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.     

Solid beef cattle manure application impacts on soil properties and 17β-estradiol fate in a clay loam soil

Livestock manure applied to agricultural land is one of the ways natural steroid estrogens enter soils. To examine the impact of long-term solid beef cattle (Bos Taurus) manure on soil properties and 17β-estradiol sorption and mineralization, this study utilized a soil that had received beef cattle manure over 35 years. The 17β-estradiol was strongly sorbed and sorption significantly increased (P < 0.05) with increasing soil organic carbon content (SOC) and with an increasing annual rate of beef cattle manure. The 17β-estradiol mineralization half-life was significantly negatively correlated, and the total amount of 17β-estradiol mineralized at 90 days (MAX) was significantly positively correlated with 17β-estradiol sorption. The long-term rate of manure application had no significant effect on MAX, but the addition of fresh beef cattle manure in the laboratory resulted in significantly (P < 0.05) smaller MAX values. None of the treatments showed MAX values exceeding one-third of the 17β-estradiol applied.     

Solid beef cattle manure application impacts on soil properties and 17β-estradiol fate in a clay loam soil

Livestock manure applied to agricultural land is one of the ways natural steroid estrogens enter soils. To examine the impact of long-term solid beef cattle (Bos Taurus) manure on soil properties and 17β-estradiol sorption and mineralization, this study utilized a soil that had received beef cattle manure over 35 years. The 17β-estradiol was strongly sorbed and sorption significantly increased (P < 0.05) with increasing soil organic carbon content (SOC) and with an increasing annual rate of beef cattle manure. The 17β-estradiol mineralization half-life was significantly negatively correlated, and the total amount of 17β-estradiol mineralized at 90 days (MAX) was significantly positively correlated with 17β-estradiol sorption. The long-term rate of manure application had no significant effect on MAX, but the addition of fresh beef cattle manure in the laboratory resulted in significantly (P < 0.05) smaller MAX values. None of the treatments showed MAX values exceeding one-third of the 17β-estradiol applied.     

Remediation of polycyclic aromatic hydrocarbon and metal-contaminated soil by successive methyl-β-cyclodextrin-enhanced soil washing–microbial augmentation: a laboratory evaluation

Polycyclic aromatic hydrocarbon (PAH) and metal-polluted sites caused by abandoned coking plants are receiving wide attention. To address the associated environmental concerns, innovative remediation technologies are urgently needed. This study was initiated to investigate the feasibility of a cleanup strategy that employed an initial phase, using methyl-β-cyclodextrin (MCD) solution to enhance ex situ soil washing for extracting PAHs and metals simultaneously, followed by the addition of PAH-degrading bacteria (Paracoccus sp. strain HPD-2) and supplemental nutrients to treat the residual soil-bound PAHs. Elevated temperature (50 °C) in combination with ultrasonication (35 kHz, 30 min) at 100 g MCD L^?1 was effective in extracting PAHs and metals to assist soil washing; 93 % of total PAHs, 72 % of Cd, 78 % of Ni, 93 % of Zn, 84 % of Cr, and 68 % of Pb were removed from soil after three successive washing cycles. Treating the residual soil-bound PAHs for 20 weeks led to maximum biodegradation rates of 34, 45, 36, and 32 % of the remaining total PAHs, 3-ring PAHs, 4-ring PAHs, and 5(+6)-ring PAHs after washing procedure, respectively. Based on BIOLOG Ecoplate assay, the combined treatment at least partially restored microbiological functions in the contaminated soil. The ex situ cleanup strategy through MCD-enhanced soil washing followed by microbial augmentation can be effective in remediating PAH and metal-contaminated soil.     

Sorption of lead in soil as a function of pH: a study case in México

Reactions of lead sorption onto soil are largely affected by properties and composition of soil and its solution. In this study, the lead sorption onto regosol eutric soil from Francisco I. Madero, Zacatecas, Mexico is evaluated at different pH values. Soil samples were suspended in lead solutions of 10, 25, 50, 100, 150, 200, 300, and 400 mg/l (as Pb(NO3)2). The pH was adjusted at 2, 3, 4, and 5.5 with nitric acid for each of the lead solution concentrations. In all the cases the ionic strength was I=0.09 M with calcium nitrate. The solid-liquid-ratios were fixed in 1:100 and 1:200 g/ml. The results show that lead sorption increases when pH increases. Experimental isotherms were adjusted by both Langmuir and Freundlich models. The Langmuir affinity parameter, K, indicates that the lead sorption capacity of Francisco I. Madero soils is largely perceptible to pH changes.     

Can we predict uranium bioavailability based on soil parameters? Part 2: soil solution uranium concentration is not a good bioavailability index

The present study aimed to quantify the influence of soil parameters on uranium uptake by ryegrass. Ryegrass was established on eighteen distinct soils, spiked with (238)U. Uranium soil-to-plant transfer factors (TF) ranged from 0.0003 to 0.0340kgkg(-1). There was no significant relation between the U soil-to-plant transfer (or total U uptake or flux) and the uranium concentration in the soil solution or any other soil factor measured, nor with the U recovered following selective soil extractions. Multiple linear regression analysis resulted in a significant though complex model explaining up to 99% of variation in TF. The influence of uranium speciation on uranium uptake observed was featured: UO(2)(+2), uranyl carbonate complexes and UO(2)PO(4)(-) seem the U species being preferentially taken up by the roots and transferred to the shoots. Improved correlations were obtained when relating the uranium TF with the summed soil solution concentrations of mentioned uranium species.     

Does monensin in chicken manure from poultry farms pose a threat to soil invertebrates?

Monensin is a carboxylic polyether ionophore used in the poultry industry as a coccidiostat. It enters the environment via manure from broiler farms. In spite of its potential presence in the environment, information concerning monensin residues in manure and soil and its toxicity to soil organisms are insufficient. In the present study, two beneficial soil invertebrate species, earthworms (Eisenia andrei) and woodlice (Porcellio scaber), were used to assess the toxicity of monensin. Animals were exposed to a range of monensin concentrations via soil or food. Earthworm reproduction was found to be the most susceptible endpoint (NOEC=3.5 mg kg(-1) dry soil; EC(50)=12.7 mg kg(-1) dry soil), while no adverse effects were recorded in isopods (NOEC?849mgkg(-1) dry soil, NOEC?357mgkg(-1) dry food). The obtained toxicity data were compared with potential concentrations of monensin in soil. In view of this, manure from broiler chickens treated with monensin at a poultry farm was sampled. According to monensin and nitrogen concentrations in the chicken manure and the degradation time of monensin, the predicted environmental concentration (PEC) was calculated. PEC of monensin is around 0.013 mg kg(-1) soil if manure is used after 3 months of composting and 0.05 mg kg(-1) soil if used without storage. Data for earthworm reproduction was used to estimate the predicted no-effect concentration (PNEC). If fresh chicken manure is applied to terrestrial ecosystems, the risk quotient (PEC/PNEC ratio) is above 1, which indicates that monensin might pose an environmental risk under certain conditions. To prevent this, it is strongly recommended to compost chicken manure for several months before using it as fertiliser.     

Release of methane from aerobic soil: an indication of a novel chemical natural process?

Methane (CH₄) formation under aerobic conditions has been intensely debated, especially since the discovery of CH₄ generation by both dried plant material and living plants. In this study we test the hypothesis that non-microbial CH₄ formation also occurs in soils. All lyophilised soil samples investigated under aerobic conditions released CH₄ at temperatures ranging from 30 to 70 °C exceeding that allowing normal enzymatic activity to proceed. No emissions were observed for single mineral soil components such as quartz sand, clay mineral and iron oxide. Methane release rates from the soils investigated were found to increase both with increasing temperature and higher organic carbon content. Addition of water to dried soils increased CH₄ release rates up to 8-fold those observed with the dried material. Our results suggest the existence of a chemical process in soils that produces CH₄ under aerobic conditions, a finding which has not been hitherto reported.     

Microbial communities to mitigate contamination of PAHs in soil—possibilities and challenges: a review

Background, aim, and scope  

Although highly diverse and specialized prokaryotic and eukaryotic microbial communities in soil degrade polycyclic aromatic hydrocarbons (PAHs), most of these are removed slowly. This review will discuss the biotechnological possibilities to increase the microbial dissipation of PAHs from soil as well as the main biological and biotechnological challenges.     

The soil–air exchange characteristics of total gaseous mercury from a large-scale municipal landfill area

The cycle of mercury (Hg) from a gigantic landfill area (area ∼2.72 km²) was investigated by conducting micrometeorological measurements of its exchange rates across soil–air boundary during the spring season of 2000. Based on this field campaign, we attempted to provide various insights into the Hg exchange processes, especially with respect to the decoupling of the mixed signatures of complex source processes. According to our analysis, the cycle of Hg in the study site appeared to be affected significantly by the vent processes; excessive amount of Hg was expected to be released via ventpipes penetrating up to 60 m depths of the deep landfilled waste layer. The influence of these vent source processes was reflected very sensitively by the windrose pattern. The data collected during the non-easterly winds were representing the typical pattern for a strong source area in which upward emission is predominant in both strength and frequency. On the other hand, the data collected from the easterly winds were characterized by excessive deposition of Hg which we suspect is due mostly to the nearest vent located easterly from our measurement spot. The unique characteristics of each data group, divided by windrose pattern, were consistent from apparent difference in: (1) the absolute magnitude of gradient/flux data sets, (2) frequency of exchange for each of two vertical directions, and (3) E/D (emission/deposition) ratios for most relevant parameters. The analysis of the short-term variability of exchange patterns over a 24-h scale, also exhibited that the patterns for two different conditions were quite contrasting as a function of time. The magnitude of bidirectional fluxes in the present study is significantly high with values of 254±224 (N=71 emissions out of 79 fluxes quantified during non-easterly winds) and −1164±1276 ng m⁻² h⁻¹ (N=14 depositions out of 16 fluxes during easterly winds), respectively. If the computed emission rate is extrapolated, we estimate that annual emission of Hg from the study area can amount to approximately 6 kg which is comparable with the estimates for other areas around the globe under strong Hg-pollution.     

Can we predict uranium bioavailability based on soil parameters? Part 1: effect of soil parameters on soil solution uranium concentration

Present study aims to quantify the influence of soil parameters on soil solution uranium concentration for (238)U spiked soils. Eighteen soils collected under pasture were selected such that they covered a wide range for those parameters hypothesised as being potentially important in determining U sorption. Maximum soil solution uranium concentrations were observed at alkaline pH, high inorganic carbon content and low cation exchange capacity, organic matter content, clay content, amorphous Fe and phosphate levels. Except for the significant correlation between the solid-liquid distribution coefficients (K(d), L kg(-1)) and the organic matter content (R(2)=0.70) and amorphous Fe content (R(2)=0.63), there was no single soil parameter significantly explaining the soil solution uranium concentration (which varied 100-fold). Above pH=6, log(K(d)) was linearly related with pH [log(K(d))=-1.18 pH+10.8, R(2)=0.65]. Multiple linear regression analysis did result in improved predictions of the soil solution uranium concentration but the model was complex.     

Uptake of heavy metals and As by Brassica juncea grown in a contaminated soil in Aznalcóllar (Spain): the effect of soil amendments

Two crops of Brassica juncea (L.) Czern. were grown in a field experiment, at the site affected by the toxic spillage of acidic, metal-rich waste in Aznalcóllar (Seville, Spain), to study its metal accumulation and the feasibility of its use for metal phytoextraction. The effects of organic soil amendments (cow manure and mature compost) and lime on biomass production and plant survival were also assessed; plots without organic amendment and without lime were used as controls. Plots, with or without organic amendment, having pH < 5 were limed for the second crop. Soil acidification conditioned plant growth and metal accumulation. The addition of lime and the organic amendments achieved higher plant biomass production, although effects concerning metal bioavailability and accumulation were masked somewhat by pH variability with time and between and within plots. Tissue metal concentrations of B. juncea were elevated for Zn, Cu and Pb, especially in leaves of plants from plots with low pH values (maxima of 2029, 71 and 55 microg g(-1), respectively). The total uptake of heavy metals in the plants was relatively low, emphasising the problems faced when attempting to employ phytoextraction for clean-up of pluri-contaminated sites.     

In situ phytoremediation of heavy metal–contaminated soil and groundwater: a green inventive approach

Environmental Science and Pollution Research - The heavy metal contamination of soil and groundwater is a serious threat to environment worldwide. The survival of human being primarily relies upon...     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco,Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-α,α,α -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g^{? 1}; short-term experiment) to 200 days (initial concentration = 689 ng g^{? 1}; long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Is phytoremediation a sustainable and reliable approach to clean-up contaminated water and soil in Alpine areas?

Background, aim and scope  

Phytoremediation does exploit natural plant physiological processes and can be used to decontaminate agricultural soils, industrial sites, brownfields, sediments and water containing inorganic and organic pollutants or to improve food chain safety by phytostabilisation of toxic elements. It is a low-cost and environment friendly technology targetting removal, degradation or immobilisation of contaminants. The aim of the present review is to highlight some recent advances in phytoremediation in the Alpine context.     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco, Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-alpha,alpha,alpha -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g(-1); short-term experiment) to 200 days (initial concentration = 689 ng g(-1); long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Chloroform – concentration gradients in soil air and atmospheric air,and emission fluxes from soil

Since we demonstrated the natural formation of chloroform in soil, the question arose to which extent this contributes to the chloroform present in the atmosphere. Concentration gradients in soil air and atmospheric air of different forests were measured. Chloroform concentration gradients indicating emission occur in forest soils and the atmosphere under the canopy, whereas this was not observed for other chlorinated solvents. Above the canopy all concentration gradients observed for chloroform and 1,1,1-trichloroethane indicate deposition. The emission flux was measured using enclosures and calculated from the observed concentration gradients in soil air and atmospheric air. Wood-degrading areas and soils with a humic layer were found to emit up to 1000 ng chloroform m⁻² h⁻¹ and seem to be larger chloroform sources than the other areas of study. Rather unexpectedly, some points of one sampling site appeared to emit 1,1,1-trichloroethane, tetrachloromethane and tetrachloroethene. A reasonable agreement was found between the fluxes using enclosures and those derived from the concentration gradients in soil air and atmospheric air.     

Where can cone penetrometer technology be applied? Development of a map of Europe regarding the soil penetrability

Over the past decades, significant efforts have been invested in the development of push-in technology for site characterization and monitoring for geotechnical and environmental purposes and have especially been undertaken in the Netherlands and Germany. These technologies provide the opportunity for faster, cheaper, and collection of more reliable subsurface data. However, to maximize the technology both from a development and implementation point of view, it is necessary to have an overview of the areas suitable for the application of this type of technology. Such an overview is missing and cannot simply be read from existing maps and material. This paper describes the development of a map showing the feasibility or applicability of Direct Push/Cone Penetrometer Technology (DPT/CPT) in Europe which depends on the subsurface and its extremely varying properties throughout Europe. Subsurface penetrability is dependent on a range of factors that have not been mapped directly or can easily be inferred from existing databases, especially the maximum depth reachable would be of interest. Among others, it mainly depends on the geology, the soil mechanical properties, the type of equipment used as well as soil-forming processes. This study starts by looking at different geological databases available at the European scale. Next, a scheme has been developed linking geological properties mapped to geotechnical properties to determine basic penetrability categories. From this, a map of soil penetrability is developed and presented. Validating the output by performing field tests was beyond the scope of this study, but for the country of the Netherlands, this map has been compared against a database containing actual cone penetrometer depth data to look for possible contradictory results that would negate the approach. The map for the largest part of Europe clearly shows that there is a much wider potential for the application of Direct Push Technology than is currently seen. The study also shows that there is a lack of large-scale databases that contain depth-resolved data as well as soil mechanical and physical properties that can be used for engineering purposes in relation to the subsurface.     

Selected chloro and bromo derivatives of triclosan—syntheses and their occurrence in Canadian sewage and biosolid samples

The occurrence of triclosan (TCS), a general purpose antibacterial agent contained in numerous consumer and personal-care products, in the aquatic environment is well known. To a lesser degree, the formation of chlorinated and brominated derivatives of TCS during the chlorination of the antibacterial has also been reported. Presumably due to the lack of authentic standards, very few reports have been published on the levels of these halogenated TCSs in the environment. For this purpose, we have synthesized six selected halogenated derivatives of TCS, namely, 3-Cl-, 5-Cl-, 3,5-Cl₂-, 3-Br-, 5-Br-, and 3,5-Br₂- TCSs, with supporting ¹H-NMR (nuclear magnetic resonance) and GC–MS (gas chromatography–mass spectrometry) data for their structural assignments. Using these model compounds together with sensitive analytical methods, we were able to identify and quantify the above compounds together with their precursor compound TCS in Canadian municipal wastewater and biosolid samples for the first time. While detected in all influent (range from 1.4 to 24.1 ng L^?1) and biosolid (range from 7.7 to 274 ng g^?1) samples, the concentrations of these chlorinated TCS were generally from 100- to 1,000-fold lower than TCS in the same sample. Even lower levels (<20 ng/g in 85 % of the results) of brominated TCS were found in biosolids, and they were mostly undetected in sewage.