Determination of cyclic volatile methylsiloxanes in water,sediment, soil,biota, and biosolid using large-volume injection–gas chromatography–mass spectrometry

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid–solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection–gas chromatography−mass spectrometry (LVI−GC−MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI–GC–MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS’s associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4 °C were stable within 29 d; however, significant depletion of D6 (60–70%) occurred only after 3 d. Whereas cVMS in sewage influent and effluent were stable at 4 °C within 21 d. cVMS in sediment sealed in amber glass jars at −20 °C and in pentane extracts in vials at −15 °C were stable during 1 month under both storage conditions.     

Potential use of DNA adducts to detect mutagenic compounds in soil

In this study, three different soils with contrasting features, spiked with 300 mg benzo[a]pyrene (BaP)/kg dry soil, were incubated at 20 °C and 60% water holding capacity for 540 days. At different time points, BaP and DNA were extracted and quantified, and DNA adducts were quantified by ³²P-postlabelling. After 540 days incubation, 69.3, 81.6 and 83.2% of initial BaP added remained in Cruden Bay, Boyndie and Insch soils, respectively. Meanwhile, a significantly different amount of DNA-BaP adducts were found in the three soils exposed to BaP over time. The work demonstrates the concept that DNA adducts can be detected on DNA extracted from soil. Results suggest the technique is not able to directly reflect bioavailability of BaP transformation products. However, this new method provides a potential way to detect mutagenic compounds in contaminated soil and to assess the outcomes of soil remediation.     

Relevance study of bare and coated zero valent iron nanoparticles for lindane degradation from its by-product monitorization

Zero-valent iron nanoparticles (NZVI) as well as polymer–stabilized nanoparticles were synthesized and used for lindane (γ-hexachlorocyclohexane) degradation in aqueous solution. To study the effectiveness of the different coated nanoparticles, simple and rapid analytical methods have been developed to measure and to detect lindane and its by-products. For the monitorization of lindane degradation solid-phase extraction (SPE) was used, while volatile by-products formation measurement was carried out by headspace-solid phase microextraction (HS–SPME) followed by GC/MS. The SPE–GC/MS method provides low detection limits (0.2 μg L⁻¹), high recovery (above 95%) and it is a valuable tool for kinetic studies of the degradation process for each polymer used, while HS–SPME–GC/MS has proved to be an effective tool for the extraction and evaluation of volatile degradation by-products.     

Effect of biosolid incorporation to mollisol soils on Cr, Cu, Ni, Pb, and Zn fractionation, and relationship with their bioavailability

Biosolid application to soil may be a supply of nutrients and micronutrients but it may also accumulate toxic compounds which would be absorbed by crops and through them be incorporated to the trophic chain.

The present study deals with the effect of biosolid application on Cr, Cu, Pb, Ni, and Zn in agricultural soils. The procedure used is sequential extraction so that the availability of those metals may be estimated and related to their bioavailability as determined through two indicator plants grown in greenhouse: ryegrass (Lolium perenne L.) and red clover (Trifolium pratense). Results showed that biosolid application to soil increased total Cu and Zn content. Sequential extraction showed that the more labile Zn fractions increased after biosolid application to soil. This was confirmed when assessing the total content of this metal in shoot and root of the plants under study, since a higher content was found in plant tissues, while no significant differences were found for Cu, Cr, Ni, and Pb.     

A comparison of POPs bioaccumulation in Eisenia fetida in natural and artificial soils and the effects of aging

The close relationship between soil organic matter and the bioavailability of POPs in soils suggests the possibility of using it for the extrapolation between different soils. The aim of this study was to prove that TOC content is not a single factor affecting the bioavailability of POPs and that TOC based extrapolation might be incorrect, especially when comparing natural and artificial soils. Three natural soils with increasing TOC and three artificial soils with TOC comparable to these natural soils were spiked with phenanthrene, pyrene, lindane, p,p'-DDT, and PCB 153 and studied after 0, 14, 28, and 56 days. At each sampling point, total soil concentration and bioaccumulation in earthworms Eisenia fetida were measured. The results showed different behavior and bioavailability of POPs in natural and artificial soils and apparent effects of aging on these differences. Hence, direct TOC based extrapolation between various soils seems to be limited.     

Fate of nickel in a lime-stabilized biosolid,a calcareous soil and soil–biosolid mixtures

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil–biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid–soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.     

Comparative bioremediation potential of four rhizospheric microbial species against lindane

Four microbial species (Kocuria rhizophila, Microbacterium resistens, Staphylococcus equorum and Staphylococcus cohnii subspecies urealyticus) were isolated from the rhizospheric zone of selected plants growing in a lindane contaminated environment and acclimatized in lindane spiked media (5-100 μg mL⁻¹). The isolated species were inoculated with soil containing 5, 50 and 100 mg kg⁻¹ of lindane and incubated at room temperature. Soil samples were collected periodically to evaluate the microbial dissipation kinetics, dissipation rate, residual lindane concentration and microbial biomass carbon (MBC). There was a marked difference (p < 0.05) in the MBC content and lindane dissipation rate of microbial isolates cultured in three different lindane concentrations. Further, the dissipation rate tended to decrease with increasing lindane concentrations. After 45 d, the residual lindane concentrations in three different spiked soils were reduced to 0%, 41% and 33%, respectively. Among the four species, S. cohnii subspecies urealyticus exhibited maximum dissipation (41.65 mg kg⁻¹) and can be exploited for the in situ remediation of low to medium level lindane contaminated soils.     

Relative bioavailability to laying hens of indicator polychlorobiphenyls present in soil

Transfer of indicator polychlorobiphenyls (PCBs) from soil into hen eggs may occur in hens reared outdoor, which ingest significant amounts of soil. This transfer depends on the bioavailability of the ingested compounds. The impact of soil on the bioavailability of indicator PCBs was assessed by means by a relative bioavailability (RBA) trial, in which their deposition in egg yolk and in abdominal fat, in response to their ingestion through contaminated-soil and through spiked-oil were compared. A sandy soil (709 μg indicator PCBs kg⁻¹ dry matter) was collected in the vicinity of a former fire involving treated wood. Twenty-eight laying hens were individually housed and fed one of the seven experimental diets during 14 d. The seven experimental diets were an uncontaminated control diet, three diets in which contaminated soil was introduced at levels of 3%, 6% and 9% and three diets in which spiked oil was introduced to achieve similar levels and profile of contaminants. Yolk, abdominal fat and liver were collected at the end of exposure. Indicator PCBs were extracted by ASE (Accelerated Solvent Extraction) and analyzed by GC-HMRS. Within each ingested matrix, the concentration of indicator PCBs in yolk and in abdominal fat linearly increased with the amount of indicator PCB ingested (P < 0.001). Except for PCB 28, the slopes of the responses to soil and to oil could not be differentiated (P > 0.1). RBA estimates did not differ from 1 for all indicator PCBs except for PCB 28, for which it was 0.58-0.59. Measurements performed on liver confirm these conclusions.     

Comparison of selected non-exhaustive extraction techniques to assess PAH availability in dissimilar soils

Recently, it has become apparent that the use of total contaminant concentrations as a measure of potential contaminant exposure to plants or soil organisms is inappropriate and that bioavailability of contaminants is a better measure of potential exposure. In light of this, non-exhaustive extraction techniques are being investigated to assess their appropriateness in determining bioavailability. In this study, phenanthrene extractability using hydroxypropyl-beta-cyclodextrin (HPCD) and desorption kinetics using butan-1-ol (BuOH) were determined in three dissimilar spiked soils. The soils were extracted after 1 d, 40 d and 80 d of soil-compound contact time. The amount of phenanthrene extracted by HPCD was compared to the rapidly desorbed fraction removed by BuOH. Further experiments using the same soils and extraction methods to assess the relative extractability of phenanthrene, pyrene and benzo(a)pyrene were conducted. Overall, the extraction methods used in this study had different extraction efficiencies. Results suggest that as compound hydrophobicity increased, BuOH became a more exhaustive extractant with respect to HPCD, especially for soils with high clay and organic matter content. These results are important as they highlight differences between two contrasting non-exhaustive extraction techniques both of which have been suggested to be appropriate in the assessment of bioavailability.     

Effect of drying and composting biosolids on the movement of nitrate and phosphate through repacked soil columns under steady-state hydrological conditions

Effects of two "enhanced" treatments (drying and composting mesophilic anaerobically digested (MAD) biosolid) on nutrient leaching were investigated. Repacked sandy or sandy loam textured soil cores amended with fresh, dried and composted MAD biosolid (250 kg N ha(-1)), were investigated under steady-state hydrological conditions. Two 24 h, 4.5 mm h(-1) rainfall events, with a 14-day interval, were simulated using water-tracers. Losses of nitrate from the sandy loam soil during rainfall event 1 (43.9-68.0 mg kg(-1)) were significantly greater (P < or = 0.05) than during event 2 (6.4-11.9 mg kg(-1)). Phosphate losses were significantly greater (P < or = 0.05) during event 2 (up to 0.30 mg kg(-1)) compared to the first (< 0.05 mg kg(-1)). The sand soil showed similar effects. Losses of nitrate-N (percentage of total N applied) from the sand soil were small (around 0.06% for fresh/dried and 0.63% for composted MAD biosolids). Losses of nitrate-N from the sandy loam soil were greater; 4% for fresh and dried and 3% for composted MAD biosolids. This research showed that drying MAD biosolid had little impact on nitrate and phosphate losses from soil compared to fresh MAD biosolid. The effect of composting MAD biosolid on nutrient losses was more variable.     

Evaluation of Quicklime Incorporation in Bench-Scale and Full-Scale Lime Stabilized Biosolids Using a Flat Surface pH Electrode

Abstract

Uniform lime incorporation into sewage sludge is critical for biosolid lime stabilization processes. There is no class B biosolids regulation for lime incorporation. The slurry method is currently used to evaluate the pH of limed biosolids, but this method homogenizes the biosolids and potentially masks poor lime mixing. In this study, a flat-surface pH electrode was used in bench-scale and full-scale experiments to measure the pH of lime-stabilized biosolids without creating slurries. The standard deviation of 15 pH measurements at different locations in a biosolid sample was used to assess mixing quality. The bench-scale experimental study showed that well-mixed limed biosolids had consistently high pHs (~12) with low standard deviations (<0.5 pH units), whereas poorly mixed biosolids had areas with low pH (<10) and high standard deviations (>2 pH units). Poorly mixed biosolids exhibited rapid and marked pH reduction, as well as offensive odor generation, whereas well-mixed biosolids resisted pH reduction and offensive odor generation. The full-scale study aimed at improving lime incorporation and biosolids quality confirmed the use of a flat surface pH electrode to capture low pH regions in biosolids that were masked by the current slurry method.     

Nitrogen mineralization potentials in three tropical soils treated with biosolids

This study attained anaerobic biosolids (DS) and aerobic biosolids (MS) from the wastewater treatment plants in Kaohsiung and Taipei, Taiwan. Three tropical soils (Lt, Cp and Ca) were selected for incubation with the two biosolids at application rates of 10, 50 and 100 Mg ha(-1) for 48 weeks. This study aims to characterize the influence of the application of biosolids on the soil potential for N mineralization (N0) and also to elucidate the kinetics of N mineralization in tropical soils treated with different biosolids. Experimental results indicate that the amounts of N mineralized accumulated in the biosolids-treated soils during the incubation period tended to match the first-order kinetics calculated by the nonlinear least squares equation. The N0 values of the MS biosolids-treated soils greatly exceeded those of the DS soils. The rates of N mineralization (k) of the DS biosolids-treated soils varied greatly from 0.047 to 0.075 week(-1) and that of the MS soils varied from 0.047 to 0.105 week(-1). Little of the organic N fraction in the biosolids remained available for further mineralization following 48 weeks of incubation. Based on the demand of N uptake by vegetables grown in Taiwanese soils, the rates of biosolids application to the soils are safe, as determined by the amount of N mineralization that does not cause nitrate accumulation.     

17 β-estradiol and 17 α-ethinylestradiol mineralization in sewage sludge and biosolids

Natural steroid estrogens (e.g., 17 β-estradiol, E2), synthetic steroid estrogens (e.g., 17 α-ethinylestradiol, EE2) and pharmaceutical antibiotics (e.g., ciprofloxacin) are chemicals detected in biosolids and sewage sludges because they partition into the solids fraction during the wastewater treatment process. This research utilized a three-way factorial design (six media × two estrogens × three antibiotic treatments) to quantify cumulative E2 and EE2 mineralization over 133 d (MAX) in a range of sewage sludge and biosolid samples in the presence (4 and 40 mg kg^?1) and absence of ciprofloxacin. The same three-way factorial design was utilized to quantify the impact of the six media, E2 or EE2, and ciprofloxacin on cumulative soil respiration over 133 d (RESP). Minimal ciprofloxacin mineralization was observed (<0.05% over 133 d), but despite its persistence, ciprofloxacin had no significant effect on MAX of E2 or EE2, and, in general, no significant effect on RESP. MAX ranged from 38.38% to 48.44% for E2 but from only 0.72% to 24.27% for EE2 although RESP was relatively similar, ranging from 101.00 to 866.54 mg CO₂ in the presence of E2 and from 69.55 to 893.95 mg CO₂ in the presence of EE2. The sorption-limited bioavailability of EE2, which is inherently resistant to biodegradation due to chemical structure, as MAX and Freundlich sorption coefficients (K_f) were negatively correlated. As such, the K_f values of EE2 were largest in composted biosolids in which EE2 was particularly resistant to microbial degradation as the MAX of EE2 was <3%. In contrast, the MAX of E2 showed a positive association with the K_f values of E2 because some steps in the E2 transformation process have been found to occur in the sorbed phase. The MAX of E2 was significantly greater in the biosolid and composted biosolid media than in any other media, whereas the MAX of E2 decreased in the following order: secondary sewage sludge > primary sewage sludge > biosolid = composted biosolid. This suggests that sewage sludges in municipal lagoons and pre-treatment holding lagoons are a more favorable media for mineralization of EE2, whereas biosolids in post-treatment storage lagoons are a more favorable media for the mineralization of E2. The presence of ciprofloxacin will have no impact on the potential E2 or EE2 mineralization rates in these cases.     

Extractability and bioavailability of zinc over time in three tropical soils incubated with biosolids

Phytotoxicity of heavy metal is the primary concern in applying biosolids (sewage sludge) to agricultural land. This study evaluates the changes in chemical speciation of Zn in three tropical soils of Taiwan measured with sequential extraction over a one-year period. Biosolids were applied to the soils at application rates of 10, 50 and 100 Mg ha(-1), and correlated diethylene triamine pentaacetic acid (DTPA) and sequential extraction as extract for prediction of Zn bioavailability to Chinese cabbage (Brassica chinensis L.). Experimental results indicated that the exchangeable (F1) and Fe-Mn oxide (F3) fractions in the sequential extractions increased with application rate of biosolids in the soils over time. Large amounts of Zn in the soils following the cessation of biosolids application were identified as soluble and were adsorbed by Fe-Mn oxides. The organically bound Zn, which is associated with readily decomposable carbon, is in limited amounts in the biosolid-treated soils. The DTPA-extractable concentrations of Zn in all biosolid-treated soils decreased over the time. A positive and significant correlation (r(2) = 0.96) was found between the Zn concentrations extracted with DTPA and sum of F1 and carbonate-bound (F2) fractions in the sequential extractions. Additionally, the concentrations of Zn extracted with DTPA were strongly correlated with the concentrations of Zn in the shoots of Chinese cabbages, indicating that F1+F2 in the sequential extractions was reliable for predicting Zn bioavailability to Chinese cabbage in the biosolid-treated soils.     

Poor efficacy of herbicides in biochar-amended soils as affected by their chemistry and mode of action

We evaluated wheat straw biochar produced at 450 °C for its ability to influence bioavailability and persistence of two commonly used herbicides (atrazine and trifluralin) with different modes of action (photosynthesis versus root tip mitosis inhibitors) in two contrasting soils. The biochar was added to soils at 0%, 0.5% and 1.0% (w/w) and the herbicides were applied to those soil-biochar mixes at nil, half, full, two times, and four times, the recommended dosage (H₄). Annual ryegrass (Lolium rigidum) was grown in biochar amended soils for 1 month. Biochar had a positive impact on ryegrass survival rate and above-ground biomass at most of the application rates, and particularly at H₄. Within any given biochar treatment, increasing herbicide application decreased the survival rate and fresh weight of above-ground biomass. Biomass production across the biochar treatment gradient significantly differed (p < 0.01) and was more pronounced in the case of atrazine than trifluralin. For example, the dose-response analysis showed that in the presence of 1% biochar in soil, the value of GR₅₀ (i.e. the dose required to reduce weed biomass by 50%) for atrazine increased by 3.5 times, whereas it increased only by a factor of 1.6 in the case of trifluralin. The combination of the chemical properties and the mode of action governed the extent of biochar-induced reduction in bioavailability of herbicides. The greater biomass of ryegrass in the soil containing the highest biochar (despite having the highest herbicide residues) demonstrates decreased bioavailability of the chemicals caused by the wheat straw biochar. This work clearly demonstrates decreased efficacy of herbicides in biochar amended soils. The role played by herbicide chemistry and mode of action will have major implications in choosing the appropriate application rates for biochar amended soils.     

Influence of humified organic matter on copper behavior in acid polluted soils

The main purpose of this work was to identify the role of soil humic acids (HAs) in controlling the behavior of Cu(II) in vineyard soils by exploring the relationship between the chemical and binding properties of HA fractions and those of soil as a whole. The study was conducted on soils with a sandy loam texture, pH 4.3-5.0, a carbon content of 12.4-41.0 g kg⁻¹ and Cu concentrations from 11 to 666 mg kg⁻¹. The metal complexing capacity of HA extracts obtained from the soils ranged from 0.69 to 1.02 mol kg⁻¹, and the stability constants for the metal ion-HA complexes formed, log K, from 5.07 to 5.36. Organic matter-quality related characteristics had little influence on Cu adsorption in acid soils, especially if compared with pH, the degree of Cu saturation and the amount of soil organic matter.     

A root exudates based approach to assess the long-term phytoavailability of metals in biosolids-amended soils

Organic acids present in the rhizosphere of growing plants are widely recognized to be responsible for dissolving the solid phase metals in the soil and making them available for plant absorption. We proposed a root exudates-based model to assess the long-term phytoavailability of metals in biosolids-amended soils. The phytoavailability of biosolids-borne metals was defined in terms of a capacity factor and an intensity factor. The plant available metal pool, C₀ (capacity factor, mg kg⁻¹), can be estimated by fitting the successive organic acids extraction data to an exponential decay kinetic equation. The field metal removal rate, k (intensity factor, yr⁻¹), can be estimated from the successive extraction-based metal release rate through an effective annual organic acid production in the rhizosphere which was found to be characteristic of plant species. The protocol was successfully used to assess the long-term phytoavailability of metals in biosolids-amended soil from two biosolids land application sites.     

Assessing the chemical and biological accessibility of the herbicide isoproturon in soil amended with biochar

Decamethylcyclopentasiloxane (D5) is a cyclic volatile methyl siloxane (cVMS) commonly found in commercially available products. D5 is expected to enter the terrestrial environment through the deposit of biosolids from sewage treatment plants onto agricultural fields for nutrient enrichment. Little to no information currently exists as to the risks of D5 to the terrestrial environment. In order to evaluate the potential risk to terrestrial organisms, the toxicity of a D5 contaminated biosolid in an agricultural soil was assessed with a battery of standardized soil toxicity tests.D5 was spiked into a surrogate biosolid and then mixed with a sandy loam soil to create test concentrations ranging from 0 to 4074 mg kg⁻¹. Plant (Hordeum vulgare (barley) and Trifolium pratense (red clover)) and soil invertebrates (Eisenia andrei (earthworm) and Folsomia candida (springtail)) toxicity tests were completed to assess for lethal and sub-lethal effects. Plant testing evaluated the effects on seedling emergence, shoot and root length, and shoot and root dry mass. Invertebrate test endpoints included adult lethality, juvenile production, and individual juvenile dry mass (earthworms only). Soil samples were collected over time to confirm test concentrations and evaluate the loss of chemical over the duration of a test. The toxicity of the D5 was species and endpoint dependent, such that no significant adverse effects were observed for T. pratense or E. andrei test endpoints, however, toxicity was observed for H. vulgare plant growth and F. candida survival and reproduction. Chemical losses of up to 50% were observed throughout the tests, most significantly at high concentrations.     

Characterization of Fe–humic complexes in an Fe-enriched biosolid by-product of water treatment

The fertilizing potential of Fe-enriched biosolids has been attributed to Fe associations with humic substances contained therein. In this study, alkaline and near-neutral aqueous extractions of humic substances from an Fe-enriched biosolid were followed by gel chromatographic fractionation and characterization (CHNS elemental analysis; UV/visible and FTIR spectroscopy; FAAS analysis). The alkaline bulk humic extract had a strong fulvic character and Fe was predominantly associated with the higher molecular weight (∼50 000 Da) molecules, possibly including organic-coated Fe oxides from which Fe may be released more slowly. Under both near-neutral and alkaline conditions, associations with lower molecular weight humic molecules were also observed, indicative of the presence of Fe in more readily available forms. Thus the biosolid appears to have good short- and long-term fertilizing potential, particularly for alkaline, Fe-deficient soils.     

Assessing biodegradation potential of PAHs in complex multi-contaminant matrices

This study sought to extend validation of a cyclodextrin based extraction method for the assessment of PAH-biodegradation potential to complex multi-contaminant matrices. To this end, four reference materials (RMs) were produced by blending, in different proportions, soils impacted with diesel, lubricating oil and spent oxide. These reference materials had modest ∑PAH (16 US EPA) concentrations that ranged from 5.6 ± 0.5 to 44.4 ± 4.5 mg kg⁻¹. However, extractable petroleum hydrocarbon (EPH) concentrations were comparatively high (up to 2520 ± 204 mg kg⁻¹). To complement these RMs, two further soils from a municipal gas plant (MGP) with highly elevated concentration of PAHs ranging from 877 ± 52 to 2620 ± 344 mg kg⁻¹ were also tested. Results showed, regardless of matrix complexity, that PAH biodegradation within the four RM substrates, and two MGP soils correlated well with biodegradation predicted by hydroxypropyl-β-cyclodextrin (HPCD) extraction.