Speciation and hydrological transport of metals in non-acidic river systems of the Lake Baikal basin: Field data and model predictions

The speciation of metals in aqueous systems is central to understanding their mobility, bioavailability, toxicity and fate. Although several geochemical speciation models exist for metals, the equilibrium conditions assumed by many of them may not prevail in field-scale hydrological systems with flowing water. Furthermore, the dominant processes and/or process rates in non-acidic systems might differ from well-studied acidic systems. We here aim to increase knowledge on geochemical processes controlling speciation and transport of metals under non-acidic river conditions. Specifically, we evaluate the predictive capacity of a speciation model to novel measurements of multiple metals and their partitioning, under high-pH conditions in mining zones within the Lake Baikal basin. The mining zones are potential hotspots for increasing metal loads to downstream river systems. Metals released from such upstream regions may be transported all the way to Lake Baikal, where increasing metal contamination of sediments and biota has been reported. Our results show clear agreement between speciation predictions and field measurements of Fe, V, Pb and Zn, suggesting that the partitioning of these metals mainly was governed by equilibrium geochemistry under the studied conditions. Systematic over-predictions of dissolved Cr, Cu and Mo by the model were observed, which might be corrected by improving the adsorption database for hydroxyapatite because that mineral likely controls the solubility of these metals. Additionally, metal complexation by dissolved organic matter is a key parameter that needs continued monitoring in the Lake Baikal basin because dependable predictions could not be made without considering its variability. Finally, our investigation indicates that further model development is needed for accurate As speciation predictions under non-acidic conditions, which is crucial for improved health risk assessments on this contaminant.

     

The effect of complex formation on the adsorption characteristics of heavy metals

In most aqueous environmental systems, inorganic and organic metal complexes represent a significant contribution to the total soluble metal. Metal adsorption is often a highly pH-dependent phenomena. Such behavior can generally be attributed to changes in metal speciation with solution acidity as well as variation in the extent of surface protonation. Thus, because adsorbability may vary drastically between different metal species, (e.g. Cu²⁺ (aq) compared to CuOH⁺) a knowledge of metal species distribution is essential to understanding and interpreting metal adsorption behavior.Organic complexation has been reported to enhance, suppress and have no perceptible effect on trace metal adsorption. Such differences arise because adsorption depends on factors such as the ligand/metal ratio, adsorbability of the free ligand, and various solution parameters (e.g. pH). Most important in determining the effect of complexation on adsorption is the adsorbability of the resulting complexes. Thus, it is difficult to make generalizations about the influence of organic complexation on metal adsorption.Adsorption of metal complexes is frequently reported to be predominantly coulombic in nature; that is, binding of an anionic or cationic complex to an oppositely charged colloidal particle. However, electrostatic forces can often represent an insignificant contribution to the total free energy of adsorption and can be overshadowed by chemical reactions with the surface, hydrogen bonding, and hydrophobic effects.     

Distribution of tritium in estuarine waters: the role of organic matter

Tritium is an important environmental radionuclide whose reactivity with ligands and solids in aquatic systems is assumed to be limited. We studied the fractionation and sorption of tritium (added as tritiated water) in river water and seawater, and found that its distribution appears to be influenced by its affinity for organic matter. Tritium rapidly equilibrates with dissolved organic ligands that are retained by a reverse-phase C18 column, and with suspended sediment particles. Significantly, a measurable fraction of sorbed tritium associates with proteinaceous material that is potentially available to sediment-feeding organisms. These characteristics have not been reported previously and cannot be accounted for solely by isotopic exchange with hydrogen. Nevertheless, they are in qualitative agreement with available measurements of tritium in estuarine and coastal waters where its principal discharge is as tritiated water. Further research into the estuarine biogeochemical behaviour of tritium is required and radiological distribution coefficients and concentration factors that are assumed for this radionuclide may require reconsideration.     

Aquatic arsenic: Toxicity,speciation, transformations,and remediation

This paper reviews the current knowledge on the toxicity, speciation and biogeochemistry of arsenic in aquatic environmental systems. The toxicity of arsenic is highly dependent on the chemical speciation. The effects of pH, E_h, adsorbing surfaces, biological mediation, organic matter, and key inorganic substances such as sulfide and phosphate combine in a complex and interwoven dynamic fashion to produce unique assemblages of arsenic species. The number of different arsenic species found in environmental samples and an understanding of the transformations between arsenic species has increased over the past few decades as a result of new and refined analytical methods. Changes in arsenic speciation and in total arsenic content of foods upon processing have suggested possible risks associated with processed and unprocessed food. Arsenic removal from water using adsorbents, chemical oxidation, photolysis and photocatalytic oxidation techniques is also reviewed.     

Comparison of laboratory uranium sorption data with 'in situ distribution coefficients' at the Koongarra uranium deposit, Northern Australia

Distribution coefficients derived from laboratory sorption experiments are commonly used to model the migration of long-lived radionuclides in the environment. However, it has been suggested that field measurements in natural systems ('in situ distribution coefficients') may provide a more accurate indication of 'true' partitioning coefficients than laboratory experiments. In this paper, the relationship between field and laboratory sorption data for uranium is evaluated, using data from the Koongarra uranium deposit in Northern Australia. An extensive suite of laboratory sorption measurements and in situ partitioning data for U has been obtained at this site. A valid comparison can only be made when the calculation of field partitioning is based on U in 'accessible' phases (rather than total U in the solid) and U species in true solution (i.e. excluding particles). In this study, accessible U was estimated using a chemical extraction and the results were verified using an isotope exchange technique. A satisfactory correspondence between field and laboratory partitioning data was obtained when the pH values and partial pressures of CO2 in laboratory sorption experiments were similar to those found in the field. Under these conditions, the measured laboratory sorption ratios (Rd) and in-field partitioning values (Pacc) for U at Koongarra were in the range between approximately 1 x 10(3) and 2 x 10(4) ml/g. However, the distribution of U in solid and groundwater phases at Koongarra is extremely heterogeneous. This variability must be taken into account when modelling radionuclide migration at this site.     

Combined toxicity of copper and phenol derivatives to Daphnia magna: effect of complexation reaction

The complexation of Cu with phenol was investigated in aqueous solution to find the changes in toxicity toward Daphnia magna in mixtures of copper and phenol derivatives and determine an appropriate prediction model for the toxicity of these mixtures. In the titration experiment, the results showed that phenol played an important role in the remarkable reduction of the Cu(2+) concentration, due to its complexation with Cu, with the subsequent reduction in the toxicity of aqueous mixtures containing both Cu and phenol. As a result, it was clearly demonstrated that Cu-phenol formed a non-toxic complex toward D. magna as the mortality declined, despite the addition of phenol to a fixed Cu concentration. Meanwhile, prediction of the combined toxicity for binary mixtures of Cu and 11 phenol derivatives more accurately followed an independent action model (p = 0.143, df = 124, and t = -1.475 in t-test) than an effect summation model (p approximately 0, df = 134, and t = 7.528 in t-test) due to the dissimilar modes of action and the complexation reactions between Cu and each of the phenolic compounds. Consequently, this study supports the importance of considering complexation reactions in assessing the combined toxicity for the formulation of water quality in mixtures of heavy metals and organic compounds, and in these cases, an independent action model was found to be appropriate.     

Toxic risk of surface water pollution--six years of experience

Assessment of an ecological quality of surface water is necessary for effective protection, abatement and successive revitalisation of river ecosystems. This quality is primarily given by biological impact of surface water pollution. Substances contained in pollution are frequently toxic to aquatic organisms. Risk of chronic impact of surface water pollution is very often underestimated due to hidden long time action of pollutants. Proper estimation of the risk is not possible from results of chemical analyses and data of substances' toxicity. Chemical analyses are not able to detect all substances presented in water including the products of reactions between them. In addition, a simultaneous presence of substances can modify their final effect on aquatic organisms. Therefore, a complex method of assessment of toxic risk of surface water pollution based on ecotoxicological approach was developed. The toxic risk of surface water pollution is determined from results of evaluation of toxic risk of organic part and inorganic part of surface water pollution. Resultant degree of toxic risk of total pollution is given by the highest degree detected in any part of the water pollution. Presented method, which is routinely used for monitoring in the Czech part of the Odra river basin, was fully standardised and published in the form of the Czech branch technical norm of water management (TNV) in the year 2000.     

Health risks from large-scale water pollution: trends in Central Asia

Limited data on the pollution status of spatially extensive water systems constrain health-risk assessments at basin-scales. Using a recipient measurement approach in a terminal water body, we show that agricultural and industrial pollutants in groundwater-surface water systems of the Aral Sea Drainage Basin (covering the main part of Central Asia) yield cumulative health hazards above guideline values in downstream surface waters, due to high concentrations of copper, arsenic, nitrite, and to certain extent dichlorodiphenyltrichloroethane (DDT). Considering these high-impact contaminants, we furthermore perform trend analyses of their upstream spatial-temporal distribution, investigating dominant large-scale spreading mechanisms. The ratio between parent DDT and its degradation products showed that discharges into or depositions onto surface waters are likely to be recent or ongoing. In river water, copper concentrations peak during the spring season, after thawing and snow melt. High spatial variability of arsenic concentrations in river water could reflect its local presence in the top soil of nearby agricultural fields. Overall, groundwaters were associated with much higher health risks than surface waters. Health risks can therefore increase considerably, if the downstream population must switch to groundwater-based drinking water supplies during surface water shortage. Arid regions are generally vulnerable to this problem due to ongoing irrigation expansion and climate changes.     

气候变化对涟水流域蓝水绿水资源的影响

利用SWAT分布式水文模型模拟分析1996~2015年过去20 a及2020~2079年未来60 a长期气候变化背景下涟水流域蓝水绿水资源的时空分布变化特征。将气候变化划分为1996~2015年、2020~2049年、2050~2079年三段气象背景时期,选用Had GEM2-AO大气模式的RCP2.6、RCP4.5、RCP6、RCP8.5四种典型浓度路径作为未来时期的气象输入条件,并细分为9种气候变化情景。运用PSO粒子群优化算法,以KGE克林效率系数为目标函数,采用湘乡站实测径流量及MOD16蒸散发数据并行校准模型参数,通过p-factor、r-factor、R2、NSE和PBIAS评价模型模拟效果和不确定性,评价结果表明校准期及验证期蓝水绿水模拟均达到可信程度。情景分析结果表明,对比1996~2015年、2020~2049年、2050~2079年三段气候背景时期,在各RCP浓度路径下蓝水均呈现了不同程度的下降趋势,大约降低了1.4%~17.3%,绿水流均表现出一定的上升趋势,约增长3.5%~12.4%,绿水蓄量则在持续降低,大致下降了7.8%~19.7%,即使将95PPU模拟不确定性范围考虑进来,绿水流的增长趋势也较为明显。因此,将绿水资源纳入涟水流域未来水资源评价体系,实现蓝水绿水综合规划管理具有实际意义。     

Behavior of a surface applied radionuclide and a dye tracer in structured and repacked soil monoliths

There has been increasing evidence in recent years about the impact of soil structure on vadose zone hydrology and the distribution of surface applied chemical substances. We have carried out a combined dye and radionuclide tracer study on two monoliths from the same location, one structured and one repacked, as part of an ongoing study to investigate the link between preferential flow, leaching of surface applied substances and their distribution within the soil.A tracer solution containing 1300 Bq/L (58)Co and 0.31 micromol/L Sulforhodamine B (SB) was added with roughly constant irrigation during a period of three weeks. The dye served as a tracer for water movement within the soil and thus allowed linkage of the radiotracer ((58)Co) with the flow pattern. Both were monitored in the outflow and measured within profile sections after monolith disassembly. Preferential flow in the structured monolith promoted the bypass and transport of both tracers, although transport was impeded at depths greater than 30 cm by compacted soil and reduced hydraulic conductivity. Eighty four percent of radiocobalt and 8% of SB were found in the upper 4 cm of the structured monolith. The homogenized monolith, on the other hand, showed mostly chromatographic infiltration and a more efficient soil filtering capacity with 91% of radiocobalt and 20% SB residing in the upper 4 cm. Furthermore no tracer was found in the outflow of the homogenized monolith during normal to high irrigation or at greater depth within the monolith. We have related flow characteristics and sorption of radiotracers by quantifying dye distributions and radionuclide activities throughout the profiles. Activities within the flow paths are up to 20-times higher than those measured in the soil matrix, and a fraction of radiocobalt follows the dye tracer in spite of cobalt's low mobility. The dye can thus be used to trace radionuclide distribution within the soil block.     

An evaluation of a river health using the index of biological integrity along with relations to chemical and habitat conditions

We evaluated the health condition of a temperate river during June-November 1999 through applications of the index of biological integrity (IBI) using fish assemblages and qualitative habitat evaluation index (QHEI) as well as chemical analyses. Overall IBI values ranged from 13 to 37 and averaged 23 (n = 25, standard error = 1.16), indicating a "poor" or "very poor" condition according to the criteria of modified Karr [Fisheries 6 (1981) 21]. The values of mean IBI declined at a rate of 0.22 km(-1) (R2 = 0.91, p < 0.05) along the longitudinal distance from the headwaters to the downstream sites. Reduced IBI values at downstream sites reflected low forest cover, high population density and high nutrient enrichments. Ecotoxicity tests using the river water also showed that toxic impacts were evident in the downriver sites. These factors resulted in decreases of riffle benthic species and insectivores and increases of tolerant species, anormalies and exotic species in the river. Spatial pattern in IBI agreed with QHEI values, which showed a linear relation (R2 = 0.998, p < 0.001) with species richness. Field measurements of conductivity and pH, an indicators for variation of conservative ions, showed that the river water was diluted by 40% fold by summer monsoon rain and surface run-off from the watershed, resulting in a physical and chemical instability during the monsoon. For these reasons, average IBI values during the monsoon and postmonsoon decreased >20% compared to the premonsoon, indicating that IBI values were also affected by flow regime. Based on the overall physico-chemical data and IBI values, the river health is rapidly degrading due to the combined effect of chemical contaminations and habitat modifications.     

丰乐河流域表层土壤有机碳空间变异特征研究

土壤有机碳含量空间变异特征的研究对于区域土壤资源的可持续利用具有重要意义。在ArcGIS技术的支持下对丰乐河流域表层土壤(0~20 cm)有机碳（SOC）含量的空间变异特征进行了研究。结果表明：丰乐河流域SOC含量为1431±4.50 g·kg-1,不同土地利用类型下SOC含量差异显著（p<001）。其中,林地SOC含量的均值最大,为1558±593 g·kg-1;水田和旱地次之（分别为1539±309 g·kg-1、1146±304 g·kg-1）;园地最小(1109±348 g·kg-1)。流域SOC含量变异系数（CV）为3144%,属中等变异程度。其中,林地的CV为3806%,在4种土地利用类型中为最大;园地、旱地的CV分别为3138%、2652%;水田的CV最小,为2007%,表明人类活动影响表层土壤有机碳含量的变异程度。研究区表层SOC半方差模型为球状模型,块金效应小于25%,存在强烈的空间自相关性,且空间变异主要由结构性因素引起。SOC含量空间分布的各向异性显著,在南北方向上变异程度最为剧烈。SOC含量空间分布表现为东北部、西南部较高,西北部偏低,总体呈斑块状分布     

Novel approach for assessing heavy metal pollution and ecotoxicological status of rivers by means of passive sampling methods

In order to study the pollution of fluvial ecosystems, it is necessary to analyze not only the levels of chemical contaminants in water, but also those accumulated in the sediment matrix, as well as to assess its ecotoxicological status. Eleven Catalan (Spain) river sections (one sampling point per river) located near urban and industrial areas were sampled during winter of 2009. Water pollutants were collected by using passive samplers as Diffusive Gradient in Thin-Films (DGTs) and Semi-Permeable Membrane Devices (SPMDs). Point water samples were also collected. The concentrations of potentially toxic elements (PTE) in water, filtered water, DGTs and sediment samples were analyzed. Aqueous and organic solvent extracts of sediments samples and organic extracts of SPMDs were performed to assess acute toxicity to Vibrio fischeri by Microtox(?), and chronic toxicity to the green alga Pseudokirschneriella subcapitata. Microtox(?) test was also performed with DGT extracts. The results show that metals content of Catalan river waters are below the freshwater screening US EPA benchmarks, excepting some industrial areas (for Hg, Pb, and Zn). In contrast, sediments levels of some rivers were far above freshwater sediment screening US EPA benchmarks (for Zn, As, Cr, Pb, Ni, Hg, and Mn), particularly in the most industrialized areas. A good correlation was found between toxicity values of extracts (from sediments and DGTs) and PTE levels in sediments. The current results support the suitability of using combined point and passive sampling methods for assessing the chemical and ecotoxicological status of aqueous environments.     

Chemical contamination of the East River (Dongjiang) and its implication on sustainable development in the Pearl River Delta

A recent survey reveals that water quality and river sediments of Dongjiang (the East River) have been mildly contaminated by heavy metals and organic chemicals, such as copper, lead, PCBs, PAHs and HCHs. According to photogrammertic surveys, the sources of contamination are closely related to human activities, such as domestic and industrial discharges, agricultural chemical applications and soil erosion due to deforestation. The level of water and sediment contamination is most serious at the mid-river section near the urban of Weizhou. Due to natural dilution and diffusion, the levels of contamination are slightly decreased at the medium low section of the River near Qiaotou and Matan. Nevertheless, the levels of contamination increase again in the lower river section near Shenzhen, which is a highly developed economic zone. Since Dongjiang is the major source of potable water supply for Hong Kong (nearly 80% of potable water of Hong Kong is abstracted from Dongjiang) and the other parts of the Pearl River Delta (PRD), such organic and inorganic pollution merit concern. Ironically, most of the industrial and commercial activities in the watershed of Dongjiang are business investments of Hong Kong citizens. Cross-border environmental efforts should be enhanced with collaboration of different jurisdictions to achieve targets of regional sustainability.     

Environmental risk assessment of metals: tools for incorporating bioavailability

In this paper, some of the main processes and parameters which affect metal bioavailability and toxicity in the aquatic environment and its implications for metal risk assessment procedures will be discussed. It has become clear that, besides chemical processes (speciation, complexation), attention should also be given to physiological aspects for predicting metal toxicity. The development of biotic ligand models (BLMs), which combine speciation models with more biologically oriented models (e.g. GSIM), has offered an answer to this need. The various BLMs which have been developed and/or refined for a number of metals (e.g. Cu, Ag, Zn) and species (algae, crustaceans, fish) are discussed here. Finally, the potential of the BLM approach is illustrated through a theoretical exercise in which chronic zinc toxicity to Daphnia magna is predicted in three regions, taking the physico-chemical characteristics of these areas into account.     

HEC RAS模型在汉江上游郧县尚家河段全新世古洪水流量重建中的应用

以汉江上游郧县尚家河段含有4期全新世古洪水事件的沉积剖面为例,采用HEC RAS模型计算出这4期最大古洪水最大洪峰流量为45 550~61 750 m3/s,与比降法重建的古洪水洪峰流量结果相比,误差为158%~309%。同时,采用相同水文参数和模型,计算了剖面附近的2010年7月18日洪痕洪峰流量,与实测流量相比,误差为491%,说明重建古洪水洪峰流量时水文参数选择与洪峰流量计算结果是合理的,同时也表明利用HEC RAS模型在重建古洪水流量中简捷,可操作性强,其研究结果为古洪水水文学研究提供一种新的方法     

鄱阳湖生态区长期施肥对稻田土壤碳汇效应与固碳潜力的影响

在施肥条件下确定平衡状态时,土壤有机碳含量水平对于正确评价土壤的固碳潜力和制定合理的有机物质分配措施具有重要意义。分析了前人研究的江西省有机碳储量数据并采用Jenny模型对长期不同施肥下有机碳动态数据进行模拟。结果表明,鄱阳湖生态区有机碳储量占全省的46%,以鹰潭地区最高,九江地区最低。施肥明显增强了土壤的碳汇作用,单施有机肥或有机无机肥配施（70F+30M、50F+50M、30F+70M、NPKM、NPK+S、NPK+P和NPK+C）处理的土壤有机碳含量明显高于施化肥处理,以南昌县的30F+70M、进贤县的NPKM和余江县的NPK+P处理最高,其平衡时有机碳含量和固碳潜力分别较施化肥处理提高了3061%和6115%、3017%和5496%、3826%和7479%。因此,提高鄱阳湖生态区农田有机碳密度和固碳潜力最有效方法是有机无机肥配施,其配施方式以猪粪配施化肥相对最好,配施比例以70%有机肥配施30%化肥为宜     

Estrogen-, androgen- and aryl hydrocarbon receptor mediated activities in passive and composite samples from municipal waste and surface waters

Passive and composite sampling in combination with in vitro bioassays and identification and quantification of individual chemicals were applied to characterize pollution by compounds with several specific modes of action in urban area in the basin of two rivers, with 400,000 inhabitants and a variety of industrial activities. Two types of passive samplers, semipermeable membrane devices (SPMD) for hydrophobic contaminants and polar organic chemical integrative samplers (POCIS) for polar compounds such as pesticides and pharmaceuticals, were used to sample wastewater treatment plant (WWTP) influent and effluent as well as rivers upstream and downstream of the urban complex and the WWTP. Compounds with endocrine disruptive potency were detected in river water and WWTP influent and effluent. Year-round, monthly assessment of waste waters by bioassays documented estrogenic, androgenic and dioxin-like potency as well as cytotoxicity in influent waters of the WWTP and allowed characterization of seasonal variability of these biological potentials in waste waters. The WWTP effectively removed cytotoxic compounds, xenoestrogens and xenoandrogens. There was significant variability in treatment efficiency of dioxin-like potency. The study indicates that the WWTP, despite its up-to-date technology, can contribute endocrine disrupting compounds to the river. Riverine samples exhibited dioxin-like, antiestrogenic and antiandrogenic potencies. The study design enabled characterization of effects of the urban complex and the WWTP on the river. Concentrations of PAHs and contaminants and specific biological potencies sampled by POCIS decreased as a function of distance from the city.     

Nutrient chemistry of River Pinios (Thessalia, Greece)

The impact of human activities with 3-year monitoring on the fluctuation of nutrients along the Pinios River and its tributaries were studied. Their seasonal variations throughout the years 1996-1998 were also presented. High temperatures, from June to August, cause a restriction of the water flow, an enhancement of nutrient concentration with the subsequent increase of eutrophication. High concentrations of nutrients were observed first in winter (wet period), caused by leaching of fertilizers from terrestrial systems after heavy rainfall, later during the warm months due to low water flow of the river, and at last in autumn when plant organisms began to decompose. The intensive algal and macrophyte growth (spring, summer) resulted in severe depletion of nutrients. Organic carbon showed no seasonal trend but its values were high near the estuaries. Nitrate fluxes were high at the initial station (sources) and the Titarisios tributary, whereas nitrites and ammonium were low. In contrary, the Kalentzis tributary with relatively low nitrate values showed increased values of nitrite ammonium or total nitrogen. On the other hand, the Enipeas tributary showed high SO4 values. Phosphates are remarkably present mainly after the city of Larissa, where sewage and industrial discharges occur. None of the nutrients measured in the Pinios River and its tributaries showed a clear seasonal cycle of concentration. Concentrations of nutrients and organic carbon increased as a consequence of anthropogenic inputs, particularly point discharges from sewage treatment plants (i.e. showing distinct, but variable, concentration peaks), as well as diffuse urban and/or agricultural runoff over long areas during storm events. The agricultural management, the urban pollution, mainly from Larissa City, and the climate conditions in the catchment basin (Thessalia Plain) of Pinios River and its tributaries greatly affect the chemical composition of their waters.     

Speciation and surface structure of inorganic arsenic in solid phases: a review

Accurate determination of individual arsenic species is critical because the toxicology, mobility, and adsorptivity of arsenic vary substantially with its chemical forms and oxidation states. Separation techniques together with techniques for chemical identification make it possible to determine the combinational forms and oxidation states of arsenic in solid phases. Selective sequential extraction is often employed to determine operationally defined fractions, but it has a poor precision and selectivity. Direct methods, based on X-ray techniques and vibrational spectroscopy, have been developed to analyze the valence, local coordination, protonation, and other properties of arsenic in solid phases. Extensive research studies in the literature have been performed to elucidate the interfacial reactions between inorganic arsenic and solid surfaces of sulfides, and Fe, Al, and Mn (hydro)oxides. Outer-sphere and inner-sphere complex (monodentate mononuclear, bidentate mononuclear, and bidentate binuclear complex) models have been proposed to interpret the sorption mechanisms. The nature of the surface complexes has been inspected by spectroscopic methods but remains controversial. This paper focuses on the recent advancement in arsenic speciation in solid phases and covers relevant methodological, analytical and modeling aspects. The identification of arsenic species in natural materials, however, is complicated by the presence of multiple species, and the applications of instrumental methods are usually limited due to their comparatively high detection limits. Development of advanced in-situ methods with high sensitivity, therefore, is required.