Behavior of chlorpyrifos and its major metabolite TCP (3,5,6-trichloro-2-pyridinol) in agricultural soils amended with drinking water treatment residuals

Purpose

Chlorpyrifos can be effectively adsorbed by drinking water treatment residuals (WTR), ubiquitous and non-hazardous by-products of potable water production. The major metabolite 3,5,6-trichloro-2-pyridinol (TCP) was found to be much more mobile and toxic than its parent chlorpyrifos. To assess the feasibility of WTR amendment for attenuation of chlorpyrifos and TCP pollution, the sorption/desorption and degradation behavior of chlorpyrifos and TCP in WTR-amended agricultural soils was examined in the present study.

Materials and methods

Two representative agricultural soils were sampled from southern and northern China, respectively. The soils were amended with WTR at the rates of 0, 2, 5, and 10 % (w/w). Batch sorption/desorption test were applied to investigate the sorption/desorption characteristics of chlorpyrifos and TCP in WTR-amended soils. The influence of WTR amendment on chlorpyrifos degradation and TCP formation was evaluated using the incubation test, and its effect on the soil bacterial abundance was further studied through DNA extraction and PCR amplification.

Results and discussion

Results showed that WTR amendment (0–10 %, w/w) significantly enhanced the retention capacity of chlorpyrifos and TCP in both soils examined (P < 0.05). Fractionation analyses further demonstrated that the bioavailability of chlorpyrifos was considerably reduced by WTR amendment, resulting in a decreased chlorpyrifos degradation rate. The WTR amendment also significantly reduced the mobility of TCP formed in chlorpyrifos-contaminated soils (P < 0.001). The chlorpyrifos toxicity to soil bacteria community was largely mitigated following WTR amendment, resulting in increased total bacterial abundance.

Conclusions

Results obtained in the present study indicate a great deal of potential for the beneficial reuse of WTR as soil amendments for chlorpyrifos and TCP pollution control.

     

Effect of equilibration time on estimates of the maximum phosphorus sorption capacity of industrial by-products using the Langmuir model

Purpose

Using reactive industrial by-products (IBPs) to reduce phosphorus (P) losses associated with diffuse water pollution is a potentially cost-effective mitigation strategy. However, IBPs must be screened to assess their effectiveness and optimum application rates. This requires accurate estimates of parameters such as the maximum P sorption capacity. Traditionally, these parameters have been derived from the Langmuir model applied to data from batch sorption experiments following a 24-h equilibration period. In this paper, we examined (i) how equilibration time can influence estimates of the maximum P sorption capacity for IBPs and (ii) the relative P sorption characteristics of a range of IBPs available in the UK.

Materials and methods

Four IBPs containing different reactive components including ochre, aluminium (Al)-based water treatment residual (WTR), iron (Fe)-based WTR and Fe-lime (CaO)-based WTR were selected for this study. The maximum P sorption capacities of these IBPs were determined using a linearized Langmuir model applied to batch sorption data collected at different equilibration times of 24 h, 5 days and 10 days.

Results and discussion

The maximum P sorption capacity of ochre, Al-based WTR, Fe-based WTR and Fe-CaO-based WTR estimated from the linearized Langmuir model following a 24-h equilibration period was 10.1, 13.7, 2.4 and 9.3 mg P g^?1, respectively. However, extending the equilibration time from 24 h to 5 days increased the estimated maximum P sorption capacity for these IBPs by factors of 2.2, 2.1, 6.8 and 2.3, respectively. No significant increase was found in estimates of the maximum P sorption capacity when further extending the equilibration time to 10 days.

Conclusions

A minimum equilibration period of 5 days is recommended to avoid underestimating the maximum P sorption capacity of the IBPs examined in this paper. Each of the IBPs we evaluated was able to sorb P from solution, although with variable capacity (maximum sorption capacity after 5 days of equilibration ranged from 16.3–28.5 mg P g^?1). These findings emphasise the importance of accurate quantification of the P sorption capacity of IBPs before application.     

Sorption isotherms and kinetics of Sb(V) on several Chinese soils with different physicochemical properties

Purpose

Sorption of antimony on soils is the primary factor that influences its immobilization and migration in the environment. In the present study, the sorption of Sb(V) onto seven Chinese soils with different physicochemical properties was investigated for exploring the relationship between the sorption capacity of Sb(V) and the physicochemical properties of the soils.

Materials and methods

Sorption isotherms and kinetics experiments were performed to ascertain the sorption capacity and the kinetic rate, respectively. The relationship between the sorption capacity of Sb(V) and the physicochemical properties of the soils was analyzed by multiple linear regressions.

Results and discussion

The results showed that the sorption isotherms fitted with both the Langmuir and Freundlich equations very well (R ²?=?0.936–0.997), and the sorption kinetic of Sb(V) onto the seven Chinese soils followed a pseudo-second-order reaction. The maximum sorption capacity of Sb(V) on the soils ranged from 134 to 1,333 mg?kg^?1. Nearly 94 % of the variability in maximum sorption of Sb(V) modeled by Freundlich equation could be described by Fe_DCB (dithionite–citrate–bicarbonicum extractable), and nearly 98 % of the variability could be described by Fe_DCB and Al_DCB.

Conclusions

Multiple linear regressions can be successfully applied to analyzing the relationship between sorption capacity and soil properties. Fe_DCB and Al_DCB played important roles in Sb(V) sorption onto soils. It would be useful to understand the environmental behaviors of Sb and for the implementation of risk assessment management and remediation strategies of Sb.     

Land Application of Aluminum Water Treatment Residual: Aluminum Phytoavailability and Forage Yield

Negative impacts of land‐applied aluminum (Al)–rich water treatment residuals (WTRs), which have been suggested to improve soil phosphorus (P) sorption, could include excessive immobilization of plant‐available P and Al phytotoxicity. We studied the impacts of an Al‐rich WTRs on agronomic returns and plant Al concentrations in glasshouse and field studies. The glasshouse study was a 4 × 2 × 3 factorial experiment with one control in a randomized complete block design and three replicates. Four sources of P were each applied at two agronomic rate [44 kg P ha^?1, P‐based rate; and 179 kg plant‐available nitrogen (PAN) ha^?1, N‐based rate] to topsoil (0–15 cm) of a sandy, siliceous, hyperthermic Arenic Alaquods. Three WTR rates (0, 10, and 25 g kg^?1 oven‐dry‐weight basis) were further applied, whereas the control received neither P source nor WTRs. Bahiagrass (Paspalum notatum Fluggae), ryegrass (Lolium perenne L.), and a second bahiagrass crop were continuously grown in succession for 18 months. Applied WTRs increased soil Al but not plant Al concentrations (22–80 mg Al kg^?1), which fell within the normal concentration range for pasture plants. In the glasshouse, when WTRs were incorporated with the soil, bahiagrass dry matter (DM) accumulation was reduced, but ryegrass DM was not affected even at 25 g kg^?1 WTR. A 2‐year field study, with same treatments but two rates of WTRs (0 and 10 g kg^?1 WTR) surface applied to established bahiagrass on the same soil type (Spodosols) showed neither reduced yields nor increased plant Al phytoavailability in the WTR treatments. The studies show no increase in plant Al is associated with Al‐WTRs applied to reduce excess soil‐soluble P and P losses but plant DM accumulation may be reduced.     

Linking Ni and Cr concentrations to soil mineralogy: does it help to assess metal contamination when the natural background is high?

Purpose

In soils from serpentinitic areas the natural background of Ni and Cr is so high that the assessment of contamination by comparing metal concentrations with some fixed thresholds may give unreliable results. We therefore sought a quantitative relation between serpentines and Ni and Cr concentrations in uncontaminated soils, evaluated if the approach may help in establishing a baseline, and discussed if additional anthropogenic inputs of Ni and Cr can be realistically individuated in these areas.

Materials and methods

We analysed the total, acid-extractable and exchangeable concentrations of Ni and the total and acid-extractable concentrations of Cr in 66 soil horizons, belonging to 19 poorly developed and uncontaminated Alpine soils. The soils had different amounts of serpentines, depending on the abundance of these minerals in the parent material. We calculated an index of abundance of serpentines in the clay fraction by XRD and related total metal contents to the mineralogical index. We then tested the regressions on potentially contaminated soils, developed on the alluvial plain of the same watershed.

Results and discussion

We found extremely high total concentrations of Ni (up to 1,887 mg kg^–1) and Cr (up to 2,218 mg kg^–1) in the uncontaminated soils, but only a small proportion was extractable. Total Ni and Cr contents were significantly related to serpentine abundance (r ²?=?0.86 and 0.74, respectively). The regressions indicated that even small amounts of serpentines induced metal contents above 200 mg kg^–1, and the 95% confidence limits were 75 and 111 mg kg^–1 of Ni and Cr, respectively. When the regressions were tested on the potentially contaminated soils, a good estimate was obtained for Cr, while the Ni concentration was overestimated, probably because of some leaching of this element.

Conclusions

The concentrations of Ni and Cr that can be expected in soils because of the presence of small amounts of serpentines are comparable to the amounts accumulated in the soil because of diffuse contamination and potentially contaminated soils had metal concentrations falling in the range expected from the presence of natural sources. Only in the case of very severe contamination events, the identification of anthropogenic sources adding to the natural background would be feasible.     

Anthropogenic environmental impact in the Mediterranean coastal area of Koper/Capodistria,Slovenia

Purpose

Heavy metal content in soils could be a consequence of geogenic and different anthropogenic sources. In ancient times, soils in the Mediterranean region were affected by agriculture and viticulture, whereas more recently, industry and traffic might contribute more to their pollution. The aim of the study is to determine the extent of multisource heavy metal pollution in soils within the Koper area.

Materials and methods

Along the northern Adriatic Sea coast, around the port city of Koper/Capodistria, 24 topsoil samples were collected; sets of six samples representing four possible pollution sources: intensive agriculture, viticulture, port activities and industry. The parent material of the soil is mainly derived from the Eocene flysch weathered marls and calcarenites and the soil types are eutric. The chemical composition of the samples was determined by ICP-ES for oxides and several minor elements and by ICP-MS for heavy metals. The mineral composition of the selected samples was checked using X-ray powder diffraction. Different statistical analyses were performed on the normally distributed data.

Results and discussion

The mean concentrations of all samples are: Cr 215 mg kg^?1, Ni 81 mg kg^?1, Zn 67 mg kg^?1, Cu 44 mg kg^?1 and Pb and Co 18 mg kg^?1. The ANOVA showed significant differences only in CaO, C/TOT, P₂O₅, Co and Pb between those locations within reach of the different contamination sources. The observed average values of heavy metals are well below Slovenia’s Directive limit for Cu, Pb and Zn, close to but not above it for Co and above the action value for Cr and Ni. According to Igeo, soils from all the sampling locations are uncontaminated with Co, Ni and Pb, and uncontaminated to moderately contaminated with Cu and Zn at one port location, and with Cr at all locations.

Conclusions

The very high Cr and Ni levels could still be geogenic because soils developed on Eocene flysch rocks are enriched in both metals. Cr and Ni are not correlated because of their different levels of sorption and retention in carbonate soils. Cr was retained and concentrated in the sand fraction but Ni has been mobilised in solution. The only serious threat to the environment seems to be an illegal waste dumping area near the port.     

How do amorphous sesquioxides affect and contribute to butachlor retention in soils?

Purpose

Sorption and desorption of butachlor were simultaneously investigated on synthesized pure amorphous hydrated Fe oxides (AHOs Fe), and soils both with and without surface coating of AHOs Fe, with special interest towards how amorphous sesquioxides affect and contribute to butachlor retention in soils.

Materials and methods

The AHOs Fe was artificially synthesized pure materials. Two soils with contrasting physicochemical properties selected for study were black soil and latosol, belonging to permanent charged soil and variable charged soil, respectively. Both soils were further treated using AHOs Fe for detecting the differentiation from native soils regarding butachlor retention produced after the soils were surface-coated by AHOs Fe. A sorption experiment was conducted using a batch equilibrium technique, and desorption was carried out immediately following sorption by three sequential dilution. Hysteresis index (HI) values were calculated to investigate desorption hysteresis by developing desorption isotherms concentration dependent and time dependent, respectively.

Results and discussion

The sorption capacity for butachlor increased in the order of AHOs Fe, uncoated soils, and soils with surface coating of AHOs Fe. The sorption capacity of both soils significantly increased after surface coating by AHOs Fe (p?<?0.01), with a bigger increase achieved by black soil (52.0 %) as compared with that by latosol (45.3 %). Desorption of butachlor was coincidently hysteretic on AHOs Fe, and soils both uncoated and coated, whereas variation in desorption hysteresis was different between AHOs Fe and soils with increasing butachlor sorption loading, indicating different sorption mechanisms were operative for AHOs Fe and soils across the entire butachlor concentration range. Hysteresis of butachlor desorption was weakened after the soils were surface coated by AHOs Fe, as suggested by the changed HI values.

Conclusions

With high specific surface area and highly reactive surfaces, the “active” AHOs Fe originally has a relatively high sorption capacity and affinity for butachlor. While in natural soils, where the inevitable association derived from soil organic matter (SOM) would restrain AHOs Fe from sequestrating butachlor directly, AHOs Fe may likely contribute in a mediator way by coordinating active sites both on and within SOM. This may enhance the availability of sorption domains both on and within soils, thereby achieved an enhanced but more reversible retention for butachlor in soils after their surfaces were coated by AHOs Fe. This study has extended the observations of the role of noncrystalline sesquioxides in retention of pesticides such as butachlor from pure clay mineral systems to natural soils.     

Effect of biosolid application to Mollisol Chilean soils on the bioavailability of heavy metals (Cu,Cr, Ni,and Zn) as assessed by bioassays with sunflower (Helianthus annuus) and DGT measurements

Purpose

This study assessed the effect of biosolid application on the bioavailable fraction of some trace elements (Cu, Cr, Ni, and Zn) using a bioassay with sunflower (Helianthus annuus) and a chemical assay, diffusion gradient in thin films (DGT).

Materials and methods

Five surface soil samples (0–20 cm) were collected from an agricultural zone in Central Chile where biosolids are likely to be applied. Municipal biosolids were mixed with the soil at concentrations of 0, 30, 90, and 200 Mg ha^?1. The experiment to determine the bioavailability of metals in the soil using the bioassay was performed using sunflower. The DGT technique and Community Bureau of Reference (BCR) sequential extraction were used to determine the bioavailable fractions of the metals.

Results and discussion

The application of biosolids increased the phytoavailability of Zn, Ni, and Cr in most of the soils, as indicated by the increasing concentrations in sunflower plants as the biosolid application rate increased. In two of the soils, Codigua and Pelvín, this increase peaked at an application rate of 90 Mg ha^?1. Decreases in the bioavailable fractions of Zn, Ni, and Cr were observed with higher biosolid application rates. The bioavailability of metals was estimated through multiple linear regression models between the metals in the sunflower plants and the different chemical fractions of metals in the soils treated with different biosolid rates, which displayed a positive contribution of the labile (water soluble, carbonate, and exchangeable), oxide, and organic metal forms in the soil, particularly with respect to Ni and Zn at application rates of 30 and 90 Mg ha^?1. The bioavailable fraction of metals was determined in soils using the DGT technique. The effective concentration (C _E) results were compared with those in sunflower plants. The DGT technique could effectively predict the bioavailable fractions of Cr, Ni, and Zn in the Taqueral soil but only that of Zn in the Polpaico soil.

Conclusions

The application of biosolids significantly increased the labile fraction of most of the metals in the studied soils, particularly at the highest biosolid application rate. C _E increased as the concentration of biosolids increased for most of the metals. The effectiveness of the DGT technique for predicting the bioavailability of metals was dependent on the soil type and the metal. However, the C _E for soil Cu was not related to plant Cu for all soils studied.     

Immobilization of Cu and Cd in a contaminated soil: one- and four-year field effects

Purpose

Many amendments have been applied to immobilize heavy metals in soil. However, little information is available on the changes of immobilization efficiencies of heavy metals in contaminated soils over time. This work investigated the immobilization efficiencies of copper (Cu) and cadmium (Cd) in contaminated soils in situ remediated with one-time application of three amendments for 1 year and 4 years.

Materials and methods

Apatite, lime, and charcoal were mixed with the topsoil of each plot with the amounts of 22.3, 4.45, and 66.8 t/ha, respectively. Soil chemical properties and fractions of Cu and Cd were examined after in situ remediation for 1 year and 4 years. Soil sorption and retention capacities and desorption proportions for Cu and Cd were investigated by batch experiments.

Results and discussion

The addition of amendments significantly increased soil pH, but decreased exchange acid and aluminum (Al). The amendments significantly decreased the CaCl₂ extractable Cu and Cd and transformed them from active to inactive fractions. After the application of amendments for 1 year, the maximum sorption capacities ranged from 35.6 to 38.8 mmol/kg for Cu and from 14.4 to 17.0 mmol/kg for Cd, which were markedly higher than those of the application of amendments for 4 years (Cu, 29.6–34.7 mmol/kg; Cd, 10.9–16.4 mmol/kg). Desorption proportions (D) of Cu and Cd using three extractants followed the order of \( {D}_{{\mathrm{NaNO}}_3}<{D}_{{\mathrm{CaCI}}_2}<{D}_{{\mathrm{MgCI}}_2} \) . Moreover, the retention capacities (R) of Cu and Cd both increased and followed the order of R _apatite?>?R _lime?>?R _charcoal, resulting in higher Cu and Cd in the amended soils than the untreated soil.

Conclusions

Apatite, lime, and charcoal increased the soil sorption and retention capacities of Cu and Cd and resulted in higher immobilization efficiencies in the amended soils than the untreated soil. However, the immobilization efficiencies of Cu and Cd decreased with the decrease of sorption capacities after 4 years. It was concluded that apatite had the best effect on the long-term stability of immobilized Cu and Cd and can be applied to immobilize heavy metals in contaminated soils.     

Optimization of arsenic and pentachlorophenol removal from soil using an experimental design methodology

Purpose

In this study, a soil-washing process was investigated for arsenic (As) and pentachlorophenol (PCP) removal from polluted soils. This research first evaluates the use of chemical reagents (HCl, HNO₃, H₂SO₄, lactic acid, NaOH, KOH, Ca(OH)₂, and ethanol) for the leaching of As and PCP from polluted soils.

Materials and methods

A Box–Behnken experimental design was used to optimize the main operating parameters for soil washing. A laboratory-scale leaching process was applied to treat four soils polluted with both organic ([PCP] _i ?=?2.5–30 mg kg^?1) and inorganic ([As] _i ?=?50–250 mg kg^?1, [Cr] _i ?=?35–220 mg kg^?1, and [Cu] _i ?=?80–350 mg kg^?1) compounds.

Results and discussion

Removals of 72–89, 43–62, 52–68, and 64–98 % were obtained for As, Cr, Cu, and PCP, respectively, using the optimized operating conditions ([NaOH]?=?1 N, [cocamidopropylbetaine] _i ?=?2 % w w^?1, t?=?2 h, T?=?80 °C, and PD?=?10 %).

Conclusions

The use of NaOH, in combination with the surfactant, is efficient in reducing both organic and inorganic pollutants from soils with different levels of contamination.     

Mineralogy and nutrient desorption of suspended sediments during a storm event

Purpose

This study investigated desorption of potassium (K) and phosphorus (P) from soil and river suspended sediments sampled during a storm event in a Brazilian watershed traditionally used for tobacco plantations.

Material and methods

Suspended sediment samples were collected automatically at the outlet of the watershed and were grouped into three phases: beginning (phase a), middle (phase b) and final stages (phase c) of the storm event. Granulometric and mineralogical characterisation of soils (0 to 0.20 m depth) and suspended sediments was determined, and K and P extractions were performed using a cation and anion exchange resin (CAER) membrane. A kinetic modelling approach was used to estimate the amount of K and P desorbed.

Results and discussion

Clay-sized (<2 μm) content of the soils were all <21 %. Kaolinite, smectite (partially with hydroxy-Al interlayer) and a small amount of illite were found in the clay fraction of the different soils. The clay-sized fractions in sediments of phases a, b and c of the storm event were 49, 52 and 72 %, respectively. Smectite (>90 %) and kaolinite (<10 %) were the dominant clay minerals in the suspended sediments. The values of labile P and potentially available P of suspended sediments were higher than those for soils. In sediments, the highest values of labile P (325 mg kg^?1) and labile K (4,458 mg kg^?1) were found in phase c and in phase a, respectively.

Conclusions

Particle size distribution and clay mineralogy of soils differed from those of suspended sediments collected during the storm event. By comparison with the watershed soils, suspended sediments collected during the storm event were enriched in fine particles composed mainly of smectite, and this may explain their P and K desorption behaviour. This suggests particle size and clay species selectivity processes during the transfer of sediment particles from soils to aquatic systems. The amounts of P and K desorbed from the suspended sediments in the three phases of the storm event were much larger than those desorbed from soils. This indicates that rainfall promoted the transfer of these nutrients to the watercourses.     

Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging

Purpose

The sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) to three different artificial soil mixtures was investigated. Artificial soils serve as model systems for improving understanding of sorption phenomena.

Materials and methods

The soils consisted of quartz, ferrihydrite, illite, montmorillonite, and charcoal. In a previous study, several selected mixtures had been inoculated with organic matter, and microbial aging (incubation) had been performed for different periods of time (3, 12, and 18?months) before conducting the sorption experiments. The effect of this pre-incubation time on the sorption behavior was determined. Interaction of MCPA with soil surfaces was monitored by aqueous phase sorption experiments, using high-performance liquid chromatography/ultraviolet and in selected cases Fourier-transformed infrared spectroscopy.

Results and discussion

The sorption behavior showed large differences between differently aged soils; Freundlich and linear sorption model fits (with sorption constants K _f , 1/n exponents, and K _d values, respectively) were given for pH?=?3 and the unbuffered pH of ??7. The largest extent of sorption from diluted solutions was found on the surfaces with a pre-incubation time of 3?months. Sorption increased at acidic pH values.

Conclusions

Regarding the influence of aging of artificial soils, the following conclusions were drawn: young artificial soils exhibit stronger sorption at lower concentrations, with a larger K _f value than aged soils. A correlation with organic carbon content was not confirmed. Thus, the sorption characteristics of the soils are more influenced by the aging of the organic carbon than by the organic carbon content itself.     

Evolution and phosphorus fractionation in saline Spolic Technosols flooded with eutrophic water

Purpose

The aim of this study was to evaluate the behaviour of P in saline Spolic Technosols flooded with eutrophic water, with and without plant rhizosphere, in order to assess the role of these soils as sinks or sources of this nutrient.

Materials and methods

Samples were taken from basic (pH?~7.8), carbonated and acidic (pH?~6.2), de-carbonated soils of salt marshes polluted by mine wastes. Three treatments were assayed: pots with Sarcocornia fruticosa, pots with Phragmites australis and pots without plants (bare soil). The pots were flooded for 15?weeks with eutrophic water (PO ₄ ^3? ~6.92?mg?L^?1) and pH, Eh and water-soluble organic carbon and PO ₄ ^3? concentrations were monitored in the soil solution. A soil P fractionation was applied before and after the flooding period.

Results and discussion

The PO ₄ ^3? concentration in the soil solution decreased rapidly in both soils, with and without plant, being diminished by 80?C90?% after 3?h of flooding. The Fe/Mn/Al oxides and the Ca/Mg compounds played an important role in soil P retention. In pots with S. fruticosa, the reductive conditions due to flooding induced P release from metal oxides and P retention to Ca/Mg compounds. In turn, P. australis may have favoured the release of P from carbonates, which was transferred to Fe/Mn/Al compounds.

Conclusions

The retention of P by the soil was the main mechanism involved in the removal of PO ₄ ^3? from the eutrophic flooding water but to evaluate the capacity of these systems as long-term P sinks, the combined effect of metals, Ca/Mg compounds and specific plant species should be considered.     

Sorption of humic acid on Fe oxides,bacteria, and Fe oxide-bacteria composites

Purpose

Sorption of humic substances on other soil components plays an important role in controlling their function and fate in soil. Sorption of humic substances by individual soil components has been studied extensively. However, few studies reported the sorption characteristic of humic substances on composites of soil components. This study aimed to investigate the sorption characteristics of humic acid on Fe oxide-bacteria composites and improve the understanding on the interaction among humic substance Fe oxide bacteria in soil.

Materials and methods

Humic acid was purchased from Sigma-Aldrich and was purified. Hematite and ferrihydrite were synthesized in the lab. Bacillus subtilis and Pseudomonas putida were cultivated in Luria-Broth medium and harvested at stationary growth phase. Batch sorption experiments were carried out at pH 5.0. Various amounts of humic acid were mixed with 20 mg of Fe oxide, bacteria, or Fe oxide-bacteria composite (oxide to bacteria of 1:1) in 10 mL of KCl (0.02 mol L^?1) to construct sorption isotherms. The effects of phosphate concentration and addition order among humic acid, Fe oxide, bacteria on the sorption of humic acid were also studied. The sorption of humic acid was calculated by the difference between the amount of humic acid added initially and that remained in the supernatant.

Results and discussion

The maximum sorption of humic acid on hematite, ferrihydrite, B. subtilis and P. putida was 73.2, 153.5, 69.1, and 56.7 mg C g^?1, respectively. The maximum sorption of humic acid on examined Fe oxide-bacteria composite was 28.2–57.2 % less than the predicted values, implying that the sorption of humic acid was reduced by the interaction between Fe oxides and bacteria. The presence of phosphate exerted negligible influence on the sorption of humic acid on bacteria while it inhibited the sorption of humic acid on Fe oxides. On Fe oxide-bacteria composites, inhibiting influences followed by promoting or weak inhibiting effects of phosphate with increasing concentration on the sorption of humic acid were found.

Conclusions

The interaction between Fe oxides and bacteria reduced the sorption of humic acid; moreover, the reduction was greater by the interaction of bacteria with ferrihydrite than that with hematite. Phosphate exerted negligible and inhibiting influence on the sorption of humic acid by bacteria and Fe oxides, respectively. On Fe oxide-bacteria composites, humic acid sorption was initially inhibited and then promoted or weakly inhibited by phosphate with increasing concentration.     

The influence of compost addition on heavy metal distribution between operationally defined geochemical fractions and on metal accumulation in plant

Purpose

Metal distribution patterns among geochemical fractions are informative for metal phytoavailability. Compost added to polluted soils may adsorb metals on the less phytoavailable fractions. A bioassay experiment was conducted to establish possible correlations between metal concentrations in different soil fractions and metal contents in edible plant parts and to investigate the influence of different compost loads on heavy metal availability to plants.

Materials and methods

Chinese cabbage plants were grown in pots with sandy and clayey soils and soils mixed with different doses of biosolid compost spiked with soluble heavy metal salts (Cd, Cu, and Pb). The metals’ distribution pattern in the soil and mixed samples was determined by sequential extraction procedure (modified BCR protocol). The studied fractions, from most to least bioavailable, were water-extractable (WE), exchangeable-adsorbed (EXC), associated with carbonates and acetic acid-soluble forms (CARB), occluded by reducible (hydro)oxides of Fe and Mn (RO), and associated with organic matter (OM) and a residual fraction (RES). Metal concentrations in soil extracts and in the digested plant tissue were measured by ICP-AES.

Results and discussion

The highest compost doses (72 and 115 Mg ha^?1) enhanced cabbage yield significantly. No excessive phytoaccumulation of metals was observed in plants grown in the clayey soil or its mixtures with compost. The compost dose of 72 Mg ha^?1 was optimal in decreasing Cu accumulation by plants grown in sandy soil, and 28.8 Mg ha^?1 was found to be effective in reducing Cd and Pb uptake. Metals were accumulated in plants primarily from the WE, EXC, and CARB fractions, whereas other fractions decreased phytoaccumulation. Compost addition suppressed heavy metal mobility, but different fractions were active in pollutant sorption, depending on soil type and metal.

Conclusions

Compost addition increased metal proportions in the RO and OM fractions, reducing metal phytoavailability. This is especially important for sandy soils with low adsorption ability and higher vulnerability to metal pollution than clayey soils. A compost dose of 20% v/v (or 28.8 Mg ha^?1) effectively reduced plant accumulation of Cd and Pb. We propose using the first three steps of the modified BCR protocol as a three-step sequential-extraction procedure for the most phytoavailable fractions of heavy metal: WE, EXC, and CARB.     

Toxicity of arsenic in relation to soil properties: implications to regulatory purposes

Purpose

The present work evaluates the influence of different soil properties and constituents on As solubility in laboratory-contaminated soils, with the aim of assessing the toxicity of this element from the use of bioassays to evaluate the soil leachate toxicity and thereby propose soil guideline values for studies of environmental risk assessment in soil contamination.

Materials and methods

Seven soils with contrasting properties were artificially contaminated in laboratory with increasing concentrations of As. Samples were incubated for 4 weeks, and afterwards, soil solution (1:1) was obtained after shaking for 24 h. The soil leachate toxicity was assessed with two commonly used bioassays (seed germination test with Lactuca sativa and Microtox ® test with Vibrio fischeri).

Results and discussion

The relationship between soluble As and soil properties indicated that iron oxides and organic matter content were the variables most closely related to the reduction of the As solubility, while pH and CaCO₃ increased As solubility in the soil solutions. Toxicity bioassays showed significant differences between soils depending on their properties, with a reduction of the toxicity in the iron-rich soil (no observed effect concentration (NOEC)?=?150 mg kg^?1) and a significant increase in the highly carbonate samples (NOEC between 15 and 25 mg kg^?1).

Conclusions

Soil guideline values for regulatory purposes usually set a single value for large areas (regions or countries) which can produce over- or underestimation of efforts in soil remediation actions. These values should consider different levels according to the main soil properties controlling arsenic mobility and the soil leachate toxicity.     

Competitive sorption of linear alkylbenzene sulfonate (LAS) surfactants and the antibiotics sulfamethoxazole and ciprofloxacin in wastewater-irrigated soils of the Mezquital Valley,Mexico

Purpose

The increasing reuse of wastewater for irrigation introduces surfactants and antibiotics into the environment. How these two kinds of compounds interact with regard to their sorption processes in soil is not clear.

Materials and methods

We performed batch experiments to investigate the sorption of linear alkylbenzene sulfonates (LAS) and its effect on sorption of sulfamethoxazole and ciprofloxacin in irrigated and non-irrigated soils with different organic matter (OM) contents.

Results and discussion

LAS sorption was non-linear in the presence of the antibiotics, and as general trend, it increased with rising OM content of soils. Free LAS was also removed from solution by complexation with Ca²⁺. Dissolved organic compounds released from soils with OM contents ≥18.4 g kg^?1 further reduced LAS sorption. Sorption of sulfamethoxazole was reduced by LAS sorption only in one soil with a small OM content of 9.5 g kg^?1.

Conclusions

The strong sorption of ciprofloxacin is not affected by LAS. Sulfamethoxazole sorption only competes with LAS sorption in organic matter-poor soils. Accumulation of organic matter in soils, for example due to long-term wastewater irrigation, provides extra sorption capacity for LAS and sulfamethoxazole so that competition for sorption sites is reduced.

     

Effect of nickel-resistant rhizosphere bacteria on the uptake of nickel by the hyperaccumulator Noccaea caerulescens under controlled conditions

Purpose

This work was conducted to determine whether Nickel-resistant rhizosphere bacteria (NiRRB) affected the Ni uptake and hyperaccumulation by Noccaea caerulescens.

Material and methods

Ni-resistant bacterial strains (10 mM Ni), Bacillus pumilus and Micrococcus spp., were originally isolated from the rhizosphere of N. caerulescens (Brassicaceae) collected from serpentine Ni-rich soil in the Vosges mountains (France). They served to inoculate axenic seeds of N. caerulescens, which were then sown aseptically into sterile soil Magenta boxes and cultured under controlled conditions.

Results and discussion

Cultures inoculated with NiRRB showed a disappearance of chlorosis signs and a significant increase of the aerial biomass compared to the axenic control (1.5-fold higher). Despite the drastic decrease of the water-extractable Ni in the soil (80 %) at the end of the growth, there was no significant effect on Ni accumulation by N. caerulescens compared to the axenic control. A highly significant promoting effect on plant growth (fourfold higher) and an increase of Ni accumulation (65-fold higher) by N. caerulescens were shown in cultures with native microorganisms (nonsterile control) compared to the axenic control.

Conclusions

The NiRRB strains used in this study reduced Ni bioavailability in the soil and did not improve the Ni uptake by N. caerulescens. Nevertheless, they induced promoting effects on the growth of this plant. They could serve as an effective metal-immobilizing and growth-promoting bioinoculant for plants in Ni-stressed soils. Optimal growth and Ni uptake by N. caerulescens requires the presence of native microbial community.     

Fractionation of Cd and Zn in Cd-contaminated soils amended by sugarcane waste products from an ethanol production plant

Purpose

Sugarcane waste products (boiler ash, filter cake, and vinasse) from an ethanol production plant were used as soil amendments by adding 3 % (w/w) in single and/or in combination, with a research focus towards stabilization of cadmium (Cd) and zinc (Zn) in contaminated soils. The objective of this laboratory study was to evaluate the effects of adding these sugarcane waste products on bioavailability of Cd and Zn over time (aging) in Cd- and Zn-contaminated agricultural soils of Thailand.

Materials and methods

Two agricultural contaminated soils of low (<3 mg kg^?1) and high (10–15 mg kg^?1) Cd concentrations were collected from Tak Province, Northwest Thailand. Fourteen treatments were sampled at 2-week intervals for 84 days for metal bioavailability using BCR extraction procedures (proposed by The Standards, Measurements and Testing Programme of the European Union, SM&T) that determined exchangeable (BCR1), reducible (BCR2), oxidizable (BCR3), and residual (BCR4) fractions, and total concentration was determined using aqua regia digestion and microwave digestion.

Results and discussion

Cd was potentially bioavailable, predominantly in exchangeable (BCR1) and reducible (BCR2) fractions, while the higher contribution of Zn was more prevalent in refractory fractions (BCR2 and BCR4). Aging had an influence on fractionation of Cd and Zn, most notably in the first two fractions (BCR1 and BCR2) of BCR sequential extraction, which resulted in reduction of exchangeable Cd during the first few weeks of incubation (T?=?0 to 28 days). At the end of pot experiment, the exchangeable Cd fraction in the low Cd (LCdS) soil was reduced from 2.3 to 4.7 % and 9.4 to 39.9 % in low and high Cd (HCdS)-contaminated soils, respectively, as compared to nonamended soils.

Conclusions

The observed reduction in exchangeable Cd (BCR1) in the amended soils at the 3 % (w/w) application rate, the low total metal concentrations, and the significant amount of essential plant nutrients (N, P, and K) within these waste products highlight the benefits of amending metal-rich soils with them.     

The transfer of heavy metals to barley plants from soils amended with sewage sludge with different heavy metal burdens

Purpose

Our main aim objective was to evaluate the transfer of Cd, Cr, Cu, Ni, Pb and Zn to barley (Hordeum vulgare) grown in various soils previously amended with two sewage sludges containing different concentrations of heavy metals. This allowed us to examine the transfer of heavv metals to barley roots and shoots and the occurrence of restriction mechanisms as function of soil type and for different heavy metal concentration scenarios.

Material and methods

A greenhouse experiment was performed to evaluate the transfer of heavy metals to barley grown in 36 agricultural soils from different parts of Spain previously amended with a single dose (equivalent to 50 t dry weight ha^?1) of two sewage sludges with contrasting levels of heavy metals (common and spiked sludge: CS and SS).

Results and discussion

In soils amended with CS, heavy metals were transferred to roots in the order (mean values of the bio-concentration ratio in roots, BCF_Roots, in brackets): Cu (2.4)?~?Ni (2.3)?>?Cd (2.1)?>?Zn (1.8)?>?Cr (0.7)?~?Pb (0.6); similar values were found for the soils amended with SS. The mean values of the soil-to-shoot ratio were: Cd (0.44)?~?Zn (0.39)?~?Cu (0.39)?>?Cr (0.20)?>?Ni (0.09)?>?Pb (0.01) for CS-amended soils; Zn (0.24)?>?Cu (0.15)?~?Cd (0.14)?>?Ni (0.05)?~?Cr (0.03)?>?Pb (0.006) for SS-amended soils. Heavy metals were transferred from roots to shoots in the following order (mean values of the ratio concentration of heavy metals in shoots to roots in brackets): Cr (0.33)?>?Zn (0.24)?~?Cd (0.22)?>?Cu (0.19)?>?Ni (0.04)?>?Pb (0.02) for CS-amended soils; Zn (0.14)?>?Cd (0.09)?~?Cu (0.08)?>?Cr (0.05)?>?Ni (0.02)?~?Pb (0.010) for SS-amended soils.

Conclusions

Soils weakly restricted the mobility of heavy metals to roots, plant physiology restricted the transfer of heavy metals from roots to shoots, observing further restriction at high heavy metal loadings, and the transfer of Cd, Cu and Zn from soils to shoots was greater than for Cr, Ni and Pb. Stepwise multiple linear regressions revealed that soils with high sand content allowed greater soil-plant transfer of Cr, Cu, Pb and Zn. For Cd and Ni, soils with low pH and soil organic C, respectively, posed the highest risk.