利用便携式X-射线荧光光谱法研究冰块对土壤元素特性的影响

Field portable X-ray fluorescence （PXRF） spectrometry has become an increasingly popular technique for in-situ elemental characterization of soils. The technique is fast, portable, and accurate, requiring minimal sample preparation and no consumables. However, soil moisture 〉 20% has been known to cause fluorescence denudation and error in elemental reporting and few studies have evaluated the presence of soil moisture in solid form as ice. Gelisols （USDA Soil Taxonomy）, permafrost-affected soils, cover a large amount of the land surface in the northern and southern hemispheres. Thus, the applicability of PXRF in those areas requires further investigation. PXRF was used to scan the elemental composition （Ba, Ca, Cr, Fe, K, Mn, Pb, Rb, Sr, Ti, Zn, and Zr） of 13 pedons in central and northern Alaska, USA. Four types of scans were completed： 1） in-situ frozen soil, 2） re-frozen soil in the laboratory, 3） melted soil/water mixture in the laboratory, and 4） moisture-corrected soil. All were then compared to oven dry soil scans. Results showed that the majority of PXRF readings from in-situ, re-frozen, and melted samples were significantly underestimated, compared to the readings on oven dry samples, owing to the interference expected by moisture. However, when the moisture contents were divided into 〉 40% and 〈 40〈 groups, the PXRF readings under different scanning conditions performed better in the group with 〈 40% moisture contents. Most elements of the scans on the melted samples with 〈 40% moisture contents acceptably compared to those of the dry samples, with R2 values ranging from 0.446 （Mn） to 0.930 （St）. However, underestimation of the melted samples was still quite apparent. Moisture-corrected sample PXRF readings provided the best correlation to those of the dry, ground samples as indicated by higher R2 values, lower root mean square errors （RMSEs）, and slopes closer to 1 in linear regression equations. However, the in-situ （frozen） sample scans did not differ appreciably from the melted sample scans in their correlations to dry sample scans in terms of R2 values （0.81 vs. 0.88）, RMSEs （1.06 vs. 0.85）, and slopes （0.88 vs. 0.92）. Notably, all of those relationships improved for the group with moisture contents 〈 40%.     

A procedure for sampling the soil microenvironment at the site of fertilizer application

Abstract

A procedure was developed to sample and analyze levels of ammonium and urea as well as pH in the soil within the immediate zone of a single urea fertilizer granule. The method involved sectioning a 2 x 3.6 cm slice of soil (0.9 cm thick) into 45 subsamples, which were analyzed individually. After analysis, the data were presented in graphical format to show the nutrient concentrations in the zone. The method was relatively easy to carry out using equipment that could be easily constructed. The precision of the procedure was high as indicated by the low variability between replicates.     

样品粒径、制样方法对波长色散X射线荧光光谱法测定土壤样品中19种元素的影响

利用波长色散X射线荧光光谱仪建立了压片、熔融土壤样品中As、Co、Cr、Cu、Mn、Ni、P、Pb、S、Ti、V、Zn、Al2O3、CaO、Fe2O3、K2O、MgO、Na2O、SiO₂ 19种元素的分析方法。探讨了样品粒径、制样方法对19种元素检测的影响。方法精密度结果表明,样品中As、Co元素含量在10 mg/kg以上时,0.149 mm(100目)样品压片、0.075 mm(200目)样品压片及样品熔融制样的19种元素的相对标准偏差(RSD)值均小于10 %,As、Co含量在10 mg/kg以下时,200目压片制样的19种元素RSD值小于10%。准确度结果表明,压片制样的标准物质含量在5 mg/kg以上的As、Co、Cu及其他16种元素准确度符合要求;熔融制样的标准物质中高含量的As、Co、Cu、Pb元素及其他15种元素准确度符合要求。不同粒径实验结果显示,元素含量在10 mg/kg以上时,100目、200目压片制样19种元素的RSD值小于10%。不同制样方法的实验结果表明,熔融制样不适用于低含量的As、Co、Cu、Pb元素分析,Cr、P、S、Mn、Ni、V、Zn、Ti、Al2O3、CaO、Fe2O3、K2O、MgO、Na2O、SiO₂ 熔融制样与压片制样RSD值小于10%。压片制样方法操作更简单,成本更低,更适用于大批量土壤样品中As、Co、Cr、Cu、Pb、P、S、Mn、Ni、V、Zn、Ti、Al2O3、CaO、Fe2O3、K2O、MgO、Na2O、SiO₂ 19种元素的分析;对于As、Co元素含量在10 mg/kg以上的样品,利用100目、200目样品压片制样均可获得准确、可靠的结果,对于As、Co含量在10 mg/kg以下的样品,建议使用200目样品压片制样。     

Method development and sample processing of water,soil, and tissue for the analysis of total and organic mercury by cold vapor atomic fluorescence spectrometry

Atomic Fluorescence-based methods have been developed for measuring ultratrace levels of mercury (Hg) in environmental (water, soil) and biological (fish tissue) samples. In addition, methods for preparation of water, soil, and tissue samples have been developed. For the analysis of total Hg in soil, sediment and fish the samples are digested with concentrated nitric acid in sealed glass ampules, and subsequently autoclaved. Water samples are digested using standard brominating procedures. A Merlin Plus, PS Analytical atomic fluorescence spectrometer (AFS) system equipped with an autosampler, vapor generator, fluorescence detector and a PC based integrator package is used in the determination of total Hg. The determination of Hg mercury species in water, without pre-derivatization, involves adsorbent pre-concentration of the organomercurials onto sulfydryl-cotton fibers. The organic Hg compounds are eluted with a small volume of acidic KBr and CuSO₄ and extracted into dichloromethane. Sediment, soil and tissue samples are homogenized and the organomercurials first released from the sample by the combined action of acidic KBr and CuSO₄ and extracted into dichloromethane. The initial extracts are subjected to thiosulfate clean-up and the organomercury species are isolated as their chloride derivatives by cupric chloride addition and subsequent extraction into a small volume of dichloromethane. Analysis of organic Hg compounds is accomplished by capillary column chromatography coupled with atomic fluorescence detection.     

Indicators of soil quality and crop productivity assessment at a long-term experiment site in the lower Indo-Gangetic plains

Deterioration of soil quality under resource-intensive modern agriculture in the face of global climate change poses a huge risk to food security. Because of the complex nature, estimators of soil quality often rely upon a limited set of soil attributes, along with statistical data reduction techniques, for developing quality indices, whilst overlooking biological aspects and regional climatic variability. This study screened the most suitable soil quality indexing approaches for a rice-oilseed-based cropping system in the lower Indo-Gangetic plains (IGP). For this, surface soil samples (0–15 cm) were collected from an ongoing long-term fertilizer experiment with a rice-mustard-sesame cropping system in the IGP. The following treatments were assessed for their effect on soil quality: T₁-control, T₂-NPK (recommended NPK doses), T₃-NPKG (NPK + in situ green manuring), T₄-NPKGB (NPK + in situ green manuring + biofertilizer) and T₅-NPKF (NPK + farm yard manure FYM). We found that total organic carbon (TOC), β-glucosidase, CaCl₂ extractable S, alkaline KMnO₄ oxidizable N, activity of urease, amidase enzyme and mean weight diameter (MWD) were sensitive key indicators of soil quality. The NPKF treatment maintained the highest soil quality status (0.80–0.91), both under productivity and environmental protection goals, owing to the availability of decomposable carbon. Regression analysis showed a better agreement of equivalent rice yield with expert opinion (EO; R² = 0.89) than principal component analysis (PCA; R² = 0.76). Finally, we found that the expert opinion approach with the nonlinear scoring function was the best tool for soil quality assessment of the region.     

A new method for continuously measuring the δ13C of soil CO2 concentrations at different depths by laser spectrometry

Soil carbon dioxide (CO₂) efflux is an important component of the carbon (C) cycle but the biological and physical processes involved in soil CO₂ production and transport are not fully understood. To improve our knowledge, we present a new approach to measure simultaneously soil CO₂ concentrations and efflux, and their respective isotopic signatures (δ¹³C‐CO₂). To quantify soil air ¹³CO₂ and ¹²CO₂ concentrations, we adapted a method based on CO₂ diffusion from soil pores into tubes with a highly gas‐permeable membrane wall. These tubes were placed horizontally at different depths in the soil. Air was sampled automatically from the tubes and injected through a diluting system into a tuneable diode laser absorption spectrometer. The CO₂ and δ¹³C‐CO₂ vertical profiles were thus obtained at hourly intervals. Our tests demonstrated the absence of fractionation in the membrane tubes for δ¹³C‐CO_2. Subsequently, we set up field experiments for two forest soils, which showed that natural soil CO₂ concentrations and δ¹³C‐CO₂ were not affected significantly by the measurement system. While δ¹³C‐CO₂ in air‐filled pores below 5 cm was constant over 3 days, we observed large diurnal variations in δ¹³C‐CO₂ efflux. However, the average difference between the two measurements was close to ?4.4‰, which supports steady‐state diffusion over this 3‐day period. This new method seems to be a very effective way to measure the δ¹³C‐CO₂ profile of the soil atmosphere, and demonstrates that the fractionation that occurs during diffusion is the main transport process that affects the δ¹³C‐CO₂ of the soil CO₂ efflux on a daily timescale while advection may account for within‐day variations.     

Evaluating a low‐cost portable NIR spectrometer for the prediction of soil organic and total carbon using different calibration models

This study aims to assess the performance of a low‐cost, micro‐electromechanical system‐based, near infrared spectrometer for soil organic carbon (OC) and total carbon (TC) estimation. TC was measured on 151 soil profiles up to the depth of 1 m in NSW, Australia, and from which a subset of 24 soil profiles were measured for OC. Two commercial spectrometers including the AgriSpec^TM (ASD) and NeoSpectra^TM (Neospectra) with spectral wavelength ranges of 350–2,500 and 1,300–2,500 nm, respectively, were used to scan the soil samples, according to the standard contact probe protocol. Savitzky–Golay smoothing filter and standard normal variate (SNV) transformation were performed on the spectral data for noise reduction and baseline correction. Three calibration models, including Cubist tree model, partial least squares regression (PLSR) and support vector machine (SVM), were assessed for the prediction of soil OC and TC using spectral data. A 10‐fold cross‐validation analysis was performed for evaluation of the models and devices accuracies. Results showed that Cubist model predicts OC and TC more accurately than PLSR and SVM. For OC prediction, Cubist showed R² = 0.89 (RMSE = 0.12%) and R² = 0.78 (RMSE = 0.16%) using ASD and NeoSpectra, respectively. For TC prediction, Cubist produced R² = 0.75 (RMSE = 0.45%) and R² = 0.70 (RMSE = 0.50%) using ASD and NeoSpectra, respectively. ASD performed better than NeoSpectra. However, the low‐cost NeoSpectra predictions were comparable to the ASD. These finding can be helpful for more efficient future spectroscopic prediction of soil OC and TC with less costly devices.     

Radish as an indicator plant for derelict land: Uptake of zinc at toxic concentrations

Abstract

Radish was grown in glasshouse experiments. Two experiments involved mixing varying ratios of calcareous zinc (Zn) mine waste with soil and in the third, radish was grown in culture solution supplemented with Zn. Zinc toxicity was seen at higher treatment concentrations. From curves for substrate Zn versus % yield the toxic threshold was estimated as 343 μg Zn/g soil which compares favourably with the British “trigger concentration” of 300 μg Zn/g. Small yields of hypocotyls were obtained at 1000 μg Zn/g. A 50% yield reduction occurred at tissue Zn concentrations from 36.1–1013 μg/g. The shape of Zn uptake curves suggested that hypocotyls were “indicators” of Zn uptake but leaves were “excluders”. The relative ease with which radish is grown in terms of climate and supervision together with its growth properties on contaminated soil suggest it is suitable as a monitor crop for derelict land.     

Temporal and spatial variation and risk assessment of soil heavy metal concentrations for water-level-fluctuating zones of the Three Gorges Reservoir

Purpose

This study aimed to reveal the temporal and spatial variation of soil heavy metal concentrations in the Three Gorges Reservoir area (TGR) water-level-fluctuating zone (WLFZ) and evaluated its pollution status and potential ecological risks and provide scientific basis for ecological risk prevention and ecological restoration of the TGR.

Materials and methods

This study was based on long-term monitoring of soil heavy metals (Cu, Pb, Cd, and Cr) before water level fluctuation (2008) and after 1 (2009), 4 (2012), or 7 (2015) cycles of water level fluctuation at the altitude of 155–172 m in the Wushan (WS) and Zigui (ZG) sections of the TGR, and pollution status and potential ecological risks of each heavy metal element were evaluated by index of geoaccumulation and potential ecological risk index.

Results and discussion

The Cd concentration increased with the increase in the number of reservoir water level fluctuations, whereas the concentrations of Cu, Cr, and Pb varied with the monitoring site. The Cd showed clear horizontal transfer characteristics. Moreover, with the increase of the frequency of water level fluctuations the Cd concentration at ZG (near the dam) were higher than those at WS (away from the dam). After 7 cycles of water level fluctuation, the concentrations of most soil heavy metal were not obvious differences between soil layers (except Pb). Before and after the reservoir water level fluctuation, Cd contamination level changed from pollution-free to strong or extremely polluted, Cu contamination level changed from pollution-free to moderately polluted, and Cr and Pb were pollution-free. Before the fluctuation of the reservoir water level, the potential ecological risk of Cd in the WS reached a classification of strongly polluted, whereas pollution at ZG was considered to be low level. However, after 4 cycles of water level fluctuation the Cd pollution level increased to a very high level, whereas Cu, Cr, and Pb remained consistently low.

Conclusions

There is an obvious temporal and spatial variation of heavy metal concentrations for WLFZ of TGR. Cd concentration increased with the increase in the number of reservoir water level fluctuations. Heavy metal concentrations changed from WS > ZG to WS < ZG after the impact of water level fluctuations. After 7 cycles of water level fluctuation, the distribution of heavy metals in different soil layers tends to be uniform (except Pb). Cd pollution is more serious, and there is a strong potential ecological risk.

     

Biological tools for the assessment of contaminated land: applied soil ecotoxicology

Abstract. Chemical analysis alone is inadequate for comprehensively assessing the impact of soil pollution on biota. The term bioavailability can only be applied in a context specific to a target biological receptor or a proven chemical surrogate. Integration of biological and chemical data can often yield significant advances in hazard assessment and act as a suitable baseline for making site-specific risk assessments. Here, the value of biological techniques is discussed and their application described. The relative merit of test selection is considered and the new direction being developed in sublethal assessments. Currently, however, one of the major limitations is the seeming lack of flexibility of many assays in that they are either applicable to agricultural systems or industrial scenarios, but rarely to both. As a consequence, few assays have internationally adopted protocols. The introduction of new methods and the continued improvement and refinement of assays make this area of soil science dynamic and responsive.     

Validation of an electrothermal atomization atomic absorption spectrometry method for the determination of aluminum, copper, and lead in grapes

An electrothermal atomization atomic absorption spectrometry method was validated to quantify aluminum, copper, and lead in grapes. The limits of detection were 1.11, 0.19, and 0.35 micro g/L for Al, Cu, and Pb, respectively. The linearity ranges under optimized conditions were 1.11-50.0, 0.19-25, and 0.35-50.0 micro g/L for Al, Cu, and Pb, respectively. The limits of quantification were 74.0, 12.5, and 11.6 ng/g of dry weight for Al, Cu, and Pb, respectively. For all of the metals, the precision for the instrumental method was lower than 5.4% and for the analytical method, lower than 10%. The accuracy of the method was evaluated by the standard additions method, the recoveries being higher than 90% for all of the concentrations added. An interference study was also carried out in a simulated matrix, and it was verified that the deviations from the expected values were lower than 3.4% for all of the metals. The method was applied to the monitoring of the metals referred to above in 35 samples of grapes obtained in marketplaces and at farmhouses. The metals were quantified in the whole grapes, washed or not, and in the peel and pulp of unwashed grapes.     

A linear functional relationship model for circular data with an application to the assessment of ocean wave measurements

This article suggests a linear functional relationship model for comparing two sets of circular data subject to unobservable errors. Unlike the corresponding and relatively well-studied model for linear data, maximum likelihood estimation for this model is very complicated and no explicit solutions are possible. Using a numerical approximation, we are able to solve the likelihood equations approximately, and to obtain good approximations to the likelihood estimates of the parameters. The quality of our estimates and the feasibility of the estimation method are illustrated via simulation. By establishing a parallel with the model for linear data, we are able to explain the various problems occurring in the process of estimation and to substantiate our numerical results. The interest in the model arose in connection with the study of ocean wave data; an application to such data is also given.     

Microbial characteristics of soils from graves: an investigation at the interface of soil microbiology and forensic science

Very little is known about the microbiology of graves. We have taken the opportunity to investigate this subject by taking advantage of the unusual opportunity afforded by the experimental burial of pigs in a forensic experiment. Selected microbial characteristics of soils from the 0–15 and 15–30 cm depths of the graves of three pigs and of control soils have been determined 430 days after burial. The grave soils contained more total C, microbial biomass C and total N, and showed increased rates of respiration and N mineralisation compared to the control soils. The grave soils also had larger amino acid and NH₄⁺ concentrations, which was consistent with the increases in both net N mineralisation and pH values. Nitrification was not detected in any of the soils and the limited NO₃⁻ supply restricted the rate of denitrification, but the large alkali-soluble S²⁻ concentration of soils from the graves indicated reducing conditions in the graves.     

From experimental research to an on‐farm tool for participatory monitoring and evaluation: an assessment of soil erosion risk in organic olive orchards

The conservation of soil in agricultural systems prone to erosion can occur as a result of conscientious soil management practices by individual farmers. Although soil is one of the world's most important and highly threatened natural resources, and should be among the top priorities in organic agriculture, soil management practices and the effect of those practices on erosion risk are rarely, if ever, taken into account as a part of organic certification. In order to fulfil the need for a tool to monitor soil erosion in organic olive orchards in Southern Spain, we have developed a methodology that assesses erosion risk through an easy to use, illustrated erosion risk field manual to be used by farmers, inspectors for certifying agencies and field technicians. The methodology developed for the assessment is based on a simplified version of the Revised Universal Soil Loss Equation (RUSLE), combined with an evaluation of key visual symptoms of soil erosion. The methodology is described, and the results from use of the assessment in the field and in workshops with farmers are presented. The potential for use of the methodology for other crops and in other regions is discussed and also the future relevance of farmer‐oriented tools in the context of changing regulations within the common agricultural policy of the European Union. Copyright © 2007 John Wiley & Sons, Ltd.     

Preferential flow and aging of NAPL in the unsaturated soil zone of a hazardous waste site: implications for contaminant transport

Flow of non‐aqueous phase liquids (NAPL) in the unsaturated zone is thought to be driven by gravity with a dominant vertical flow direction, and lateral spreading to be limited to the gradient of the relative permeabilities. The effect of soil profile build‐up, preferential flow, aging, and groundwater level fluctuations is mostly neglected. The objective of our study was to check the effects of such processes on the fate of NAPL in the unsaturated soil zone. At a hazardous waste site, we conducted a field survey of the unsaturated soil zone and monitored the groundwater for a two year period. We conducted spatially resolved and depth dependent soil sampling and analysis and the evaluation of former ram and core drilling protocols. The samples were analyzed for the 16 EPA PAH and alkanes with GC‐MS and GC‐FID. ¹³C‐NMR spectroscopy was used to assess structural changes of the NAPL phase. Flow of bulk NAPL along macropores and along preferential permeability structures, like sedimentation discontinuities, are the dominant transport pathways which cause large lateral spreading beyond those expected by the relative permeability gradient. Accumulation of NAPL was found at locations with abrupt textural changes and within the zone of capillary rise. Aging of NAPL results in the depletion in soluble and volatile compounds but also in oxidation and polymerization. It increases the chemical diversity and decreases the mobility of the NAPL. Thus, NAPL flow ceases much earlier than expected from the capillary forces. As chemical transformation is restricted to the NAPL water/air interface, a skin‐like thin film is formed which encapsulates and preserves the bulk NAPL from further hardening, limiting contaminant mass transfer from the NAPL to the aqueous phase.     

Treatment of an acid soil with bentonite used for wine fining: effects on soil properties and the growth of Lolium multiflorum

When used to fine wines, bentonite acquires a protein load that makes it a potentially useful fertilizer. Other properties of bentonite are also potentially useful for soil amendment. In the work described in this paper, waste bentonite from a winery was applied to an acid soil, and its effects on soil properties and on the growth of Lolium multiflorum were evaluated. Soil N, K, and P contents all increased, as did pH and cation exchange capacity. Biomass production increased as the dose of bentonite increased up to 5 g kg(-1), decreasing at larger doses (possibly as a result of falling potassium/magnesium ratio and increasing electrical conductivity). Environmental drawbacks of waste bentonite include its high soluble copper content, although its conversion in the soil to less soluble forms reduces its potential phytotoxicity. The copper, manganese, and zinc contents of the ryegrass crop were low.     

Influence of soil pH on the toxicity of aluminium for Eisenia andrei (Oligochaeta: Lumbricidae) in an artificial soil substrate

Toxicity of aluminium for the earthworm Eisenia andrei was studied in artificial soil at different pH levels. In a range-finding test, effects of three different aluminium salts on earthworm survival were determined. AlCl₃ appeared to be most toxic, with LC₅₀ values of 316, 359 and >1000 mg Al/kg dry soil at pH_KCl of 3.5, 4.4 and 6.7, respectively in the control soils. Effects of this salt interfered with a strong decrease of soil pH with increasing aluminium concentration. Al₂(SO₄)₃ was less toxic with LC₅₀ values of 457, >4000 and >4000 mg Al/kg dry soil at pH 3.24, 4.86 and 7.22, respectively. Al₂O₃ did not affect earthworm survival at concentrations of 5000 mg Al/kg and pH levels between 2.4 and 7.1.In the main test, earthworms were exposed for 6 weeks to soils treated with Al₂(SO₄)₃. As in the range-finding test, aluminium sulfate was most toxic at a pH of 3.4 with an LC₅₀ of 589 mg Al/kg dry soil. At this pH, growth and cocoon production of earthworms were significantly reduced at 320 mg Al/kg dry soil, while at 1000 mg Al/kg dry soil all earthworms died. Survival was not affected by 1000 mg Al/kg dry soil at pH 4.3 and 7.3. At pH 4.3, growth was significantly reduced at 1000 mg Al/kg dry soil and cocoon production at 320 and 1000 mg Al/kg dry soil. At pH 7.3, aluminium only affected cocoon production at the two highest exposure levels. At the highest two exposure levels at pH 7.3, growth was significantly increased, suggesting a trade-off between growth and reproduction. These effects of aluminium at the highest soil pH could not be explained from the concentration of extractable, monomeric (labile) aluminium in soil, which decreased with increasing soil pH.