Formation of hazardous by-products resulting from the irradiation of natural organic matter: comparison between UV and VUV irradiation

The use of ultraviolet (UV) or vacuum ultraviolet (VUV) photo-oxidation followed by biological treatment for the removal of natural organic matter (NOM) in drinking water is a potential water treatment technique under investigation. This paper reports on the trihalomethane formation potential (THMFP), the haloacetic acid formation potential (HAAFP), and formation of nitrite and peroxide following both UV and VUV irradiation of NOM prior to biological treatment. The total THMFP was found to decrease with increasing UV and VUV irradiation dose, although there was a linear increase in bromoform formation. Determination of the THMFP of NOM fractions obtained after irradiation, showed that the hydrophobic fraction was dominated by chlorinated species which accounted for the majority of the total THMFP, while bromoform was observed only in the hydrophilic fraction of NOM. VUV irradiation reduced the HAAFP with increasing dose, in contrast, UV irradiation had a limited effect on the overall HAAFP. Following UV or VUV irradiation, the chlorinated species accounted for the majority of HAAFP; however, significant formation of brominated haloacetic acid (HAA) was observed. The nitrate concentration of the untreated water directly influenced the concentration of nitrite produced as a consequence of UV and VUV irradiation. Hydrogen peroxide formation was greater during VUV irradiation than during UV irradiation. Samples exposed to various doses of UV or VUV irradiation (up to 138 J cm(-2)) were deemed non-cytotoxic (African green monkey kidney cells) and non-mutagenic (Ames test).     

Ozonation of aqueous solution of alpha endosulfan

Ozonation of alpha endosulfan and the effects of some parameters such as pH, temperature and partial pressure on ozonation were investigated and the kinetic constants were calculated in this study. Alpha endosulfan solutions were ozonated in a lab-scale semi-batch reactor under variable experimental conditions. Increase in dissolved ozone concentration had a positive effect on oxidation rate. Alpha endosulfan could be removed up to 94% at pH 4 for an ozonation time of 60 minutes. The oxidation reaction was found to be of second order and of first order with respect to both ozone and alpha endosulfan. The temperature dependent reaction expression of alpha endosulfan was obtained as kd = (1.889 exp(- 2.21 x 10(-3)/T). It was concluded that, although the rate of reaction was lower than the rate of other pesticide oxidation reported in the literature. alpha endosulfan presented an obvious reaction to ozonation.     

Characterizing dissolved organic matter and evaluating associated nanofiltration membrane fouling

Natural organic matter (NOM) characteristics were determined for three ground waters exhibiting different water quality conditions. The water quality of the three feed waters collected at various water table depths was characterized by XAD-8/-4 resin adsorption, high performance size exclusion chromatography with ultraviolet and dissolved organic carbon (DOC) detections, and Fourier transform infrared spectroscopy (FTIR) to determine NOM fractionation, molecular weight, and NOM functional groups, respectively. Systematic studies were conducted to identify potential NOM foulants in ground water for nanofiltration (NF) membrane fouling. The results show that the hydrophobic fraction of NOM in all of the samples was significantly high (71-93%) compared to the hydrophilic (1.7-22.6%) and transphilic (5.3-6.6%) fractions. However, insignificant flux-decline (less than 5%) was observed for the highest DOC (36.9 mg l(-1)) and hydrophobic NOM (93%) containing groundwater compared to the other lesser DOC and hydrophobic NOM containing ground waters. This is presumably due to either higher fractions of hydrophilic and transphilic NOM or inorganic interactions that may be major foulants. Based on FTIR, aromatic foulants were observed at 1662 cm(-1) (CO-NH2 or CO conjugated with aromatic rings) for the fouled NF membrane with the relatively low DOC source waters. The contact angle of the clean membrane (52 degrees ) decreased with fouling up to 42-47 degrees for fouled membranes with the various samples.     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题，分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究，同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示，水中的有机物为腐殖酸类物质，分子量分别为1600和3500，腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳，处理前后水样DOC浓度无明显变化，而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5，经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时，DOC降至7．6mg／L，然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外，当反应初始pH值为3，过氧化氢投加量为0．5％（v／v），亚铁和双氧水摩尔比为0．05时，出水DOC降至5．6mg／L，氧化后有小分子有机物生成。     

Ozonation of Procaine Penicillin G formulation effluent Part I: Process optimization and kinetics

Ozonation characteristics of synthetic Procaine Penicillin G (PPG) formulation effluent were investigated in a semi-batch ozone reactor at different pH (3, 7 and 12), ozone feed rates (600-2600 mg h-1) and COD values (200-600 mg l-1). Ozonation of aqueous PPG effluent resulted in 37 (82)% COD removal after 60 (120) min ozonation when the reaction pH was kept constant at pH=7.900 mg l-1 (corresponding to 50% of the total introduced) ozone was absorbed during a reaction period of 1 h. The effects of increasing the applied ozone dose and the initial COD on the COD abatement rates of PPG effluent were also studied. Results have indicated that increasing the ozone dose and decreasing the COD content both have positive effects on COD removal rates. The significant contribution of the free radical (.OH) reaction pathway to PPG ozonation could be traced using tert-butyl alcohol as the .OH probe compound at varying concentrations. The bimolecular reaction rate constants for the direct reaction of PPG with ozone were found as 152 and 2404 M-1 h-1 at pH=3 and 7, respectively, using the gas phase ozone partial pressures determined from of the outlet gas stream analysis. It could be demonstrated that ozone decomposition to free radicals being triggered by increasing the pH from 3 to 7 is essential for the rate enhancement of PPG effluent ozonation.     

An investigation into reservoir NOM reduction by UV photolysis and advanced oxidation processes

A comparison of four treatment technologies for reduction of natural organic matter (NOM) in a reservoir water was made. The work presented here is a laboratory based evaluation of NOM treatment by UV-C photolysis, UV/H(2)O(2), Fenton's reagent (FR) and photo-Fenton's reagent (PFR). The work investigated ways of reducing the organic load on water treatment works (WTWs) with a view to treating 'in-reservoir' or 'in-pipe' before the water reaches the WTW. The efficiency of each process in terms of NOM removal was determined by measuring UV absorbance at 254 nm (UV(254)) and dissolved organic carbon (DOC). In terms of DOC reduction PFR was the most effective (88% removal after 1 min) however there were interferences when measuring UV(254) which was reduced to a lesser extent (31% after 1 min). In the literature, pH 3 is reported to be the optimal pH for oxidation with FR but here the reduction of UV(254) and DOC was found to be insensitive to pH in the range 3-7. The treatment that was identified as the most effective in terms of NOM reduction and cost effectiveness was PFR.     

Removal of selected endocrine disrupting chemicals and personal care products in surface waters and secondary wastewater by ozonation

This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).     

Removal of NOM from drinking water: Fenton's and photo-Fenton's processes

The control of disinfection by-products during water treatment is primarily undertaken by reducing the levels of precursor species prior to chlorination. As many waters contain natural organic matter at levels of up to 15 mgl(-1) there is a need for a range of control methods to support conventional coagulation. Two such processes are the Fenton and photo-Fenton's processes and in this paper they are assessed for their potential to remove NOM from organic rich waters. The performance of both processes is shown to be depentent on pH, Fe: H2O2 ratio as well as Fe2+ dose. Under optimum conditions both processes achieved greater than 90% removal of DOC and UV254 absorbance. This removal lead to the trihalomethane formation potential of the water being reduced from 140 to below 10 microgl(-1), well below UK and US standards.     

Advanced oxidation of natural organic matter using hydrogen peroxide and iron-coated pumice particles

The oxidative removal of natural organic matter (NOM) from waters using hydrogen peroxide and iron-coated pumice particles as heterogeneous catalysts was investigated. Two NOM sources were tested: humic acid solution and a natural source water. Iron coated pumice removed about half of the dissolved organic carbon (DOC) concentration at a dose of 3000 mg l(-1) in 24 h by adsorption only. Original pumice and peroxide dosed together provided UV absorbance reductions as high as 49%, mainly due to the presence of metal oxides including Al(2)O(3), Fe(2)O(3) and TiO(2) in the natural pumice, which are known to catalyze the decomposition of peroxide forming strong oxidants. Coating the original pumice particles with iron oxides significantly enhanced the removal of NOM with peroxide. A strong linear correlation was found between iron contents of coated pumices and UV absorbance reductions. Peroxide consumption also correlated with UV absorbance reduction. Control experiments proved the effective coating and the stability of iron oxide species bound on pumice surfaces. Results overall indicated that in addition to adsorptive removal of NOM by metal oxides on pumice surfaces, surface reactions between iron oxides and peroxide result in the formation of strong oxidants, probably like hydroxyl radicals, which further oxidize both adsorbed NOM and remaining NOM in solution, similar to those in Fenton-like reactions.     

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.     

Removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation and biotreatment.

The removal of pyrene and benzo(a)pyrene from contaminated water by sequential and simultaneous ozonation-bioremediation techniques was investigated. During the sequential treatment, ozonation using 0.5 or 2.5 mg/L ozone was used as a pretreatment process, whereas, during the simultaneous treatment process, ozonation of hydrocarbon-contaminated water at a predetermined duration using 0.5 mg/L ozone was made in the presence of microbial biomass. Ozonation was not beneficial for the removal of pyrene. However, despite a decreased specific biodegradation rate, ozonation improved the overall elimination of benzo(a)pyrene during both treatment processes. The overall removal of benzo(a)pyrene increased from 23 to 91% after exposure of the water to 0.5 mg/L ozone for 30 minutes during the simultaneous treatment process and further to 100% following exposure to 2.5 mg/L ozone for 60 minutes during the sequential treatment mode, demonstrating the benefits of combined ozonation-biological treatment for the removal of polycyclic aromatic hydrocarbons.     

Effect of pre-ozonation on optimized coagulation of a typical North-China source water

Although ozone is widely used as a pre-oxidant before coagulation in water treatment, the effect of pre-ozonation on optimized coagulation for removal of particle and natural organic matter (NOM) is still not fully understood. In this paper, pilot-scale investigation was conducted to examine the impact of pre-ozonation on coagulation for particle and NOM removal. Changes in the particle and NOM distributions were characterized by various methods, including laser light granularity system, particle counter, ultrafiltration, and resin absorbent fractionation. A novel composite flocculant–HPAC was compared with the traditional ferric chloride coagulant in terms of coagulation efficiency under the influence of pre-ozonation. Typical micro-polluted North China surface water was used for pilot coagulation tests. The results show that the effect of pre-ozonation on coagulation is associated with the dosage of ozone, coagulant type, and water contamination characteristics. For FeCl₃, pre-ozonation acts as a coagulation aid at low dosage (1.0 mg L⁻¹ O₃) for turbidity and UV₂₅₄ removal; while at higher dosage (2.0 mg L⁻¹ O₃), pre-ozonation is detrimental to UV₂₅₄ removal although it is still beneficial for turbidity removal. In the case of composite flocculant–HPAC, pre-ozonation demonstrates negligible influence on both turbidity and UV₂₅₄ removal. Ozone can simultaneously aggregate fine particles and break down large ones, making them more mineralized and easier to remove. NOM with intermediate molecular weight and hydrophobic neutral property increases at lower ozone dosage, favoring removal by coagulation. At higher ozone dosages, NOM becomes more hydrophilic and its molecular weight becomes smaller, decreasing NOM removal.     

污泥减量过程中臭氧氧化对硝化和反硝化影响的试验研究

采用AO工艺,考察了在污泥减量过程中臭氧(O3)氧化对生物系统硝化和反硝化能力的影响.结果表明,在每克SS中O3投量为0.05 g时,氧化后污泥中的CODcr由37.5 mg/L增至700mg/L,TN由4.86 mg/L增至36.6 mg/L,NH4 -N由0.353mg/L增至7.49 mg/L,NO3--N由2.19 mg/L增至5.15 mg/L.虽然氧化系统出水NH4 -N浓度略高于对照系统,但氧化系统NH4 -N的去除率大于98%,硝化能力基本没有受到O3氧化的影响.O3氧化污泥后增加的有机物作为附加的碳源循环至缺氧段,提高了反硝化的效果,当污泥氧化比例分别为10%、20%、30%时,进入缺氧段的CODCr/TN分别平均增至11.21、11.56、11.88,氧化系统的反硝化效果也随之分别提高5%、25%、37%.     

微气泡曝气O3／H2O2处理RO浓水的效能及影响因素

采用O3／H2O2高级氧化工艺处理炼油厂反渗透（RO）浓水，用溶气泵加压溶气并产生微气泡强化传质，确定装置运行条件，考察气体中臭氧浓度、O3／H2O2初始摩尔比、pH和温度对O3／H2O2处理RO浓水效果的影响，并对RO浓水处理效能进行研究。结果表明，随着气体中臭氧浓度的增加，COD的去除率基本呈线性增加；加入适当量H，0，能提高臭氧氧化RO浓水的效果，O3／H2O2初始摩尔比在0～0．8范围内，COD的去除率先增加后下降，O3／H2O2初始摩尔比为O．5时COD去除率最大；pH从6．84增加到9．01，COD去除率逐渐增大，pH为10．03时COD去除率反而降低；在14～28℃范围内，温度低时，升高温度COD去除率增加较大，温度较高时，升高温度对COD去除率的影响较小。为考察该工艺的稳定性，在H：0：／0，初始摩尔比为O．5、溶液pH为8～9、臭氧浓度为80～100mg／L、温度为10-28℃条件下，对COD为90～140mg／L的RO浓水氧化处理4～10h，出水COD维持在39．9～49．9mg／L，达到《城镇污水处理厂污染物排放标准（GB18918—2002）》中的一级A标准；去除1gCOD消耗031．4～3．3g，消耗0，与H，02的总氧量为2．2～4．4g。     

Effect of Pre-ozonation on Optimized Coagulation of a Typical North-China Source Water

Although ozone is widely used as a pre-oxidant before coagulation in water treatment, the effect of pre-ozonation on optimized coagulation for removal of particle and natural organic matter (NOM) is still not fully understood. In this paper, pilot-scale investigation was conducted to examine the impact of pre-ozonation on coagulation for particle and NOM removal. Changes in the particle and NOM distributions were characterized by various methods, including laser light granularity system, particle counter, ultrafiltration, and resin absorbent fractionation. A novel composite flocculant–HPAC was compared with the traditional ferric chloride coagulant in terms of coagulation efficiency under the influence of pre-ozonation. Typical micro-polluted North China surface water was used for pilot coagulation tests. The results show that the effect of pre-ozonation on coagulation is associated with the dosage of ozone, coagulant type, and water contamination characteristics. For FeCl₃, pre-ozonation acts as a coagulation aid at low dosage (1.0 mg L⁻¹ O₃) for turbidity and UV₂₅₄ removal; while at higher dosage (2.0 mg L⁻¹ O₃), pre-ozonation is detrimental to UV₂₅₄ removal although it is still beneficial for turbidity removal. In the case of composite flocculant–HPAC, pre-ozonation demonstrates negligible influence on both turbidity and UV₂₅₄ removal. Ozone can simultaneously aggregate fine particles and break down large ones, making them more mineralized and easier to remove. NOM with intermediate molecular weight and hydrophobic neutral property increases at lower ozone dosage, favoring removal by coagulation. At higher ozone dosages, NOM becomes more hydrophilic and its molecular weight becomes smaller, decreasing NOM removal.     

Treatment of distillery spent-wash by ozonation and biodegradation: significance of pH reduction and inorganic carbon removal before ozonation.

This study is aimed at exploring strategies for mineralization of refractory compounds in distillery effluent by anaerobic biodegradation/ozonation/aerobic biodegradation. Treatment of distillery spent-wash used in this research by anaerobic-aerobic biodegradation resulted in overall COD removal of 70.8%. Ozonation of the anaerobically treated distillery spent-wash was carried out as-is (phase I experiments) and after pH reduction and removal of inorganic carbon (phase II experiments). Introduction of the ozonation step resulted in an increase in overall chemical oxygen demand (COD) removal, with the highest COD removals of greater than 95% obtained when an ozone dose of approximately 5.3 mg ozone absorbed/mg initial total organic carbon was used. The COD removal during phase II experiments was slightly superior compared with phase I experiments at similar ozone doses. Moreover, efficiency of ozone absorption from the gas phase into distillery spent-wash aliquots was considerably enhanced during phase II experiments.     

Influence of Suwannee River humic acid on particle properties and toxicity of silver nanoparticles

Adsorption of natural organic matter (NOM) on nanoparticles can have dramatic impacts on particle dispersion resulting in altered fate and transport as well as bioavailability and toxicity. In this study, the adsorption of Suwannee River humic acid (SRHA) on silver nanoparticles (nano-Ag) was determined and showed a Langmuir adsorption at pH 7 with an adsorption maximum of 28.6 mg g⁻¹ nano-Ag. It was also revealed that addition of <10 mg L⁻¹ total organic carbon (TOC) increased the total Ag content suspended in the aquatic system, likely due to increased dispersion. Total silver content decreased with concentrations of NOM greater than 10 mg TOC L⁻¹ indicating an increase in nanoparticle agglomeration and settling above this concentration. However, SRHA did not have any significant effect on the equilibrium concentration of ionic Ag dissolved in solution. Exposure of Daphnia to nano-Ag particles (50 μg L⁻¹ and pH 7) produced a linear decrease in toxicity with increasing NOM. These results clearly indicate the importance of water chemistry on the fate and toxicity of nanoparticulates.     

Spectral attenuation of solar ultraviolet radiation in humic lakes in Central Finland

The attenuation of solar ultraviolet (UV) radiation in five lakes in Central Finland was evaluated through field measurements and/or by determining the optical properties of the lake water during summer 1999. Spectral UV irradiance in the air and at several depths underwater was measured in three lakes (Lake Palosj?rvi, Konnevesi, and Jyv?sj?rvi) with dissolved organic carbon (DOC) ranging from 4.9 to 8.7 mg l(-1) and chlorophyll a ranging from 1.6 to 16 g l(-1). According to the field measurements, 99% of the UV-B radiation was attenuated in approximately a half meter water column in the clearest lake. In the UV-A region at 380 nm, the corresponding attenuation occurred in the upper one meter. In a small humic lake (DOC 13.2-14.9 mg l(-1)) UV-B radiation was attenuated to 1% of the subsurface irradiance within the top 10 cm water column, whereas UV-A radiation (at 380 nm) penetrated more than twice as deeply (maximum 25 cm), as predicted from the absorption coefficients. These results suggest the importance of the dissolved fraction of lake water in governing the UV attenuation in lakes. This was seen from the significant relationship between the vertical attenuation coefficients (Kd) based on field measurements and the absorption coefficients (ad) derived from spectrophotometric laboratory scannings, as well as between Kd and DOC.     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Copper toxicity to Lemna minor modelled using humic acid as a surrogate for the plant root

Humic acids are chemically analogous to plant root cell walls in that their surface sites are principally comprised of carboxylic and phenolic acids which bind both metals and protons. Based on this analogy, we developed a biotic-ligand type of model to predict Cu toxicity to Lemna minor, using particulate humic acid (HA(part)) of the Windermere Humic Aqueous Model (WHAM), and 7d static-renewal exposures with five surface waters and one nutrient media which varied in DOC (1-10 mg L(-1)), pH (6.9-8.7), and water hardness (35-236 mg equivalent CaCO(3)L(-1)). Although the range of waters tested resulted in a 36-fold variation in 50% inhibitory concentration (IC50) values, the calculated concentration of Cu bound to HA(part) using this framework was highly correlated with pooled percent net root elongation (%NRE) (R(2)=0.95). Ten and fifty percent IC values based on [Cu-HA(part)] were additionally within a factor of ±1.5 and ±1.4, respectively, inclusive of 95% confidence limits. This model construct, which defines the free metal ion and the first hydrolysis product (but not metal carbonate complexes) as being bioavailable, provides an alternative means of defining the binding surface in bioavailability models, whereby a heterogeneous mixture of ligands collectively influence root-metal sorption and toxicity.