Toxicity of imidacloprid to the earthworm Eisenia andrei and collembolan Folsomia candida in three contrasting tropical soils

Purpose

Imidacloprid is a widely used seed dressing insecticide in Brazil. However, the effects of this pesticide on non-target organisms such as soil fauna still present some knowledge gaps in tropical soils. This study aimed to assess the toxicity and risk of imidacloprid to earthworms Eisenia andrei and collembolans Folsomia candida in three contrasting Brazilian tropical soils.

Materials and methods

Acute and chronic toxicity assays were performed in the laboratory with both species in a tropical artificial soil (TAS) and in two natural soils (Oxisol and Entisol), at room temperature of 25 °C. The ecological risk was calculated for each species and soil by using the toxicity exposure ratio (TER) and hazard quotient (HQ) approaches.

Results and discussion

Acute toxicity for collembolans and earthworms was higher in Entisol (LC₅₀?=?4.68 and 0.55 mg kg^?1, respectively) when compared with TAS (LC₅₀?=?10.8 and 9.18 mg kg^?1, respectively) and Oxisol (LC_{50collembolans}?=?25.1 mg kg^?1). Chronic toxicity for collembolans was similar in TAS and Oxisol (EC_{50 TAS}?=?0.80 mg kg^?1; EC_{50 OXISOL}?=?0.83 mg kg^?1), whereas higher toxicity was observed in Entisol (EC₅₀?=?0.09 mg kg^?1). In chronic assays with earthworms, imidacloprid was also more toxic in Entisol (EC₅₀?=?0.21 mg kg^?1) when compared to TAS (EC₅₀?=?1.89 mg kg^?1). TER and HQ values indicated a significant risk of exposure of the species to imidacloprid in all soils tested, and the risk in Entisol was at least six times higher than in Oxisol or TAS.

Conclusions

The toxicity and risk of imidacloprid varied significantly between tropical soils, being the species exposure to this pesticide particularly hazardous in very sandy natural soils such as Entisol.

     

Decarboxylation of organic anions to alleviate acidification of red soils from urea application

Purpose

Decarboxylation of organic anions in crop straw is recognized as one of the mechanisms for increasing pH in acidified soils. However, the effectiveness of specific compounds in alleviating soil acidification from nitrification has not been well determined. This study examined three organic anions commonly found in crop straws and their effect on soil acidity and N transformation processes following urea application to a red soil (Ferralic Cambisol).

Materials and methods

A 35-day incubation experiment was conducted using soil after receiving 26 years of two different nutrient treatments: (1) chemical nitrogen, phosphorus, and potassium fertilization (NPK, pH 4.30) and (2) NPK plus swine manure (NPKM, pH 5.88). Treatments included three rates (0.25, 0.5, and 1.0 g C kg^?1) of calcium citrate, 0.5 g C kg^?1 calcium oxalate, 0.5 g C kg^?1 calcium malate, urea-only (control) soil, and a non-treated soil as a reference. Soil acidity, mineral N species, decarboxylation, and their correlations were determined.

Results and discussion

All three organic anions significantly increased pH in both soils and the effectiveness was positively correlated with application rate. The change in total exchangeable soil acidity was dominated by aluminum concentration in the NPK soil, but by proton concentration in the NPKM soil. At ≥?0.5 g C kg^?1, the anions decreased soil exchangeable acidity by 25–68% in NPK soil and by 63–88% in NPKM soil as compared with control. Oxalate was the most effective in increasing soil pH by 0.70 and 1.31 units and reducing exchangeable acidity by 3.79 and 0.33 cmol₍₊₎ kg^?1 in NPK and NPKM soils, respectively, and also resulted in the highest CO₂ production rate. Addition of organic anions led to a lower nitrification rate in NPKM soil relative to the NPK soil.

Conclusions

These results imply that crop straws rich in organic anions, especially oxalate, would have a higher potential to alleviate soil acidification.

     

Response of soil C:N:P stoichiometry,organic carbon stock,and release to wetland grasslandification in Mu Us Desert

Purpose

Wetlands in Mu Us Desert have severely been threatened by grasslandification over the past decades. Therefore, we studied the impacts of grasslandification on soil carbon (C):nitrogen (N):phosphorus (P) stoichiometry, soil organic carbon (SOC) stock, and release in wetland-grassland transitional zone in Mu Us Desert.

Materials and methods

From wetland to grassland, the transition zone was divided into five different successional stages according to plant communities and soil water conditions. At every stage, soil physical and chemical properties were determined and C:N:P ratios were calculated. SOC stock and soil respirations were also determined to assess soil carbon storage and release.

Results and discussion

After grasslandification, SOC contents of top soils (0–10 cm) decreased from 100.2 to 31.79 g kg^?1 in June and from 103.7 to 32.5 g kg^?1 in October; total nitrogen (TN) contents of top soils (0–10 cm) decreased from 3.65 to 1.85 g kg^?1 in June and from 6.43 to 3.36 g kg^?1 in October; and total phosphorus (TP) contents of top soils (0–10 cm) decreased from 179.4 to 117.4 mg kg^?1 in June and from 368.6 to 227.8 mg kg^?1 in October. From stages Typha angustifolia wetland (TAW) to Phalaris arundinacea L. (PAL), in the top soil (0–10 cm), C:N ratios decreased from 32.2 to 16.9 in June and from 19.0 to 11.8 in October; C:P ratios decreased from 1519.2 to 580.5 in June and from 19.0 to 11.8 in October; and N:P ratios decreased from 46.9 to 34.8 in June and changed from 34.9 to 34.0 in October. SOC stock decreased and soil respiration increased with grasslandification. The decrease of SOC, TN, and TP contents was attributed to the reduction of aboveground biomass and mineralization of SOM, and the decrease of soil C:N, C:P, and N:P ratios was mainly attributed to the faster decreasing speeds of SOC than TN and TP. The reduction of aboveground biomass and increased SOC release led by enhanced soil respiration were the main reasons of SOC stock decrease.

Conclusions

Grasslandification led to lowers levels of SOC, TN, TP, and soil C:N, C:P, and N:P ratios. Grasslandification also led to higher SOC loss, and increased soil respiration was the main reason. Since it is difficult to restore grassland to original wetland, efficient practices should be conducted to reduce water drainage from wetland to prevent grasslandification.

     

A 3-year assessment of nitrous oxide emission factors for urine and dung of grazing sheep in a subtropical ecosystem

Purpose

Grazing livestock has strong impact on global nitrous oxide (N₂O) emissions by providing N sources through excreta. The scarcity of information on factors influencing N₂O emissions from sheep excreta in subtropical ecosystems such as those of Southern Brazil led us to conduct field trials in three different winter pasture seasons on an integrated crop–livestock system (ICL) in order to assess N₂O emission factors (EF-N₂O) in response to variable rates of urine and dung.

Materials and methods

The equivalent urine-N loading rates for the three winter seasons (2009, 2010, and 2013) ranged from 96 to 478 kg ha^?1, and the dung-N rates applied in 2009 and 2010 were 81 and 76 kg ha^?1, respectively. Air was sampled from closed static chambers (0.20 m in diameter) for approximately 40 days after excreta application and analyzed for N₂O by gas chromatography.

Results and discussion

Soil N₂O-N fluxes spanned the ranges 4 to 353 μg m^?2 h^?1 in 2009, ??47 to 976 μg m^?2 h^?1 in 2010, and 46 to 339 μg m^?2 h^?1 in 2013. Urine addition resulted in N₂O-N peaks within for up to 20–30 days after application in the 3 years, and the strength of the peaks was linearly related to the N rate used. Emission factors of N₂O (EF-N₂O, % of N applied that is emitted as N₂O) of urine ranged from 0.06 to 0.34% and were essentially independent of N rate applied. By considering a ratio of N excreted by urine and dung of 60:40, a single combined excretal EF-N₂O of 0.14% was estimated.

Conclusions

Our findings showed higher mean EF-N₂O for sheep urine than that for dung (0.21% vs 0.03%), irrespective of the occurrence or not of urine patches overlap. This value is much lower than default value of 1% of IPCC’s Tier 1 and reinforces the needs of its revision.

     

Phosphorus desorption from calcareous soils with different initial Olsen-P levels and relation to phosphate fractions

Purpose

Calcareous soils are characterized by high pH and phosphorus (P) fixation capacity. Increasing application of P fertilizer recently has significantly improved soil P concentration, especially available P (Olsen-P) and inorganic phosphate (P_i) fractions. However, there are few data available on the ability of soils with different initial Olsen-P levels to continuously supply P (i.e., P desorption capacity) to crops without additional P fertilization and on which P_i fraction exerts the greatest influence on P desorption capacity.

Materials and methods

Five soils with different initial Olsen-P levels (0.5, 14.3, 38.4, 55.4, 72.3 mg kg^?1, hereafter refer as OP1, OP2, OP3, OP4, and OP5) but similar other soil properties were selected to evaluate the capacity of P desorption and its relationship with P_i fractions. Soil P was sequentially extracted once daily for 16 consecutive days using Olsen solution.

Results and discussion

The content and proportions of dicalcium phosphate fraction (Ca₂-P), octacalcium phosphate fraction (Ca₈-P), aluminum phosphorus fraction (Al-P), and iron phosphorus fraction (Fe-P) in P_i increased significantly with the increase of initial Olsen-P (P?<?0.01). Applied P fertilizer was mostly stored as Ca₈-P in the soil. Soil P desorbed reached an equilibrium after 16 extractions for all soils, and P desorption capacity (12–358 mg kg^?1) showed a significant linear relationship with initial Olsen-P (P?<?0.01), with an increase of 4.2 mg kg^?1 desorbed P per 1 mg kg^?1 increase of initial Olsen-P. Ca₂-P exerted the conclusive effect on P desorption in the first four extractions, but Ca₈-P played a more important role in the 16 extractions.

Conclusions

Ca₈-P was the greatest potential pool for P desorption after Ca₂-P was depleted. P desorption capacity was significantly linearly related to initial Olsen-P (P?<?0.01). Different fertilizer use strategies were developed based on P desorption capacity for soils with different initial Olsen-P levels. The present study provided basic data on how to reduce effectively the application amount of chemical P fertilizer.

     

Source relationships between streambank soils and streambed sediments in a mercury-contaminated stream

Purpose

In contaminated streams, understanding the role of streambank and streambed source contributions is essential to developing robust remedial solutions. However, identifying relationships can be difficult because of the lack of identifying signatures in source and receptor pools. East Fork Poplar Creek (EFPC) in Oak Ridge, TN, USA received historical industrial releases of mercury that contaminated streambank soils and sediments. Here, we determined relationships between the contaminated streambank soils and sand-sized streambed sediments.

Materials and methods

Field surveys revealed the spatial trends of the concentrations of inorganic total mercury (Hg) and methyl mercury (MeHg), Hg lability as inferred by sequential extraction, particle size distribution, and total organic carbon. Statistical tests were applied to determine relationships between streambank soil and streambed sediment properties.

Results and discussion

Concentrations of Hg in streambank soils in the upper reaches averaged 206 mg kg^?1 (all as dry weight) (n?=?457), and 13 mg kg^?1 in lower reaches (n?=?321), while sand-sized streambed sediments were approximately 16 mg kg^?1 (n?=?57). Two areas of much higher Hg and MeHg concentrations in streambank soils were identified and related to localized higher Hg concentrations in the streambed sediments; however, most of the streambank soils have similar Hg concentrations to the streambed sediments. The molar ratio of Hg to organic carbon, correlation between MeHg and Hg, and particle size distributions suggested similarity between the streambank soils and the fine sand-sized fraction (125–250 μm) collected from the streambed sediments. Mercury in the fine sand-sized streambed sediments, however, was more labile than Hg in the streambank soils, suggesting an in-stream environment that altered the geochemistry of sediment-bound Hg.

Conclusions

This study revealed major source areas of Hg in streambank soils, identified possible depositional locations in streambed sediments, and highlighted potential differences in the stability of Hg bound to streambank soils and sediments. This work will guide future remedial decision making in EFPC and will aid other researchers in identifying source–sink linkages in contaminated fluvial systems.

     

Response of phosphorus fractions to land-use change followed by long-term fertilization in a sub-alpine humid soil of Qinghai–Tibet plateau

Purpose

Identification of phosphorus (P) species is essential to understand the transformation and availability of P in soil. However, P species as affected by land use change along with fertilization has received little attention in a sub-alpine humid soil of Tibet plateau.

Materials and methods

In this study, we investigated the changes in P species using Hedley sequential fractionation and liquid-state ³¹P-NMR spectroscopy in soils under meadow (M) and under cropland with (CF) or without (CNF) long-term fertilization for 26 years in a sub-alpine cold-humid region in Qinghai–Tibet plateau.

Results and discussion

Land-use change and long-term fertilization affected the status and fractions of P. A strong mineralization of organic P (OP) was induced by losing protection of soil organic matter (SOM) and Fe and Al oxides during land-use change and resulted in an increase of orthophosphate (from 56.49 mg kg^?1 in M soils to 130.07 mg kg^?1 in CNF soils) and great decreases of orthophosphate diesters (diester-P, from 23.35 mg kg^?1 in M soils to 10.68 mg kg^?1 in CNF soils) and monoesters (from 336.04 mg kg^?1 in M soils to 73.26 mg kg^?1 in CNF soils). Long-term fertilization boosted P supply but failed to reclaim soil diester-P (from 10.68 mg kg^?1 in CNF soils to 7.79 mg kg^?1 in CF soils). This may be due to the fragile protection from the combination of SOM with diester-P when long-term fertilization had only improved SOM in a slight extent.

Conclusions

These results suggest that SOM plays an important role in the soil P cycling and prevents OP mineralization and losses from soil. It is recommended that optimization of soil nutrient management integrated with SOM was required to improve the P use efficiency for the development of sustainable agriculture.

     

Carbon decomposition in broiler litter-amended soils

Organic carbon (OC) is generally low in Alabama (U.S.A.) soils and varies considerably with cropping systems. Information on decomposition rates of the added C is a prerequisite to designing strategies that improve C sequestration in farming systems. Different models including exponential models have been used to describe OC mineralization in soils as well as to describe its potential as CO₂ to be released into the environment. We investigated the decomposition of broiler litter added to ten non-calcareous soils (Appling, Troup, Cecil, Decatur, Sucarnoochee, Linker, Hartsells, Dothan, Maytag, and Colbert soils). A non-linear regression approach for N mineralization was used to estimate the potentially mineralizable OC pools (C_o) and the first-order rate constant (k) in the soil samples. Results showed that the non-amended soils have distinct differences in their ability to release their native OC as CO₂ and can be divided into four groups depending on their potentially mineralizable C (C_o) and their ability to protect stable organic matter. Sucarnoochee soil represents the first group and contains a moderate amount of OC (11.4 g C kg⁻¹) but had the highest C_o (7.30 g C kg⁻¹ soil). The second distinct group of soils has C_o varying between 5.50 and 5.00 g C kg⁻¹ soil (Decatur, Hartsells, Dothan, and Maytag). The third group has C_o between 5.00 and 4.00 (Appling, Cecil, and Linker). The fourth group has C_o less than 4.00 g C kg⁻¹ soil (Troup and Colbert). Half-life of C remaining in non-amended soils varied from 26 days in Maytag soil to 139 days in Cecil soil. The OC in these non-amended soils represents a very stable form of organic C and thus, not easily decomposed by soil microorganisms. In the broiler litter-amended soils, the C_o varied from 3.82 g C kg⁻¹ in Appling soil amended with broiler litter 1-7.04 g C kg⁻¹ soil in Maytag amended with broiler litter 2. Decomposition of the added OC proceeded in two phases with less than 31% decomposed in 43 days. Potentially mineralizable organic C (C_o) was related to soil organic C (r = 0.661**) and soil C/N ratio (r = 0.819*).     

Forms and buffering potential of aluminum in tropical and subtropical acid soils cultivated with Pinus taeda L

Purpose

Several interactions between Al and the solid phase of soil influence Al buffering in soil solution. This work evaluated soils cultivated with Pinus taeda L. to determine Al forms in organic and mineral horizons using various extraction methods and to relate acidity with clay mineralogy.

Materials and methods

Organic and mineral horizons of 10 soil profiles (up to 2.1 m deep) in southern Brazil were sampled. Organic horizons were separated into fresh, aged, and fermented/humified litter. The following Al extraction methods were utilized: 0.5 mol L^?1 pH 2.8 CuCl₂–Al complexed in organic matter; 1.0 mol L^?1 KCl–exchangeable Al; water–Al soluble in soil solution; HF concentrated?+?HNO₃ concentrated?+?H₂O₂ 30% (v/v)–total Al. Six sequential extractions were carried out to isolate different forms of amorphous minerals that can buffer Al on soil solution: 0.05 and 0.1 mol L^?1 sodium pyrophosphate; 0.1 and 0.2 mol L^?1 ammonium oxalate; 0.25 and 0.5 mol L^?1 NaOH. Samples of clay were also analyzed by XRD.

Results and discussion

There was a clear effect of litter age on increasing total Al concentration. In the aged litter and fermented and/or humified litter, levels of total Al were 1.4 to 3.8 and 1.5 to 7.8 times greater than in fresh litter, respectively. The CuCl₂ method had higher Al extraction capacity than the KCl method for litter. The lowest Al–pyrophosphate values were observed in the Oxisol, which also had a predominance of gibbsite and the lowest levels of Al–KCl and Al–CuCl₂. There was an inverse relationship between degree of soil weathering and soluble and exchangeable Al in soils. Available Al increased with higher Si proportion in minerals of the clay fraction (2:1?>?1:1?>?0:1).

Conclusions

The worst scenario was soils with the combination of high soluble and exchangeable Al levels and high concentrations of amorphous forms of Al minerals. The best predictors of Al accumulation in the youngest litter horizon were extractions of amorphous minerals with pyrophosphate and NaOH. These extractors are normally used to predict the level of Al buffering in soils. Organic matter had less influence on Al dynamics in soils.

     

Methyl-mercury affects microbial activity and biomass,bacterial community structure but rarely the fungal community structure

Monomethyl-mercury is one of the most toxic compounds. Methylation of Hg usually appears under anoxic conditions. In Swiss forest soils, methyl-Hg concentrations of up to 3 μg kg⁻¹ soil dw have been observed, but the impact of methyl-Hg on soil microorganisms have rarely been examined so far. In this study, we investigated the effect of increasing concentrations of methyl-Hg (0, 5, 20, 90 μg kg⁻¹ soil dw) on the microbial communities in various forest soils differing in their physico-chemical properties. Experiments were conducted in microcosms under controlled conditions and the basal respiration (BR), the microbial biomass carbon (MBC) and the bacterial and fungal community structures using T-RFLP-profiling were investigated. BR was significantly affected by methyl-Hg. In general, the BR increased with increasing methyl-Hg concentrations, whereas the MBC was significantly reduced. Bacterial communities were more sensitive to methyl-Hg than fungal communities. In five out of seven soils, the bacterial community structures differed significantly between the treatments whereas the fungal communities did not. The impact of methyl-Hg on the soil bacterial communities was site specific. In one soil, a methyl-Hg concentration of already 5 μg kg⁻¹ soil dw significantly affected the relative abundance of 13% bacterial operational taxonomic units (OTU), whereas in other soils concentrations of even 90 μg kg⁻¹ soil dw rarely affected the abundance of OTUs. In this study, for the first time, the impact of methyl-Hg on soil bacterial and fungal communities in forest soils was assessed. We showed that its impact strongly depends on the physico-chemical conditions of the soil and that bacterial communities were more sensitive to methyl-Hg than fungi.     

Distribution and availability of fungicide-derived copper in soil aggregates

Purpose

Soil consists of various sizes of aggregates, and different soil aggregates vary in their abilities to adsorb or transport metals. This study aimed to investigate the distribution behaviors of Cu from different fungicides in soil aggregates after a 15-month incubation.

Materials and methods

Bordeaux mixture (CuSO₄/Ca(OH)₂?=?1/1 by weight, BR), copper nitrate (Cu(NO₃)₂·4H₂O, CN), and copper oxychloride (3Cu(OH)₂·CuCl₂, CO) were applied to a representative Chinese Mollisol to reach the Cu content 200 mg kg^?1. Five soil aggregate fractions, i.e., >?2000 μm, 2000–1000 μm, 1000–500 μm, 500–250 μm, and <?250 μm, were obtained by the wet sieving method. The modified Bureau Communautaire de Références (BCR) sequential extraction was applied to assess the Cu distribution among the main soil fractions.

Results and discussion

The highest Cu mass loading was found for the >?2000-μm soil aggregate. The input Cu was mainly in stable fractions, and the highest proportion was found for the residual fraction. The bioavailability and mobility of Cu from different fungicides in soils varied from each other, and they presented an order of CO > CN > BR. High bioavailability and transferring coefficients were found in the <?250-μm and >?2000-μm soil aggregates.

Conclusions

This study indicated that the input Cu from fungicides mainly distributed in the >?2000-μm soil aggregates. Moreover, the CO-derived Cu presented a higher availability than the BR- and CN-derived Cu in the soil.

     

Effects of NTA on Pb phytostabilization efficiency of Athyrium wardii (Hook.) grown in a Pb-contaminated soil

Purpose

Chelate-assisted phytoremediation with biodegradable chelates has been considered to be a promising technique to enhance phytoremediation efficiency, while little information is available on phytostabilization. This study aims to assess NTA-assisted phytostabilization of Pb-contaminated soils by Athyrium wardii (Hook.).

Materials and methods

A pot experiment was carried out to investigate the effects of different application days (1, 3, 5, 7, 10, 14, 21) of nitrilotriacetic acid (NTA) on plant growth, Pb accumulation, and Pb availability in rhizosphere soils of A. wardii grown in soils contaminated with low (200 mg kg^?1) and high (800 mg kg^?1) concentrations of Pb.

Results and discussion

With the application of NTA, better growth for A. wardii was observed when treated with NTA for 5–14 days for both low and high Pb soils, suggesting potential harvest time. Pb concentrations and Pb accumulation in underground parts of A. wardii grown in low and high Pb soils increased with increasing application time of NTA generally. Similar changes were also found for bioaccumulation coefficients (BCFs) of A. wardii. The greatest remediation factors (RFs) for underground parts and whole plant of A. wardii were observed for NTA application time of 7 and 5 days for low and high Pb soils, suggesting the greatest remediation efficiency. Furthermore, plant growth, BCF, and RF of A. wardii grown in low Pb-contaminated soils were greater than those grown in high Pb-contaminated soils. Pb availability in rhizosphere soils of A. wardii grown in low Pb soils was lower than those in high Pb-contaminated soils.

Conclusions

It seems to be the optimum for A. wardii to phytostabilize slightly Pb-contaminated soils with the application of NTA for 7 days as taking plant growth, Pb remediation efficiency, and environmental risk into consideration.

     

Application of white mustard and oats in the phytostabilisation of soil contaminated with cadmium with the addition of cellulose and urea

Purpose

Determination of the effectiveness of white mustard and oats in immobilising cadmium as a soil contaminant and determining the role of cellulose and urea in restoring homeostasis in soil under pressure from Cd²⁺.

Materials and methods

Soil samples were contaminated with cadmium (CdCl₂·2¹/₂H₂O) at 0, 4, 8 and 16 mg Cd²⁺ kg^?1. In order to reduce the negative impact of Cd²⁺, cellulose was introduced to the soil at the following rates: 0 and 15 g kg^?1 and urea at 80 and 160 mg N kg^?1. The yield of the above-ground parts and roots was determined on days 40 and 80 of the experiment, along with the cadmium content in the plant material. The enzyme activity was also determined, and the physical and chemical properties of the soil were determined on the day of the oats’ (aftercrop) harvest.

Results and discussion

Contamination of soil with Cd²⁺ at 4 to 16 mg kg^?1 d.m. of soil reduced the yield of white mustard and oats. The tolerance index (TI) values indicate that oats (aftercrop) is more tolerant than white mustard of soil contamination with Cd²⁺. Cadmium accumulated more intensely in roots compared with the above-ground parts of the plants. The translocation index (TF) indicates smaller Cd²⁺ translocation from roots to above-ground parts, as it was below 1 in both plants. An addition of cellulose and nitrogen offsets the adverse impact of cadmium on plants. Arylsulphatase was the most sensitive to soil contamination with Cd²⁺, followed by dehydrogenases, catalase, β-glucosidase and urease, and alkaline phosphatase and acid phosphatase were the least sensitive. Contamination of soil with Cd²⁺ changed its physical and chemical properties only slightly.

Conclusions

White mustard and oats have phytostabilisation potential with respect to soil contaminated with cadmium. Cellulose introduced to the soil and fertilisation with urea alleviated the negative impact of cadmium on the growth and development of plants.

     

Underlying dynamics and effects of humic acid on selenium and cadmium uptake in rice seedlings

Purpose

Natural organic acids, such as humic acid (HA), play crucial roles in biogeochemistry of anions and cations in soil due to their numerous functional groups on their surfaces. Selenium (Se) and cadmium (Cd) could bind strongly to HA; nevertheless, it is still unclear as to the effects of HA on Se and Cd uptake in rice which will be focused on in this paper.

Materials and methods

Pot experiments were carried out at Huazhong Agricultural University, Wuhan City, Hubei Province, China. Agricultural soils were treated with different concentrations of HA (0, 4, and 8 g kg^?1 soil) and Se (Se^IV or Se^VI) (0 and 2 mg kg^?1 soil) as well as with base fertilizer 3 days prior to planting. For Cd treatment, experimental soils were treated with Cd (0 and 2 mg kg^?1 soil) 1 month before sowing. For element determination, root (after DCB extraction) and shoot samples were digested with a mixed solution of HNO₃-HClO₄, and the Se and Cd in digest solution were measured by HG-AFS and ICP-MS, respectively. Fe, Se, and Cd in iron plaque were extracted by DCB extraction and measured by AAS, HG-AFS, and ICP-MS, respectively.

Results and discussion

HA reduced Se (or Cd)-induced growth stimulation and Se and Cd uptake in rice seedlings, whereas iron plaque formation varied little with different treatments. HA inhibited Se^IV (or Se^VI) uptake in rice seedlings by reducing Se translocations from soil to iron plaque (or by increasing Se adsorption capacity of iron plaque and decreasing Se transport from iron plaque to root). HA reduced Cd uptake in rice seedlings by reducing Cd transport from soil to iron plaque and from iron plaque to root. Compared with single addition of Se^IV or Se^VI or HA, adding HA combined with Se^IV or Se^VI could further reduce Cd uptake in rice seedlings, whereas Se contents of aerial tissues did not change obviously.

Conclusions

HA inhibited the accumulation of Se (Se^IV or Se^VI) and Cd in rice seedlings; nevertheless, the mechanism was different. Compared with adding Se (or HA) alone, application of Se mixed with HA might be a more effective way to produce Se-enriched and Cd-deficient crop in Cd-contaminated soil.

     

Phytoextraction of cobalt (Co)-contaminated soils by sweet alyssum (Lobularia maritima (L.) Desv.) is enhanced by biodegradable chelating agents

Purpose

Combining biodegradable chelating agents with phytoextraction is an efficient technique to amend metal-contaminated soils, but most studies have addressed remediation efficiency rather than a comprehensive understanding of the interactions among plant stress, metal accumulation, and metal bioavailability. This study aimed to investigate the effects of biodegradable chelating agents on improving the efficiency of phytoextraction for cobalt (Co)-contaminated soil by sweet alyssum (Lobularia maritima (L.)) and to explore the interrelationships among plant stress, Co accumulation, and Co bioavailability.

Materials and methods

Sweet alyssum (three plants per pot) was grown in pots containing soil with Co added at 0, 40, and 60 mg kg^?1, respectively. After 70 days of growth, we added four biodegradable chelating agents (EDDS, NTA, CA, and OA) at various concentrations (0, 2.5, 5.0, and 7.5 mmol kg^?1). The plants were harvested after 7 days, and the biomass, reactive oxygen species (ROS) parameters, Co concentrations of the shoot and root, and available Co content in the soil were analyzed.

Results and discussion

The results demonstrate that chelating agents significantly (p?<?0.05) improved the phytoextraction capability of sweet alyssum and influenced plant growth and stress. The capability of EDDS to activate Co was higher than that of other chelating agents at identical concentrations in Co-contaminated soils. Furthermore, we observed that a moderate concentration (40 mg kg^?1) of Co could promote plant growth and that high concentrations of Co (60 mg kg^?1) and EDDS (7.5 mmol kg^?1) cause enhanced stress to plant growth, even resulting in lower shoot Co accumulation than that in the moderate EDDS treatment (5.0 mmol kg^?1).

Conclusions

The present study demonstrates that the application of EDDS may be a better choice for Co phytoextraction than NTA, CA, and OA; nevertheless, a high concentration of EDDS may enhance the negative effects on plant growth, physiological traits, and Co accumulation.

     

Coupled effects of biochar use and farming practice on physical properties of a salt-affected soil with wheat–maize rotation

Purpose

Being carbon-rich and porous, biochar has the potential to improve soil physical properties, so does conventional farming practice. Here, a field trial was conducted to investigate the combined effects of biochar use and farming practice on the physical properties of a salt-affected compact soil for wheat–maize rotation in the Yellow River Delta region.

Materials and methods

Salix fragilis L. was used as feedstock to produce biochar in the field via aerobic carbonization at an average temperature of 502 °C, terminated by a water mist spray, for use as a soil amendment at 0, 1, 2, and 4 g kg^?1 doses (CK, T1, T2, and T3, respectively). Farming practices included rotary tillage/straw returning for wheat sowing, spring irrigation, no-tillage seeding of maize, and autumn irrigation. Both cutting ring and composite samples of the soil were collected at four stages of wheat–maize rotation (22, 238, 321, and 382 d after the benchmark date of land preparation for wheat sowing) for the determination of soil properties by established methods.

Results and discussion

Rotary tillage/straw returning reduced soil bulk density (BD) from 1.48 to 1.27 g cm^?3 (CK) and 1.14 g cm^?3 (T3) and increased saturated hydraulic conductivity (Ks) from 0.05?×?10^?5 to 0.75?× 10^?5 cm s^?1 (CK) and 1.25?× 10^?5 cm s^?1 (T3). This tillage effect on BD and Ks gradually disappeared due to the disturbance from the subsequent farming practice. Biochar use lessened the disturbance. At maize harvest, BD was 1.47 (CK) vs. 1.34 g cm^?3 (T3), and Ks was 0.06?×?10^?5 (CK) vs. 0.28?×?10^?5 cm s^?1(T3); in comparison with CK, T3 increased Na⁺ leaching by 65%, Cl^? leaching by 98%, organic carbon content by 40.3%, and water-stable aggregates (0.25–2 mm) by 38%, indicating an improvement in soil properties.

Conclusions

Biochar use and rotary tillage improved soil physical properties (BD, Ks) and favored soil aeration, water filtration, and salt leaching, which further helped the accumulation of soil organic carbon, the formation of water-stable aggregates, and the amelioration of salt-affected compact soil.

     

Soil organic carbon changes in particle-size fractions following cultivation of Black soils in China

Soil texture can be an important control on soil organic carbon (SOC) retention and dynamics. The (clay + silt)-sized SOC pool (SOC < 20 μm) in non-cultivated or grassland soils has been proposed to reach an equilibrium or maximum level named protective capacity. Proper knowledge of SOC in this size fraction in non-cultivated and cultivated Black soils is important to evaluate management-induced changes in SOC in NE China. Twenty-seven paired soil samples (non-cultivated vs. cultivated) were collected in the Black soil zone in Heilongjiang and Jilin provinces. Bulk soil was dispersed in water with an ultrasonic probe and then soil size fractions were collected using the pipette technique for SOC analyses. Soil organic carbon in bulk soil and size fractions was measured by dry combustion. Average content of SOC < 20 μm was 23.2 g C kg⁻¹ at the 0–30 cm depth for the non-cultivated soils, accounting for 75.1% of the total SOC at the same depth. There was significant positive relationship between soil clay plus silt content and SOC < 20 μm in non-cultivated soils. Accordingly, a model of the maximum SOC < 20 μm in 0–30 cm depth of non-cultivated Black soils was developed: y = 0.36x where y is the maximum SOC < 20 μm pool (g C kg⁻¹) and x is the percentage of clay + silt (<20 μm) content. The average content of SOC < 20 μm was 18.7 g C kg⁻¹ at 0–30 cm depth for cultivated soils, accounting for 81.5% of total SOC. This average value of SOC was 4.4 g C kg⁻¹ less than the maximum value (23.1 g C kg⁻¹) and accounted for 55.0% of the difference of SOC between non-cultivated and cultivated Black soils. Cultivation resulted in 45.0% loss of sand-sized (>20 μm) SOC concentration relative to SOC < 20 μm. This result indicates that SOC < 20 μm and sand-sized SOC both play important roles in SOC dynamics resulting from management practices. This model can be applied to calculate the actual potential to restore SOC for cultivated Black soils under conservation tillage in NE China.     

Distribution and provenance implication of rare earth elements and Sr-Nd isotopes in surface sediments of Jiulong River,Southeast China

Purpose

The purposes of this paper are to investigate the geochemical characteristics of rare earth elements (REEs) in the surface sediments of Jiulong River, southeast China, to probe the provenance compositions of the sediments, and to analyze the potential anthropogenic influence on REEs in the sediments. REEs and Sr-Nd isotopes were selected as the tools because REEs can be used to identify the anthropogenic effects on sediments and Sr-Nd isotopes have been widely known as powerful tracers for provenance analysis.

Materials and methods

Fifty-three samples of surface sediments (0~5 cm) were collected from Jiulong River. The concentrations of REEs and Sr-Nd isotopic compositions in the surface sediments were determined by inductively coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS), respectively. The chondrite-normalized and WRAS-normalized REEs patterns, enrichment factor, plots of La-Th-Sc and La/Yb-∑REE, and plots of ε_Nd(0) vs ⁸⁷Sr/⁸⁶Sr and ε_Nd(0) vs δEu are presented.

Results and discussion

The mean concentration of ΣREEs in the surface sediments of Jiulong River was 254.25 mg kg^?1. The mean values of ΣLREEs (227.6 mg kg^?1), ΣHREEs (26.64 mg kg^?1), and (La/Yb)_N ratios (9.24) suggested an enrichment of LREEs compared to HREEs. Negative Eu anomalies were observed in the surface sediments. The distribution patterns of REEs in the surface sediments from different areas of Jiulong River were remarkably similar. The values of ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, and ε_Nd(0) were 0.714091~0.733476, 0.511875~0.512271, and ??14.88~??7.16, respectively. The plots of ε_Nd(0) vs ⁸⁷Sr/⁸⁶Sr, ε_Nd(0) vs 1/[Nd], and ε_Nd(0) vs δEu indicated that the sediments in Jiulong River were mainly derived from natural geological processes and the REEs might be also influenced by anthropogenic activities such as Fujian Pb-Zn deposit, coal ash, and industrial sludge.

Conclusions

The REEs in the surface sediments at different sites are similar in geochemical characteristics, with a right-inclined distribution pattern and higher enrichment of light REEs (LREEs) compared to heavy REEs (HREEs), and a negative Eu anomaly but no evidence of Ce anomaly. The sediments in Jiulong River were mainly derived from natural geological processes (granite and magmatic rocks), and the REEs in the sediments were also influenced by anthropogenic activities (Fujian Pb-Zn deposit, coal ash, and industrial sludge).

     

Lanthanides and yttrium in the sediments of the lower Minho River (NW Iberian Peninsula): imprint of tributaries

Purpose

Rare earth elements have been used as sediment tracers in river, estuarine and coastal environments but rarely applied as fluvial tributary tracers. Lanthanides (Ln) and yttrium (Y) were quantified in fluvial sediments of the Minho River lower course (NW Iberian Peninsula), where the catchment contains heterogeneous lithologies, to define the characteristic imprints of tributaries and their relevance in the riverine system.

Materials and methods

Surface sediments were sampled at 36 points in the lower Minho riverbed and its nine main tributaries.The <?2-mm fraction was sieved and ground, and ≈?100 mg was completely acid-digested with HF and aqua regia in closed Teflon bombs at 100 °C for 1 h. The residue was evaporated, re-dissolved with HNO₃ and Milli-Q water, heated 20 min at 75 °C and diluted to 50 cm³ with Milli-Q water. Lanthanides and yttrium were determined using a quadrupole ICP-MS equipped with a Peltier impact bead spray chamber and a concentric Meinhard nebuliser. Blanks accounted for less than 1% of the element concentrations in the samples. The precision and accuracy of the analytical procedures were controlled through reference materials AGV-1 and MAG-1.

Results and discussion

Contents ranged from 22 to 153 mg Ln kg^?1 and 1.5–22.9 mg Y kg^?1 and ES-normalised light-heavy Ln fractionation, (L_N/H_N), varied between 0.6 and 2.6. These wide ranges, together with Eu and Ce anomalies and element-by-element Ln, varied with changes in parental rocks of the lower Minho basin. Minho sediments showed negative Ce anomalies (0.81?±?0.29) and positive Eu anomalies (1.23?±?0.18). Sediments received traces of granitic pegmatites and gneissic peralkaline rocks from two tributaries: the Gadanha (22.9 mg Y kg^?1; 83 mg Ln kg^?1; 0.60 L_N/H_N; 0.51 Eu/Eu*; 0.88 Ce/Ce*) and the Louro (15.9 mg Y kg^?1; 110 mg Lnkg^?1; 0.97 L_N/H_N; 0.69 Eu/Eu*; 1.49 Ce/Ce*). The Tamuxe tributary, flowing through a slate and quartzite fault, provided the lowest source (1.6 mg Y kg^?1; 28 mg Ln kg^?1; 2.48 L_N/H_N; 1.01 Eu/Eu*; 0.55 Ce/Ce*).

Conclusions

Lanthanide and Y signatures in sediments may be used to trace land-tributary-river influences. The imprints are observed downstream of fluvial confluences but not in all cases, responding to basin lithological changes, particularly for pegmatites and peralkaline rocks. The general REE trend is described using Y contents only. Tributaries, which are responsible for one-fifth of the Minho water load, provide one-half of their sediments. Non-homogeneous sediment patterns may be magnified in dammed rivers such as the Minho.

     

Application of VNIR and machine learning technologies to predict heavy metals in soil and pollution indices in mining areas

Purpose

Soil pollution indices are an effective tool in the computation of metal contamination in soil. They monitor soil quality and ensure future sustainability in agricultural systems. However, calculating a soil pollution index requires laboratory measurements of multiple soil heavy metals, which increases the cost and complexity of evaluating soil heavy metal pollution. Visible and near-infrared spectroscopy (VNIR, 350–2500 nm) has been widely used in predicting soil properties due to its advantages of a rapid analysis, non-destructiveness, and a low cost.

Methods

In this study, we evaluated the ability of the VNIR to predict soil heavy metals (As, Cu, Pb, Zn, and Cr) and two commonly used soil pollution indices (Nemerow integrated pollution index, NIPI; potential ecological risk index, RI). Three nonlinear machine learning techniques, including cubist regression tree (Cubist), Gaussian process regression (GPR), and support vector machine (SVM), were compared with partial least squares regression (PLSR) to determine the most suitable model for predicting the soil heavy metals and pollution indices.

Results

The results showed that the nonlinear machine learning models performed significantly better than the PLSR model in most cases. Overall, the SVM model showed a higher prediction accuracy and a stronger generalization for Zn (R²_V?=?0.95, RMSE_V?=?6.75 mg kg^?1), Cu (R²_V?=?0.95, RMSE_V?=?8.04 mg kg^?1), Cr (R²_V?=?0.90, RMSE_V?=?6.57 mg kg^?1), Pb (R²_V?=?0.86, RMSE_V?=?4.14 mg kg^?1), NIPI (R²_V?=?0.93, RMSE_V?=?0.31), and RI (R²_V?=?0.90, RMSE_V 3.88). In addition, the research results proved that the high prediction accuracy of the three heavy metal elements Cu, Pb, and Zn and their significant positive correlations with the soil pollution indices were the reason for the accurate prediction of NIPI and RI.

Conclusion

Using VNIR to obtain soil pollution indices quickly and accurately is of great significance for the comprehensive evaluation, prevention, and control of soil heavy metal pollution.