual behaviour and risk assessment of flubendiamide on chickpea (Cicer arietinum L.)

The study was undertaken to determine the disappearance trends of flubendiamide residues on chickpea under field conditions and thereby, ensure consumer safety. Average initial deposits of flubendiamide on chickpea pods were found to be 0.68 and 1.17 mg kg⁻¹, respectively, following three applications of flubendiamide 480SC @ 48 and 96 g a.i. ha⁻¹ at 7 d intervals. Half-life of flubendiamide on chickpea pods was observed to be 1.39 and 1.44 d, respectively, at single and double dosages whereas with respect to chickpea leaves, these values were found to be 0.77 and 0.86 d. Desiodo flubendiamide was not detected at 0.05 mg kg⁻¹ level on chickpea samples collected at different intervals. Theoretical maximum residue contribution (TMRC) for flubendiamide was calculated and found to be well below the maximum permissible intake (MPI) on chickpea pods and leaves at 0-day (1 h after spraying) for the both dosages. Thus, the application of flubendiamide at the recommended dose on chickpea presents no human health risks and is safe to the consumers.     

Metals pollution and human bioaccessibility of topsoils in Grugliasco (Italy)

Polluted soils can present a significant health risk especially in an urban environment. Most current legislation and health risk frameworks are based on pseudototal metal content. However, only a fraction of these concentrations is available for plant and human uptake. The aim of this work was to study the diffuse metal contamination in the soils of a municipality in Northern Italy in terms of: (i) metal availability, and (ii) metal accessibility to the human body and its relationship to soil properties, considering lead, copper, zinc, nickel, and chromium. Soil metal content was measured simulating availability conditions. Human bioaccessibility was derived from a modified physiologically-based extraction test. The human bioaccessible content was then estimated taking into account the relationships between pseudototal content and selected soil parameters. For the case study, the prediction of human bioaccessibility based on pseudototal content, organic matter and soil texture produced statistically significant models, with r² = 0.60 for Cu, r² = 0.53 for Pb and r² = 0.42 for Zn.     

Determination of anti-anxiety and anti-epileptic drugs in hospital effluent and a preliminary risk assessment

In this study, an analytical methodology was developed for the determination of psycho-active drugs in the treated effluent of the University Hospital at the Federal University of Santa Maria, RS – Brazil. Samples were collected from point A (Emergency) and point B (General effluent). The adopted methodology included a pre-concentration procedure involving the use of solid phase extraction and determination by liquid chromatography coupled to mass spectrometry. The limit of detection for bromazepam and lorazepam was 4.9 ± 1.0 ng L⁻¹ and, for carbamazepine, clonazepam and diazepam was 6.1 ± 1.5 ng L⁻¹. The limit of quantification was 30.0 ± 1.1 ng L⁻¹, for bromazepam, clonazepam and lorazepam; for carbamazepine was 50.0 ± 1.8 ng L⁻¹ and was 40.0 ± 1.0 ng L⁻¹ for diazepam. The mean concentrations in the Emergency and General effluent treated currents were as follows: for bromazepam, 195 ± 6 ng L⁻¹ and 137 ± 7 ng L⁻¹; for carbamazepine, 590 ± 6 ng L⁻¹ and 461 ± 10 ng L⁻¹; for diazepam, 645 ± 1 ng L⁻¹ and 571 ± 10 ng L⁻¹; for lorazepam, 96 ± 7 ng L⁻¹ and 42 ± 4 ng L⁻¹; and for clonazepam, 134 ± 10 ng L⁻¹ and 57 ± 10 ng L⁻¹. A preliminary risk assessment was conducted: carbamazepine and diazepam require considerable attention owing to their environmental toxicity. The occurrence of these psychoactive-drugs and the environmental risks that they pose demonstrated the need for a more efficient treatment system. As far we are aware, there have been no comparable studies to this on the hazards of hospital effluents in Brazil, and very few that have carried out a risk assessment of psycho-active drugs in hospital effluent in general.     

Spatial variability of arsenic and chromium in the soil water at a former wood preserving site

Contamination of industrial sites by wood preservatives such as chromated copper arsenate (CCA) may pose a serious threat to groundwater quality. The objective of this study was to characterise the spatial variability of As and Cr concentrations in the solid phase and in the soil water at a former wood impregnation plant and to reveal the fundamental transport processes. The soil was sampled down to a depth of 2m. The soil water was extracted in situ from the vadose zone over a period of 10 months at depths of 1 and 1.5m, using large horizontally installed suction tubes. Groundwater was sampled from a depth of 4.5m. Results showed that arsenic and chromium had accumulated in the upper region of the profile and exhibited a high spatial variability (As: 21-621 mg kg(-1); Cr: 74-2872 mg kg(-1)). Concentrations in the soil water were high (mean As 167 microg L(-1); Cr: 62 microg L(-1)) and also showed a distinct spatial variability, covering concentration ranges up to three orders of magnitude. The variability was caused by the severe water-repellency of the surface soil, induced by the concurrent application of creosote wood preservatives, which leads to strong preferential flow as evident from a dye experiment. In contrast to soil water concentrations, only low As concentrations (<12 microg L(-1)) were detected in the groundwater. High Cr concentrations in the groundwater (approx. 300 microg L(-1)), however, illustrated the pronounced mobility of chromium. Our study shows that at sites with a heterogeneous flow system in the vadose zone a disparity between flux-averaged and volume-averaged concentrations may occur, and sampling of soil water might not be adequate for assessing groundwater concentrations. In these cases long-term monitoring of the groundwater appears to be the best strategy for a groundwater risk assessment.     

Specific accumulation of arsenic compounds in green turtles (Chelonia mydas) and hawksbill turtles (Eretmochelys imbricata) from Ishigaki Island, Japan

Concentrations of total arsenic (As) and individual compounds were determined in green and hawksbill turtles from Ishigaki Island, Japan. In both species, total As concentrations were highest in muscle among the tissues. Arsenobetaine was a major compound in most tissues of both turtles. High concentrations of trimethylarsine oxide were detected in hawksbill turtles. A significant negative correlation between standard carapace length (SCL), an indicator of age, and total As levels in green turtles was found. In contrast, the levels increased with SCL of hawksbill turtles. Shifts in feeding habitats with growth may account for such a growth-dependent accumulation of As. Although concentrations of As in marine sponges, the major food of hawksbill turtles are not high compared to those in algae eaten by green turtles, As concentrations in hawksbill turtles were higher than those in green turtles, indicating that hawksbill turtles may have a specific accumulation mechanism for As.     

A pharmacokinetic modeling of inorganic arsenic: a short-term oral exposure model for humans

This study presents a pharmacokinetic modeling of inorganic arsenic disposition in human body for short-term oral exposures. Effort on the development of the model is directed toward the prediction of the kinetic behavior of inorganic arsenic and its metabolites in the body. The current model considers the 4 circulating species; As^III, As^v, and two metabolites such as monomethylarsenic (MMA) and dimethylarsenic (DMA) in the blood and tissue groups. While it is difficult to estimate some parameters used in the models at this time, the current model assumptions and predictions seem to be consistent with the experimental observations found in the literature. Hence, the current model, when more fully developed, is expected to provide insight into the behavior of inorganic arsenic and its methylated metabolites within the body, and may help increase the understanding of risk assessment issues associated with inorganic arsenic in drinking water.     

The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: A critical review

This article provides a critical review of the environmental chemistry of inorganic antimony (Sb) in soils, comparing and contrasting findings with those of arsenic (As). Characteristics of the Sb soil system are reviewed, with an emphasis on speciation, sorption and phase associations, identifying differences between Sb and As behaviour. Knowledge gaps in environmentally relevant Sb data for soils are identified and discussed in terms of the limitations this imposes on understanding the fate, behaviour and risks associated with Sb in environmental soil systems, with particular reference to mobility and bioavailability.