Formation of aerobic granules in the presence of a synthetic chelating agent

This paper examines the development of aerobic granular sludge in the presence of a synthetic chelating agent, nitrilotriacetic acid (NTA), in sequencing batch reactors (SBR). The growth of seed sludge at 0.26 mM, 0.52 mM and 1.05 mM of NTA was found to be significantly lower as compared to that in the absence of NTA. Aerobic granulation was significantly enhanced in the three SBRs (R2, R3 and R4), which were fed with 0.26 mM, 0.52 mM and 1.05 mM of NTA as a co-substrate, in comparison to the acetate-alone fed SBR (R1). After 2 months of operation, the mean diameter of the biomass stabilized at 0.35 mm in R1 (acetate alone), as compared to 2.18 mm in R4 (1.05 mM NTA+acetate). NTA degradation was established in SBRs, with almost complete removal during the SBR cycle. Batch experiments also showed efficient degradation of NTA by the aerobic granules.     

Phytoextraction of metals from a multiply contaminated soil by Indian mustard

The effects of nitrilotriacetate (NTA) and citric acid applications on metal extractability from a multiply metal-contaminated soil, as well as on their uptake and accumulation by Indian mustard (Brassica juncea) were investigated. Desorption of metals from the soil increased with chelate concentration, NTA being more effective than citric acid in solubilising the metals. Plants were grown in a sandy soil collected from a contaminated field site and polluted by Cd, Cr, Cu, Pb and Zn. After 43 days of plant growth, pots were amended with NTA or citric acid at 5 mmol kg-1 soil. Control pots were not treated with any chelate. Harvest of plants was performed 1 week after chelate addition. Soil water-, NH4NO3- and DTPA-extractable Cd, Cu, Pb and Zn fractions were enhanced only in the presence of NTA. In comparison to unamended plants, Indian mustard shoot dry weights suffered significant reductions following NTA application. NTA treatment increased shoot metal concentrations by a factor of 2-3, whereas citric acid did not induce any difference compared to the control. Chromium was detected in the above-ground tissues only after NTA amendment. Due to differences in dry matter yield, a significant enhancement of metal uptake was observed in NTA-treated plants for Cu and Zn.     

pH-Dependent fate and transport of NTA-complexed cobalt through undisturbed cores of fractured shale saprolite

The codisposal of toxic metals and radionuclides with organic chelating agents has been implicated in the facilitated transport of the inorganic contaminants away from primary waste disposal areas. We investigated the transport of Co(II)NTA through undisturbed cores of fractured shale saprolite. Experiments were conducted across the pH range 4 to 8 by collecting cores from different locations within the weathering profile. Aqueous complexation, adsorption, dissociation and oxidation reactions influenced Co(II)NTA transport. The suite of reaction products identified in column effluent varied with experimental pH. At low pH and in the presence of abundant exchangeable aluminum, Co transport occurred predominantly as the Co2+ ion. At higher pH, Co was transported primarily as Co(II)NTA and the Co(III) species Co(III)(HNTA)2 and Co(III)(IDA)2. The formation of the geochemical oxidation products (Co(III) species) has far reaching implications as these compounds are kinetically and thermodynamically stable, are transported more rapidly than Co(II)NTA, and are resistant to biodegradation. These results demonstrate that natural minerals, in the physical structure encountered naturally, can be more important in the formation of mobile, stable contaminant forms than they can be for the retardation and dissociation of the contaminants.     

Nitrilotriacetate- and citric acid-assisted phytoextraction of cadmium by Indian mustard (Brassica juncea (L.) Czernj, Brassicaceae)

In a pot experiment the effects of nitrilotriacetate (NTA) and citric acid applications on Cd extractibility from soil as well as on its uptake and accumulation by Indian mustard (Brassica juncea) were investigated. Plants were grown in a sandy soil with added CdS at four levels ranging from 50 to 200 mg Cd kg(-1) soil. After 30 days of growth, pots were amended with NTA or citric acid at 10 and 20 mmol kg(-1). Control pots were not treated with chelates. Harvest of plants was performed immediately before and one week after chelate addition. Soil water-, NH(4)NO(3)- and EDTA-extractable Cd fractions increased constantly with both increasing soil metal application and chelate concentration. Shoot dry weights did not suffer significant reductions with increasing Cd addition to the soil except for both NTA treatments in which at 200 mg Cd kg(-1) a 30% decrease in dry matter was observed. Generally, following NTA and citric acid amendments, Cd concentration in shoots increased with soil Cd level. However, due to Cd toxicity, at the highest metal application rate both NTA treatments lowered Cd concentration in the above-ground parts. Compared to the control, at 10 mmol kg(-1) citric acid did not change Cd concentration in shoots, whereas NTA-treated plants showed an about 2-fold increase. The addition of chelates at 20 mmol kg(-1) further enhanced Cd concentration in shoots up to 718 and 560 microg g(-1) dry weight in the NTA and citrate treatments, respectively.     

Sequential extraction analysis of heavy metals in sediments of variable composition using nitrilotriacetic acid to counteract resorption

Artificial sediments were made that contained variable amounts (up to 20% by weight) of feldspar, calcite, Fe-oxide or organic matter. Analysis of samples spiked with Pb and Zn in the presence and absence of nitrilotriacetic acid (NTA) showed that 400 mg l(-1) of chelating agent greatly reduced or eliminated sorption in each case. Further study showed that this NTA concentration did not cause significant mineral dissolution. Resorption during sequential extraction analysis of artificial sediments is indicated by the fact that with NTA, levels of metals are higher in the first step and lower during subsequent steps, compared with levels obtained without NTA. However, the addition of 400 mg l(-1) of NTA to each extracting solution in the sequence appears to be effective for counteracting resorption in feldspathic, calcareous, ferruginous and carbonaceous sediments.     

The use of NTA and EDDS for enhanced phytoextraction of metals from a multiply contaminated soil by Brassica carinata

The potential of nine different species to grow in the presence of metals (As, Cd, Cu, Pb and Zn) and to accumulate them in the shoots was assessed for each metal separately by germination and root length tests, and successively by hydroponic experiments. Of the nine species tested, Brassica carinata was the species that accumulated the highest amounts of metals in shoots without suffering a significant biomass reduction. To further evaluate the potential of B. carinata for chelant-enhanced phytoextraction of a natural, multiply metal-polluted soil (As, Cd, Cu, Pb and Zn), both hydroponic and pot experiments were carried out with nitrilotriacetic acid (NTA) or (S,S)-ethylenediamine disuccinic acid (EDDS) as complexing agents. The hydroponic study with solutions containing the five metals together showed that accumulation of Cd, Cu, Pb and Zn in shoots was higher following EDDS addition compared to NTA. EDDS was more effective than NTA in desorbing Cu, Pb and Zn from the soil, whereas As and Cd were poorly extracted. B. carinata plants were grown for 4 weeks in the multiply metal-contaminated soil and then the soil was amended with 5 mmol kg(-1) NTA or EDDS. All plants were harvested 1 week after amendment. In comparison to NTA, EDDS was more effective in enhancing the concentrations of Cu, Pb and Zn in B. carinata shoots (2- to 4-fold increase compared to the control). One week after chelant addition, the DTPA-extractable metal concentrations in the polluted soil were lower in the EDDS treatment in comparison with the NTA amendment. Even though B. carinata showed a reduced growth and a relatively low metal uptake, it demonstrated the ability to survive and tolerate the presence of more metals simultaneously.     

Environmental chemicals and biomembranes 1. Nitrilotriacetic acid

Nitrilotriacetic acid (NTA) is readily taken up by yeast cells through simple diffusion and is metabolized. Concentrations of NTA in the millimolar range do not interfere with various membrane functions of yeast and bacteria.     

Polyelectrolyte enhanced ultrafiltration (PEUF) for the removal of Cd(II): effects of organic ligands and solution pH

This study focused on the effects of pH and organic ligands, namely ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and citric acids, on the removal and recovery of Cd(II) in polyelectrolyte enhanced ultrafiltration (PEUF). Polyethylenimine (PEI), which can bind with both positively charged metal ions by coordination bonding and negatively charged ligand-metal complexes by charge attraction, was employed as a chelating polymer. The removal and recovery of Cd species was greatly dependent on the chemistry of organic ligands according to solution pH, particularly being related to the distribution of Cd-ligand complexes at different pH levels. In the presence of EDTA, the dominant Cd species are negatively charged Cd(EDTA)(2-) and CdH(EDTA)(-) over the range of pH levels investigated, interacting with PEI via electrostatic attraction and being less pH dependent. On the other hand, the pH effects of both NTA and citric acid systems are similar to that for the system without organic ligands. This was associated with the fact that free Cd ions were predominant at the acidic pH range in both NTA and citric acid systems.     

An evaluation of the green chelant EDDS to enhance the stability of hydrogen peroxide in the presence of aquifer solids

Hydrogen peroxide is a widely used in situ chemical oxidation reagent which relies on catalysts to generate the suite of reactive species that are required to aggressively remediate contaminated soils and groundwater. In the subsurface environment these catalysts are usually transition metals that are added to the injected solution, or are naturally occurring. Chelating agents are widely used to maintain an adequate dissolved transition metal concentration in near-neutral pH conditions; however, they can also be used to improve the persistence of H(2)O(2) in situations when the aquifer solids have sufficient transition metal content. Ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) have been considered to be the most effective chelants and therefore are the most widely used. While previous research efforts have focused on the chelating agent efficiency, the long-term fate of these chelants in the natural subsurface environment is a concern since both EDTA and NTA are non-readily biodegradable. The focus of this investigation was to evaluate the potential of using the environmentally friendly or green chelating agent ethylenediaminedisuccinate (EDDS) as an alternative to EDTA or NTA to suppress the catalytic activity of naturally-occurring transition metals. A series of batch reactor and column experiments were performed using five different aquifer materials and the results demonstrate that EDDS has a comparative chelating efficiency to that of EDTA. The addition of EDDS was able to reduce the H(2)O(2) decomposition rates in the presence of the aquifer materials used in this investigation by 24-97% in well-mixed batch systems, and by 20% and 38% in the column trials where H(2)O(2) was detected in the effluent.     

Sequential extraction analysis of heavy metals using a chelating agent (NTA) to counteract resorption

The geochemical partitioning of Pb, Ni and Zn in contaminated quartz-rich sediment and soil samples was characterized by sequential extraction analysis in the presence and absence of nitrilotriacetic acid (NTA). With NTA, levels of metals recovered are higher in the earlier steps and lower in the later steps of the procedure. This suggests that post-extraction resorption is effectively counteracted by chelation, thereby improving the accuracy of the method. An NTA concentration of 200 mg liter(-1) appears to be sufficient for counteracting resorption without causing significant dissolution of non-targeted phases in the samples studied. However, experiments using reference materials spiked with solutions containing Pb, Ni, Cu and Zn suggest that resorption will remain a problem when large amounts of strong sorbents such as organic matter are present. The results also show that although post-extraction resorption does occur in the absence of NTA, the magnitude of resorption is small (<20 to 30% of the summed total of metal present in the sample) in quartz-rich sediments.     

Influence of sodium nitrilotriacetate (NTA) and citric acid on phenolic and organic acids in Brassica juncea grown in excess of cadmium

Brassica juncea cv. 426308 was grown in soils containing 150 mg Cd(2+)kg(-1) soil. After 38 days, the soil was amended with two rates of citric acid or NTA (10 and 20 mmol kg(-1) soil). Control soil was not amended with chelates. Plants were harvested during growth, immediately before and seven days after chelate addition. Shoot composition of organic and phenolic acids and shoot Cd(2+) concentration were determined. Cadmium concentration remained constant during the growth and increased following NTA and citric acid amendments depending on chelate type and concentration. The highest increments in Cd(2+) were measured after the addition of NTA. Compared to the control, 10 and 20 NTA-treated plants showed two- and three-fold increases, respectively. At 150 mg Cd(2+)kg(-1) soil the amount of organic and phenolic acids in the leaves of B. juncea was always higher than that detected in the control. A direct correlation between organic acid concentration and cadmium content was detected both during growth and after chelate addition. On the contrary, the amount of phenols seemed to be correlated with the metal content only in non-amended and NTA-treated plants. The 10 and 20 citric acid additions caused 45% and 90% increases in shoot phenolic acids although cadmium content rose to a smaller extent. The inhibition of citrate synthase and the entrance of phosphoenolpyruvate in shikimate pathway leading to the formation of aromatic compounds might come into play. The increase in phenylalanine ammonialyase activity following citric acid amendments suggested this metabolic response.     

The impact of Bt maize expressing the Cry1Ac protein on non-target arthropods

Environmental Science and Pollution Research - From 2014 to 2016, individuals of the principal non-target arthropod (NTA) species in a field of Bt maize expressing the Cry1Ac protein (Bt38) were...     

Enhanced uptake of As, Zn, and Cu by Vetiveria zizanioides and Zea mays using chelating agents

Vetiveria zizaniodes (vetiver) is commonly known for its effectiveness in soil and sediment erosion control. It can tolerate to extreme soil conditions and produce a high biomass even growing in contaminated areas. Zea mays (maize) can also produce a very high biomass with a fast growth rate and possesses some degree of metal tolerance. A greenhouse study was conducted to investigate the feasibility of using vetiver and maize for remediation of arsenic (As)-, zinc (Zn-), and copper (Cu)-amended soils and evaluate the effects of chelating agents on metal uptake by these plants. Vetiver had a better growth (dry weight yield of root and shoot) than maize under different treatment conditions. The effects of different chelating agents on As, Zn, and Cu extraction from soil to soil solution were studied. Among the nine chelating agents used, it was noted that 20 mmol NTA could maximize As and Zn bioavailability, while 20 mmol HEIDA could maximize Cu bioavailability in the soil solution. The surge time in maximizing metal uptake ranged from 16 to 20 days which indicated that timing on plant harvest was an important factor in enhanced metal accumulation. In general, vetiver was a more suitable plant species than maize in terms of phytoextraction of metals from metal-contaminated soil. Application of NTA in As-amended soil and HEIDA in Cu-amended soil at the rate of 20 mmol kg(-1) increased 3-4-fold of As and Cu in shoot of both plants, whereas application of NTA (20 mmol kg(-1)) increased 37- and 1.5-fold of Zn accumulation in shoot of vetiver and maize, respectively. The potential environmental risk of metal mobility caused by chelating agents used for phytoextraction should not be overlooked.     

Occurrence and behavior of wastewater indicators in the Santa Ana River and the underlying aquifers.

The occurrence and behavior of wastewater indicator compounds in the Santa Ana River (SAR) water and the underlying aquifer recharged by the SAR has been studied. The SAR contains a high proportion of tertiary treated wastewater effluents, up to 100% during summer and fall. The following water quality parameters were quantified: four specific wastewater indicator compounds, ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), a naphthalene dicarboxylate (NDC) isomer, alkylphenol polyethoxy carboxylates (APECs), and selected haloacetic acids (HAAs), nitrate, dissolved oxygen (DO), DOC, total carbohydrate, and phenolic substances. Statistical analysis indicated that normal distribution was adequate to describe the probability distribution of the constituents in most cases. In the river, the concentrations of wastewater indicator compounds decreased as the fraction of storm runoff increased. EDTA and NDC were detected in a monitoring well near the river and in two production wells 1.8 and 2.7 km down gradient with little apparent attenuation. By contrast, NTA, APECs, bromochloro- and dibromoacetic acids appeared to be attenuated significantly during infiltration of river water and groundwater transport.     

Biodegradable chelating agents for industrial,domestic, and agricultural applications—a review

Aminopolycarboxylates, like ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), are chelating agents widely used in several industrial, agricultural, and domestic applications. However, the fact that they are not biodegradable leads to the presence of considerable amounts in aquatic systems, with serious environmental consequences. The replacement of these compounds by biodegradable alternatives has been the object of study in the last three decades. This paper reviews the most relevant studies towards the use of environmentally friendly chelating agents in a large number of applications: oxidative bleaching, detergents and cleaning compositions, scale prevention and reduction, remediation of soils, agriculture, electroplating, waste treatment, and biocides. Nitrilotriacetic acid (NTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) are the most commonly suggested to replace the nonbiodegradable chelating agents. Depending on the application, the requirements for metal complexation might differ. Metal chelation ability of the most promising compounds [NTA, EDDS, IDS, methylglycinediacetic acid (MGDA), l-glutamic acid N,N-diacetic acid (GLDA), ethylenediamine-N,N′-diglutaric acid (EDDG), ethylenediamine-N,N′-dimalonic acid (EDDM), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), 2-hydroxyethyliminodiacetic acid (HEIDA), pyridine-2,6-dicarboxylic acid (PDA)] with Fe, Mn, Cu, Pb, Cd, Zn, Ca, and Mg was simulated by computer calculations. The advantages or disadvantages of each compound for the most important applications were discussed.     

Substitutes for phosphate containing washing products: Their toxicity and biodegradability in the aquatic environment

The toxicity of nitrolotriacetic acid (NTA), citrex-S-5, sodium alluminium silicate (NAS), carboxymethyloxysuccinate (CMOS), linear alkylbenzene sulfonate (LAS) and soap was examined using bacteria ($\text{Pseudomonas}$$\text{fluorescens}$), algae ($\text{Chlorella}$$\text{vulgaris}$ and $\text{Microcystis}$$\text{aeruginosa}$), crustaceans ($\text{Daphnia}$$\text{magna}$), insects ($\text{Aedes}$$\text{aegypti}$), fishes ($\text{Poecilia}$$\text{reticulata}$ and $\text{Oryzias}$$\text{latipes}$) and amphibians ($\text{Xenopus}$$\text{laevis}$). The biodegradability of NTA, citrex-S-5, CMOS and LAS was studied in the OECD-test.The acute toxicity of the compounds differed largely with the organisms tested (up to a factor 1,000). Based on the results of the short-term toxicity tests (with all test organisms) and the long-term toxicity tests (with $\text{Daphnia}$$\text{magna}$ and in case of LAS also with $\text{Poecilia}$$\text{reticulata}$) the following no-observed-effect concentrations (NOEC) could be derived: LAS 3.2 mg/1; NAS and soap 10 mg/1; CMOS 32 mg/1; NTA 100 mg/1 and citrex-S-5 320 mg/1. However, testing different samples of one test compound may result in marked differences in toxicity (e.g. NAS: a factor 32).All compounds tested showed to be biodegradable as the percentage DOC decreased more than 80% within four weeks. CMOS biodegraded quickly, whereas citrex-S-5 and LAS showed a somewhat slower rate of degradation. In contrast to the other compounds NTA required an adaptation period of 1 week.     

Effect of EDTA and NTA on cadmium distribution and translocation in Pennisetum purpureum Schum cv. Mott

The primary objective of this research was to investigate the cadmium (Cd) distribution in Pennisetum purpurem (Napier grass) in the presence of 30 mg/L of Cd and different types and concentrations of chelating agents (ethylenediaminetetraacetic acid disodium dihydrate (EDTA), nitrilotriacetic acid (NTA), and EDTA-NTA mixtures). Plant samples were collected every 15 d during a 105-d experimental period. Accumulation of Cd in each part of the plant was determined using atomic absorption spectrometer (AAS), and the distribution of Cd was determined by laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) and synchrotron radiation micro X-ray fluorescence (SR-micro-XRF). The highest concentrations of Cd accumulation of 889?±?53 mg kg^?1 in the underground part (roots) and 265?±?26 mg kg^?1 in the aboveground part (stems and leaves) in the presence of 1:1 M ratio of Cd:EDTA after 30 d of exposure were observed. Plants grown in the presence of either NTA or EDTA-NTA mixtures showed significant lower Cd accumulation levels. The LA-ICP-MS analysis showed that Cd was primarily accumulated in the aboveground part (stems and leaves), especially in the xylem and intercalary meristem. In addition, translocation factor was very low. Thus, P. purpurem could be considered as a candidate plant for cadmium phytostabilization.

     

Identification of relevant micropollutants in Austrian municipal wastewater and their behaviour during wastewater treatment

The European Union has defined environmental quality standards (EQSs) for surface waters for priority substances and several other pollutants. Furthermore national EQSs for several chemicals are valid in Austria. The study investigated the occurrence of these compounds in municipal wastewater treatment plant (WWTP) effluents. In a first screening of 15 WWTPs relevant substances were identified, which subsequently were monitored in 9 WWTPs over 1 year (every 2 months). Out of 77 substances or groups of substances (including more than 90 substances) 13 were identified as potentially relevant in respect to water pollution and subjected to the monitoring, whereas most other compounds were detected in concentrations far below the respective EQS for surface waters and therefore not further considered. The preselected 13 compounds for monitoring were cadmium (Cd), nickel (Ni), copper (Cu), selenium (Se), zinc (Zn), diuron, polybrominated diphenyl ethers (PBDEs), di(ethyl-hydroxyl)phthalate (DEHP), tributyltin compounds (TBT), nonylphenoles (NP), adsorbable organic halogens (AOX) and the complexing agents ethylenediaminetetraacetic acid (EDTA) as well as nitrilotriacetic acid (NTA). In the effluents of WWTPs the concentrations of the priority substances Cd, NP, TBT and diuron frequently exceeded the respective EQS, whereas the concentrations for DEHP and Ni were below the respective EQS. The effluent concentrations for AOX, EDTA, NTA, Cu, Se and Zn frequently are in the range or above the Austrian EQS for surface waters. Besides diuron and EDTA all compounds are removed at least partially during wastewater treatment and for most substances the removal via the excess sludge is the major removal pathway. For the 13 compounds which were monitored in WWTP effluents population equivalent specific discharges were calculated. Since for many compounds no or only few information is available, these population equivalent specific discharges can be used to assess emissions from municipal WWTPs to surface waters as well as to make a first assessment of the impact of a discharge on surface waters chemical status. Comparing discharges and river pollution on a load basis, the influence of diffuse sources becomes obvious and therefore should also be taken into consideration in river management.     

Effects of lead and chelators on growth, photosynthetic activity and Pb uptake in Sesbania drummondii grown in soil

Effects of lead (Pb) and chelators, such as EDTA, HEDTA, DTPA, NTA and citric acid, were studied to evaluate the growth potential of Sesbania drummondii in soils contaminated with high concentrations of Pb. S. drummondii seedlings were grown in soil containing 7.5 g Pb(NO(3))(2) and 0-10 mmol chelators/kg soil for a period of 2 and 4 weeks and assessed for growth profile (length of root and shoot), chlorophyll a fluorescence kinetics (F(v)/F(m) and F(v)/F(o)) and Pb accumulations in root and shoot. Growth of plants in the presence of Pb+chelators was significantly higher (P<0.05) than the controls grown in the presence of Pb alone. F(v)/F(m) and F(v)/F(o) values of treated seedlings remained unaffected, indicating normal photosynthetic efficiency and strength of plants in the presence of chelators. On application of chelators, while root uptake of Pb increased four-five folds, shoot accumulations increased up to 40-folds as compared to controls (Pb only) depending on the type of chelator used. Shoot accumulations of Pb varied from 0.1 to 0.42% (dry weight) depending on the concentration of chelators used.     

Fe3+(NTA)还原菌的固定化小球制备及还原特性

采用海藻酸钠包埋驯化得到的优势铁还原菌,用于还原络合吸收法脱除NOx过程中形成的中间副产物Fe³⁺(NTA)。结果表明,最佳包埋条件为海藻酸钠质量浓度4%,菌体质量浓度0.2%,CaCl₂质量浓度3%,此条件下制备的小球还原性能好,在微生物用量为20 g（湿重）/L时还原10 mmol/L Fe³⁺(NTA),经12 h反应后还原率达到96.1％,而相同条件下游离微生物的还原率仅为11.8％,但反应16 h后游离微生物与固定化小球的还原率相近,均为97％左右。但此法制备的小球机械强度不高,溶胀、破裂现象严重。通过添加聚乙烯醇和硅藻土改良固定化小球,可强化小球的机械强度、降低小球的溶胀及破裂现象,对Fe³⁺(NTA)的还原效果也较改良前的小球有所提高,两者最佳添加量均为20 g/L。改良后的小球与游离微生物相比,耐酸性增强,在pH=5的条件下,仍具有79.8％的还原效率,远高于相同条件下游离微生物的39.5％,但对温度的适应范围两者基本一致。