Using supercritical fluid extraction to measure the desorption and bioaccessibility of phenanthrene in soils

The aim of this paper was to measure the changing desorbable fraction and bioaccessibility of phenanthrene in two different soils with increasing soil-phenanthrene contact time using supercritical fluid extractions (SFE). Both soils were spiked with 100 mg kg⁻¹ phenanthrene and aged for 28 d. Desorption profiles were measured every 7 d using selective SFE conditions and the results were compared to ¹⁴C-phenanthrene mineralisation assays. Selective SFE showed significant differences in the rates and extents of desorption in the two soils, likely to be due to different organic matter composition. Post-extraction fitting of data yielded consistent SFE extraction times within ageing soils for bioaccessibility prediction.     

Effects of dissolution kinetics on bioaccessible arsenic from tailings and soils

Dissolution kinetics of arsenic from soils and tailings were studied under simulated gastrointestinal conditions to determine the effects of residence time, pH and soil composition on the bioaccessibility of arsenic. The samples were sieved to four particle size fractions from bulk to <45 μm, and included arsenic minerals, soils and tailings with total arsenic concentrations ranging from 19 to 420 00 mg kg⁻¹. The bioaccessible arsenic concentrations varied from 2.8 to 10 000 mg kg⁻¹, and the highest concentrations were associated with the smallest particle size fractions. Kinetic parameters were determined for each sample extracted under gastric conditions (pH = 1.8) followed by intestinal conditions (pH = 7.0). Under gastric pH conditions, dissolution appeared to be diffusion-controlled and followed an exponential curve, whereas a logarithmic or linear model was used to describe the mixed dissolution mechanisms observed under intestinal conditions. Nine of the 13 samples tested reached a steady state bioaccessible arsenic concentration within the 5-h physiologically-based extraction test (PBET). However the bioaccessible arsenic concentrations in four tailings samples increased significantly (p = 0.034) between the 5-h and the extended 24-h extraction under intestinal conditions. Since arsenic absorption may occur along the entire digestive tract, assessments based on the standard 5-h PBET extraction may not adequately estimate the risks associated with arsenic absorption in such cases. The slow dissolution kinetics associated with secondary arsenic minerals in some tailings samples may require extending the PBET extractions to longer periods, or extrapolating using the proposed kinetic models, to reach steady state concentrations in simulated gastrointestinal fluids.     

The ageing effect on the bioaccessibility and fractionation of arsenic in soils from China

Ingestion of contaminated soil has been recognized as an important exposure pathway of arsenic for humans, especially for children through outdoor hand-to-mouth activities. An improved sequential extraction procedure was employed in an attempt to reveal the relationship between bioaccessibility and fractionation of As in five soils from China. Arsenic bioaccessibility in acidic ( approximately pH 4.5) soils reached approximately stable levels after a sharp decline within one week of ageing. In contrast, As bioaccessibility in higher pH (>6.0) soils was found to be significantly higher and took two weeks of ageing to reach stable levels. The artificially added As was more labile than indigenous As. The main proportions of added As were found in the specifically sorbed and amorphous and poorly-crystalline hydrous Fe/Al oxide-bound fractions. Correlation analysis shows that the non-specifically and specifically sorbed As are likely to constitute the main proportion of bioaccessible soil As. The soil content of amorphous and crystalline Fe/Al oxides and soil pH appear to be the key factors controlling, not only the time needed to reach a steady state, but also the magnitude of the bioaccessibility of As added to the soils.     

Phytoextraction by arsenic hyperaccumulator Pteris vittata L. from six arsenic-contaminated soils: Repeated harvests and arsenic redistribution

This greenhouse experiment evaluated arsenic removal by Pteris vittata and its effects on arsenic redistribution in soils. P. vittata grew in six arsenic-contaminated soils and its fronds were harvested and analyzed for arsenic in October, 2003, April, 2004, and October, 2004. The soil arsenic was separated into five fractions via sequential extraction. The ferns grew well and took up arsenic from all soils. Fern biomass ranged from 24.8 to 33.5 g plant(-1) after 4 months of growth but was reduced in the subsequent harvests. The frond arsenic concentrations ranged from 66 to 6,151 mg kg(-1), 110 to 3,056 mg kg(-1), and 162 to 2,139 mg kg(-1) from the first, second and third harvest, respectively. P. vittata reduced soil arsenic by 6.4-13% after three harvests. Arsenic in the soils was primarily associated with amorphous hydrous oxides (40-59%), which contributed the most to arsenic taken up by P. vittata (45-72%). It is possible to use P. vittata to remediate arsenic-contaminated soils by repeatedly harvesting its fronds.     

Bioaccessibility of arsenic in various types of rice in an in vitro gastrointestinal fluid system

Rice can be a major contributor to dietary arsenic exposure because of the relatively high total arsenic concentration compared to other grains, especially for people whose main staple is rice. This study employed in vitro gastrointestinal fluid digestion to determine bioaccessible or gastrointestinal fluid extractable arsenic concentration in rice. Thirty-one rice samples, of which 60 % were grown in the United States, were purchased from food stores in New York City. Total arsenic concentrations in these samples ranged from 0.090 ± 0.004 to 0.85 ± 0.03 mg/kg with a mean value of 0.275 ± 0.161 mg/kg (n = 31). Rice samples with relatively high total arsenic (>0.20 mg/kg, n = 18) were treated by in vitro artificial gastrointestinal fluid digestion, and the extractable arsenic ranged from 53 % to 102 %. The bioaccessibility of arsenic in rice decreases in the general order of extra long grain, long grain, long grain parboiled, to brown rices.     

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.     

Effect of short-chain organic acids and pH on the behaviors of pyrene in soil–water system

The effects of five short-chain organic acids (SCOAs) on the behaviors of pyrene in soil–water system were investigated. The influences of the quantity and species of organic acids, pH, and soil dissolved organic matter were considered. The results showed the presence of SCOAs inhibited the adsorption and promoted the desorption of pyrene in the following order: citric acid > oxalic acid > tartaric acid > lactic acid > acetic acid. The decreased extents of pyrene adsorption performance enhanced with increasing SCOA concentrations, while the decreasing rate became less pronounced at high SCOA concentrations. In the presence of organic acids, the adsorption ability of pyrene decreased with increasing pH. However, there was a slight increase of pyrene adsorption with the addition of oxalic acid, tartaric acid and citric acid above pH 8. The capacity for pyrene retention differentiated significantly between the soils with and without dissolved organic matter. The presence of SCOAs was also favorable for the decrease of pyrene adsorption on soil without dissolved organic matter. The results of this study have important implications for the remediation of persistent organic pollutants in soil and groundwater.     

Characterization of extractable and non-extractable polycyclic aromatic hydrocarbons in soils and sediments from the Pearl River Delta, China

Formation of bound residues of pollutants in soils and sediments is an important process to control the fate of pollutants in the environment. The most of bound residue is not solvent extractable. In this paper, we measured both extractable and non-extractable polycyclic aromatic hydrocarbons (PAHs) in different organic matter fractions of samples from the Pearl River Delta, China. Non-extractable PAHs concentration was 234.45-1424.57 μg/kg and accounted for 33.78-57.44% of total PAHs. 2-3 Ring PAHs were the dominant species and differed in concentration substantially between the samples. The atomic ratio of PAHs over organic-C in the fractions ordered as solvent soluble organic matter > humin > humic acids, matching the content of aliphatic moieties in the fractions of organic matter. The ratio of extractable and non-extractable PAHs may relate to the aging process of PAHs in soil and sediment.     

Influence of aggregated particles on biodegradation activities for dimethylarsinic acid (DMA) in Lake Kahokugata

Aquatic arsenic cycles mainly depend on microbial activities that change the arsenic chemical forms and influence human health and organism activities. The microbial aggregates degrading organic matter are significantly related to the turnover between inorganic arsenic and organoarsenic compounds. We investigated the effects of microbial aggregates on organoarsenic mineralization in Lake Kahokugata using lake water samples spiked with dimethylarsinic acid (DMA). The lake water samples converted 1 μmol L⁻¹ of DMA to inorganic arsenic for 28 d only under anaerobic and dark conditions in the presence of microbial activities. During the DMA mineralization process, organic aggregates >5.0 μm with bacterial colonization increased the densities. When the organic aggregates >5.0 μm were eliminated from the lake water samples using filters, the degradation activities were reduced. DMA in the lake water would be mineralized by the microbial aggregates under anaerobic and dark conditions. Moreover, DMA amendment enhanced the degradation activities in the lake water samples, which mineralized 50 μmol L⁻¹ of DMA. The DMA-amended aggregates >5.0 μm completely degraded 1 μmol L⁻¹ of DMA with a shorter incubation time of 7 d. The supplement of KNO₃ and NaHCO₃ to lake water samples also shortened the DMA-degradation period. Presumably, the bacterial aggregates involved in the chemical heterotrophic process would contribute to the DMA-biodegradation process in Lake Kahokugata, which is induced by the DMA amendment.     

Arsenic Background Concentrations in Florida,U.S.A. Surface Soils: Determination and Interpretation

Background concentrations of soil arsenic have been used as an alternative soil cleanup criterion in many states in the U.S. This research addresses issues related to the interpretation of background concentrations of arsenic in near pristine soils in Florida. Total arsenic was measured in 448 taxonomic and geographic representative surface soil samples using USEPA Method 3052 (HCl-HNO₃-HF, microwave digestion) and graphite furnace atomic absorption spectrophotometry analysis procedure. Values were log-normally distributed, with geometric mean and baseline concentration (defined as 95% of the expected range of background concentrations) providing the most satisfactory statistical results. An upper baseline concentration of 6.21 mg As/kg was estimated for undisturbed soils (n = 267) compared to 7.63 mg As/kg for disturbed soils (n = 181). Temporal trend of total soil arsenic concentrations from 1967 to 1989 paralleled decreased usage of arsenic in U.S. agriculture. Soil arsenic background concentrations were generally higher in south Florida than in north and central Florida, and associated with wet soils. Individual high arsenic sites were scattered throughout the state, but the most highly concentrated of these occurred in the Leon-Lee belt along the Ocala uplift district extending to the southwestern flatwoods district. Extrapolation of the data using a single arsenic value regardless of the taxonomic and geographical differences in soil arsenic distribution would underestimate potential arsenic contamination in upland soils.     

Bioaccessibility of trace elements as affected by soil parameters in smelter-contaminated agricultural soils: a statistical modeling approach

An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using: (i) a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.     

Relating dissolved organic matter fluorescence and functional properties

The fluorescence excitation–emission matrix properties of 25 dissolved organic matter samples from three rivers and one lake are analysed. All sites are sampled in duplicate, and the 25 samples include ten taken from the lake site, and nine from one of the rivers, to cover variations in dissolved organic matter composition due to season and river flow. Fluorescence properties are compared to the functional properties of the dissolved organic matter; the functional assays provide quantitative information on photochemical fading, buffering capacity, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Optical (absorbance and fluorescence) characterization of the dissolved organic matter samples demonstrates that (1) peak C (excitation 300–350 nm; emission 400–460 nm) fluorescence emission wavelength; (2) the ratio of peak T (excitation 220–235 nm; emission 330–370 nm) to peak C fluorescence intensity; and (3) the peak C fluorescence intensity: absorbance at 340 nm ratio have strong correlations with many of the functional assays. Strongest correlations are with benzo[a]pyrene binding, alumina adsorption, hydrophilicity and buffering capacity, and in many cases linear regression equations with a correlation coefficient >0.8 are obtained. These optical properties are independent of freshwater dissolved organic carbon concentration (for concentrations <10 mg L⁻¹) and therefore hold the potential for laboratory, field and on-line monitoring and prediction of organic matter functional properties.     

Sorption and desorption of sulfentrazone in Brazilian soils

This study was undertaken to obtain information about the behavior of sulfentrazone in soil by evaluating the sorption and desorption of the herbicide in different Brazilian soils. Batch equilibrium method was used and the samples were analyzed by high performance liquid chromatography. Based on the results obtained from the values of Freundlich constants (Kf), we determined the order of sorption (Haplic Planosol < Red-Yellow Latosol < Red Argisol < Humic Cambisol < Regolitic Neosol) and desorption (Regolitic Neosol < Red Argisol < Humic Cambisol < Haplic Planosol < Red-Yellow Latosol) of sulfentrazone in the soils. The process of pesticide sorption in soils was dependent on the levels of organic matter and clay, while desorption was influenced by the organic matter content and soil pH. Thus, the use of sulfentrazone in soils with low clay content and organic matter (low sorption) increases the probability of contaminating future crops.     

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.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Magnetic signature,geochemistry, and oral bioaccessibility of “technogenic” metals in contaminated industrial soils from Sindos Industrial Area,Northern Greece

The objective of this study was to assess the contamination level of potentially harmful elements (PHEs) in industrial soils and how this relates to environmental magnetism. Moreover, emphasis was given to the determination of the potential mobile fractions of typically “technogenic” metals. Therefore, magnetic and geochemical parameters were determined in topsoils (0–20 cm) collected around a chemical industry in Sindos Industrial Area, Thessaloniki, Greece. Soil samples were presented significantly enriched in “technogenic” metals such Cd, Pb, and Zn, while cases of severe soil contamination were observed in sampling sites north-west of the industrial unit. Contents of Cd, Cr, Cu, Ni, Pb, Mo, Sb, Sn, and Zn in soils and pollution load index (PLI) were highly correlated with mass specific magnetic susceptibility (χ _lf). Similarly, enrichment factor (EF) and geoaccumulation index (I _geo) for “technogenic” Pb and Zn exhibited high positive correlation factors with χ _lf. Principal component analysis (PCA) classified PHEs along with the magnetic variable (χ _lf) into a common group indicating anthropogenic influence. The water extractable concentrations were substantially low, while the descending order of UBM (Unified BARGE Method) extractable concentrations in the gastric phase was Zn > Pb > As > Cd, yet Cd showed the highest bioaccessibility (almost 95%).

     

Bioaccessibility and health risk of arsenic, mercury and other metals in urban street dusts from a mega-city, Nanjing, China

The oral bioaccessibility and the human health risks of As, Hg and other metals (Cu, Pb, Zn, Ni, Co, Cd, Cr, Mn, V and Fe) in urban street dusts from different land use districts in Nanjing (a mega-city), China were investigated. Both the total contents and the oral bioaccessibility estimated by the Simple Bioaccessibility Extraction Test (SBET) of the studied elements varied with street dusts from different land use districts. Cd, Zn, Mn, Pb, Hg and As showed high bioaccessibility. SBET-extractable contents of elements were significantly correlated with their total contents and the dust properties (pH, organic matter contents). The carcinogenic risk probability for As and Cr to children and adults were under the acceptable level (<1 × 10⁻⁴). Hazard Quotient values for single elements and Hazard Index values for all studied elements suggested potential non-carcinogenic health risk to children, but not to adults.     

Removal of organic contaminants in bioretention medium amended with activated carbon from sewage sludge

Bioretention, also known as rain garden, allows stormwater to soak into the ground through a soil-based medium, leading to removal of particulate and dissolved pollutants and reduced peak flows. Although soil organic matter (SOM) is efficient at sorbing many pollutants, amending the bioretention medium with highly effective adsorbents has been proposed to optimize pollutant removal and extend bioretention lifetime. The aim of this research was to investigate whether soil amended with activated carbon produced from sewage sludge increases the efficiency to remove hydrophobic organic compounds frequently detected in stormwater, compared to non-amended soil. Three lab-scale columns (520 cm³) were packed with soil (bulk density 1.22 g/cm³); activated carbon (0.5% w/w) was added to two of the columns. During 28 days, synthetic stormwater—ultrapure water spiked with seven hydrophobic organic pollutants and dissolved organic matter in the form of humic acids—was passed through the column beds using upward flow (45 mm/h). Pollutant concentrations in effluent water (collected every 12 h) and polluted soils, as well as desorbed amounts of pollutants from soils were determined using GC-MS. Compared to SOM, the activated carbon exhibited a significantly higher adsorption capacity for tested pollutants. The amended soil was most efficient for removing moderately hydrophobic compounds (log K _ow 4.0–4.4): as little as 0.5% (w/w), carbon addition may extend bioretention medium lifetime by approximately 10–20 years before saturation of these pollutants occurs. The column tests also indicated that released SOM sorb onto activated carbon, which may lead to early saturation of sorption sites on the carbon surface. The desorption test revealed that the pollutants are generally strongly sorbed to the soil particles, indicating low bioavailability and limited biodegradation.

     

Factors influencing on the bioaccessibility of polybrominated diphenyl ethers in size-specific dust from air conditioner filters

Size-specific concentrations and bioaccessibility of polybrominated diphenyl ethers (PBDEs) in dust from air conditioner filters were measured, and the factors influencing the PBDE bioaccessibility were determined. Generally, the PBDE concentrations increased with decreasing dust particle size, and BDE209 (deca-BDE) was generally the predominant congener. The bioaccessibility ranged from 20.3% to 50.8% for tri- to hepta-BDEs, and from 5.1% to 13.9% for BDE209 in dust fractions of varied particle size. The bioaccessibility of most PBDE congeners decreased with increasing dust particle size. The way of being of PBDE (adsorbed to dust surface or incorporated into polymers) in dust significantly influenced the bioaccessibility. There was a significant negative correlation between the tri- to hepta-BDE bioaccessibility and organic matter (OM) contents in dust. Furthermore, tri- to hepta-BDE bioaccessibility increased with increasing polarity of OMs, while with decreasing aromaticity of OMs. The tri- to hepta-BDE bioaccessibility significantly positively correlated with the surface areas and pore volumes of dust. Using multiple linear regression analysis, it was found that the OM contents and pore volumes of dust were the most important factors to influence the tri- to hepta-BDE bioaccessibility and they could be used to estimate the bioaccessibility of tri- to hepta-BDEs according to the following equation: bioaccessibility (%) = 45.05 − 0.49 × OM% + 1.79 × pore volume. However, BDE209 bioaccessibility did not correlate to any of these factors.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.