An empirical map of critical loads of acidity for soils in Great Britain

The method used to produce a critical load map of acidity for soils in Great Britain is described. Critical loads were assigned to the dominant soil in each 1 km grid square of the UK national grid. Mineral soils were assigned a critical load based on mineralogy and chemistry, using approaches appropriate to UK conditions. Critical loads for peat soils are based primarily on a maximum acceptable reduction of peat pH, and results from laboratory equilibration studies. The map shows that soils with small critical loads (<0.5 kmol_c ha⁻¹ year⁻¹) i.e. highly sensitive to acidic deposition, dominate in the north and west of Britain; the south and east are dominated by soils with large critical loads, with small areas of more sensitive soils associated with sandy soil-forming materials. A modified critical load map illustrates the potential impact of agricultural liming on soil critical loads.     

Estimates of critical acid loads and exceedances for forest soils across the conterminous United States

Concern regarding the impacts of continued nitrogen and sulfur deposition on ecosystem health has prompted the development of critical acid load assessments for forest soils. A critical acid load is a quantitative estimate of exposure to one or more pollutants at or above which harmful acidification-related effects on sensitive elements of the environment occur. A pollutant load in excess of a critical acid load is termed exceedance. This study combined a simple mass balance equation with national-scale databases to estimate critical acid load and exceedance for forest soils at a 1-km(2) spatial resolution across the conterminous US. This study estimated that about 15% of US forest soils are in exceedance of their critical acid load by more than 250eqha(-1)yr(-1), including much of New England and West Virginia. Very few areas of exceedance were predicted in the western US.     

Characterizing the uncertainty of pesticide leaching in agricultural soils

A Monte-Carlo numerical simulation procedure for making regional assessments of pesticide leaching has been developed. This procedure uses probability density functions for organic matter, field capacity, and wilting point developed from information on approximately 3000 soils. Variations in climatic conditions were incorporated by random selection of yearly rainfall data. The procedure was demonstrated for aldicarb applied to corn grown in Ohio. A total of 2000 parameter sets were evaluated using the unsaturated zone model PRZM. The simulation results indicated that convergence of the 90th, 95th, and 99th percentiles for movement past 0.3, 0.6, 0.9, and 1.5 m was obtained after 500 simulations. The relative uncertainty associated with these percentiles was approximately 50% after 1500 simulations. The downward movement of aldicarb residues was most sensitive to changes in field capacity. These simulations, coupled with additional soil-specific simulations, indicated no significant movement of aldicarb residues beyond 1.8 m for applications to Ohio corn.     

A statistical approach to the regional use of critical loads

The premise of this paper is that: (1) effects of spatial heterogeneity of watershed response to acid deposition must be considered when models are used to set abatement policies, and (2) the evaluation of critical chemical values is a better measure off the effects of abatement policies than the comparison of deposition values to critical loads. The authors used Monte Carlo methods to apply a site-specific version of the RAINS-Lake-Model to a regional data set from The Netherlands. Statistical methods were then used to identify the important parameters affecting the spatial and temporal response, i.e. a change in pH, of watersheds to acid deposition and a subset of sensitive and insensitive watersheds were derived. The results show that the failure to subset a region into sensitive and insensitive zones may result in an erroneous estimation of the effect of abatement policies based on critical loads alone.     

Soil vapor extraction in sandy soils: influence of airflow rate

Airflow rate is one of the most important parameters for the soil vapor extraction of contaminated sites, due to its direct influence on the mass transfer occurring during the remediation process. This work reports the study of airflow rate influence on soil vapor extractions, performed in sandy soils contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene and perchloroethylene. The objectives were: (i) to analyze the influence of airflow rate on the process; (ii) to develop a methodology to predict the remediation time and the remediation efficiency; and (iii) to select the most efficient airflow rate. For dry sandy soils with negligible contents of clay and natural organic matter, containing the contaminants previously cited, it was concluded that: (i) if equilibrium between the pollutants and the different phases present in the soil matrix was reached and if slow diffusion effects did not occur, higher airflow rates exhibited the fastest remediations, (ii) it was possible to predict the remediation time and the efficiency of remediation with errors below 14%; and (iii) the most efficient remediation were reached with airflow rates below 1.2 cm(3)s(-1) standard temperature and pressure conditions.     

Changes in acidity and cation pools of south Swedish soils between 1949 and 1985

The pH of south Swedish soils have decreased considerably during the last 15–35 years. The decrease has occurred throughout the soil profile, not only in the rhizosphere, and is particularly marked in the originally less acid soils. The pH decrease was accompanied by considerable losses of exchangeable Na, K, Mg and Ca, as well as of Zn and (in the originally less acid soils) of Mn. The changes can be prognosticated from the current relationship between soil pH and base saturation and from budget calculations based on lysimeter data.     

Forest biomass accumulation is an important source of acidity to forest soils: Data from Swedish inventories of forests and soils 1955 to 2010

The input of acidity to Swedish forest soils through forestry between 1955 and 2010 is compared with the acid input from atmospheric deposition. Depending on region, input of acidity from forestry was the minor part (25–45%) of the study period’s accumulated acid input but is now the dominating source (140–270 mol_c ha⁻¹ year⁻¹). The net uptake of cations due to the increase in standing forest biomass, ranged between 35 and 45% of the forestry related input of acidity while whole-tree harvesting, introduced in the late 1990s, contributed only marginally (< 2%). The geographical gradient in acid input is reflected in the proportion of acidified soils in Sweden but edaphic properties contribute to variations in acidification sensitivity. It is important to consider the acid input due to increases in standing forest biomass in acidification assessments since it is long-term and quantitatively important.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-021-01540-y.     

Using sequential indicator simulation to assess the uncertainty of delineating heavy-metal contaminated soils

Mapping the spatial distribution of soil pollutants is essential for delineating contaminated areas. Currently, geostatistical interpolation, kriging, is increasingly used to estimate pollutant concentrations in soils. The kriging-based approach, indicator kriging (IK), may be used to model the uncertainty of mapping. However, a smoothing effect is usually produced when using kriging in pollutant mapping. The detailed spatial patterns of pollutants could, therefore, be lost. The local uncertainty of mapping pollutants derived by the IK technique is referred to as the conditional cumulative distribution function (ccdf) for one specific location (i.e. single-location uncertainty). The local uncertainty information obtained by IK is not sufficient as the uncertainty of mapping at several locations simultaneously (i.e. multi-location uncertainty or spatial uncertainty) is required to assess the reliability of the delineation of contaminated areas. The simulation approach, sequential indicator simulation (SIS), which has the ability to model not only single, but also multi-location uncertainties, was used, in this study, to assess the uncertainty of the delineation of heavy metal contaminated soils. To illustrate this, a data set of Cu concentrations in soil from Taiwan was used. The results show that contour maps of Cu concentrations generated by the SIS realizations exhausted all the spatial patterns of Cu concentrations without the smoothing effect found when using the kriging method. Based on the SIS realizations, the local uncertainty of Cu concentrations at a specific location of x', refers to the probability of the Cu concentration z(x') being higher than the defined threshold level of contamination (z(c)). This can be written as Prob(SIS)[z(x')>z(c)], representing the probability of contamination. The probability map of Prob(SIS)[z(x')>z(c)] can then be used for delineating contaminated areas. In addition, the multi-location uncertainty of an area A,delineated as contaminated based on the probability map of Prob(SIS)[z(x')>z(c)], can be calculated to assess the reliability of delineation. Multi-location uncertainty refers to the probability of Cu concentrations in several locations, x'(1), x'(2), em leader, x'(m,) in the area A, being higher than the threshold (z(c)) as denoted by Prob(SIS)[z(x'(1))>z(c), z(x'(2))>z(c), em leader, andz(x'(m))>z(c)] or Prob(SIS)[z(A)>z(c)]. The multi-location uncertainty Prob(SIS)[z(A)>z(c)], obtained from the SIS, can be used to assess the reliability of delineation for regions suspected of contamination, (A), which has been delineated as contaminated. Reliance on this information facilitates the decision making process in determining which areas are contaminated and require cleanup action.     

中国主要湖泊营养氮沉降临界负荷的研究

水体营养氮沉降临界负荷是不致使水体产生富营养化的最高氮沉降量。文中探讨了一种依据湖泊氮质量平衡原理计算营养氮沉降临界负荷的方法。用该方法计算表明 ,我国主要湖泊的营养氮沉降临界负荷比较低 ,大部分小于 1keq· hm- 1 · a- 1 ,部分已为目前的氮沉降量或者两者相当接近 ,意味着只接受氮沉降也能导致这些湖泊产生富营养化。但实际统计结果表明 ,氮沉降在导致受工农业生产和生活影响很大的城市和郊区湖泊的水质富营养化的所有氮污染源中所占比例较低 ,而其它来源的氮输入如河道入湖、工业生活废水和农田径流等才是导致富营养化的最主要因素 ,它们的量已远远超过了这些水体可随最高允许氮负荷。因此 ,对控制这些湖泊的水质富营养化而言 ,控制氮沉降并不是目前最紧迫的任务 ,而其它人为污染源的控制才是最急需的。但氮沉降临界负荷在湖泊富营养化的中长远控制中仍具有十分重要的意义。     

Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

A simple effective procedure for the determination of adenosine triphosphate in soils

A simple method for the extraction and determination of adenosine 5′-triphosphate (ATP) in soil is described. ATP was extracted by stirring with dimethyl sulphoxide (DMSO), followed by adding 0.01 M trisodium phosphate (Na₃PO₄) buffer solution for a further dispersion. The ATP content was quantitatively measured by luciferin-luciferase system employing a standard addition technique. The method was most efficient in comparison with 7 other extraction procedures. The recoveries of ATP in spiked soil were found to be approximately 100 %. ATP contents in 16 selected soils were in ranges of 0.76±0.05 – 7.79±0.83 μg/g (dry weight). A significant correlation between ATP amounts and biomasses in these soils was also observed.     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.     

Estimate of the uncertainty in measurement for the determination of mercury in seafood by TDA AAS

An approach for the estimate of the uncertainty in measurement considering the individual sources related to the different steps of the method under evaluation as well as the uncertainties estimated from the validation data for the determination of mercury in seafood by using thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) is proposed. The considered method has been fully optimized and validated in an official laboratory of the Ministry of Agriculture, Livestock and Food Supply of Brazil, in order to comply with national and international food regulations and quality assurance. The referred method has been accredited under the ISO/IEC 17025 norm since 2010. The approach of the present work in order to reach the aim of estimating of the uncertainty in measurement was based on six sources of uncertainty for mercury determination in seafood by TDA AAS, following the validation process, which were: Linear least square regression, Repeatability, Intermediate precision, Correction factor of the analytical curve, Sample mass, and Standard reference solution. Those that most influenced the uncertainty in measurement were sample weight, repeatability, intermediate precision and calibration curve. The obtained result for the estimate of uncertainty in measurement in the present work reached a value of 13.39%, which complies with the European Regulation EC 836/2011. This figure represents a very realistic estimate of the routine conditions, since it fairly encompasses the dispersion obtained from the value attributed to the sample and the value measured by the laboratory analysts. From this outcome, it is possible to infer that the validation data (based on calibration curve, recovery and precision), together with the variation on sample mass, can offer a proper estimate of uncertainty in measurement.     

Estimation of sampling uncertainty for determination of pesticide residues in plant commodities

In order to provide residue data for refining the estimated sampling uncertainty, a coordinated research program was initiated for performing field studies on residues in individual items of leafy vegetables, small and large crops. The trials were carried out in 13 countries with 3 small fruits, 5 large crops, 2 medium/large crops and 3 leafy vegetables. The 25 pesticide active ingredients applied represented the dicarboximide (3), organophosphorus (8), synthetic pyrethroids (5), phthalimides (2), organochlorine (1) and other types of pesticides (6). In addition, 11 supervised field trials were performed in grapes and lettuce by the pesticide manufacturers, and their results were provided for evaluation. The studies represented actual agriculture practice around the world, and provide reliable data for estimation of sampling uncertainty. Based on the 12346 residue data, the best estimate for the relative sampling uncertainty for composite samples, assuming sample size of 10 for small crops and leafy vegetables and 5 for large crops, with 95% confidence limits in brackets are: small commodities: 0.25 (0.20–0.29); Brassica leafy vegetables: 0.20 (0.16–0.24); large commodities: 0.33 (0.29–0.38).     

Gran's titrations: Inherent errors in measuring the acidity of precipitation

Gran's titrations are commonly used to differentiate strong and weak acidity in precipitation. However, in the course of such titrations, dissociation of the weak organic acids found in precipitation causes overestimates of both strong and free acidity. In addition, the reaction of NH₄⁺ with OH⁻ in the alkaline range of titrations causes overestimates of total acidity. Because of these effects, Gran's technique and related modifications have limited usefulness in characterizing the acidity of precipitation.     

The potential of diffuse reflectance spectroscopy for the determination of carbon inventories in soils

Investigations have shown that near- and mid-infrared reflectance spectroscopy can accurately determine organic-C in soil. Efforts have also demonstrated that both can differentiate between organic and inorganic-C in soils, but the mid-infrared produces more accurate calibrations. Nevertheless, the greatest benefit would come with in situ determinations where factors such as particle size, sample heterogeneity and moisture can be important. While the variations in large (> 20 mesh) particle size can adversely effect calibration accuracy, efforts have demonstrated that the scanning of larger amounts of sample can overcome this, but the effects of moisture have not been fully explored. While under in situ conditions C distribution and sample heterogeneity are a problem for any analytical method, the rapid analysis possible with spectroscopic techniques will allow many more samples to be analyzed. In conclusion, near- and mid-infrared spectroscopy have great potential for providing the C values needed for C sequestration studies.     

An application and review of the critical load concept to the soils of northern England

In common with other member states of UN-ECE, maps of critical loads of transboundary air pollutants are to be produced in the UK for different receptor (waters, soils and vegetation) types. These maps will be used as a tool for assessing different deposition scenarios with proposed pollution abatement strategies. This paper presents the methodology, results and a discussion of the principles used in applying critical loads of sulphur as a pilot study for soils in northern England. For the study area, critical load classes for soils vary with geology, drift cover and slope/elevation. The area of soils in which the critical load is exceeded varies significantly according to the type of deposition data utilised.