水体酸化条件下Cu(II)对斑马鱼胚胎的毒性效应

为评价由酸雨、酸性矿山排水等环境污染导致的水体酸化及水体重金属联合作用对水生生物的生态毒性效应,研究了不同pH值(pH=3、4、5、6、7和7.8)条件下Cu2+对斑马鱼胚胎发育的影响。结果表明,酸性水体及Cu2+单一存在时,酸对斑马鱼胚胎24h半数效应浓度值EC50为pH=3.65,Cu2+(pH=7.8)对斑马鱼胚胎24h-EC50为0.267mg·L-1;当水体酸化及水体中的Cu2+共存时,较低的pH对Cu2+的生物毒性起协同作用,表现为随溶液pH的降低,各浓度Cu2+对斑马鱼胚胎的24h凝结率显著增高(P24h致死率=0.001),而斑马鱼胚胎96h孵化率显著降低(P96h孵化率=0.002),且不同浓度的Cu2+之间的生物毒性效应存在显著性差异(P24h致死率=0.0321;P96h孵化率=0.0028)。这说明酸性水体和Cu2+都显著影响斑马鱼胚胎的发育,且Cu2+在酸性水体中对斑马鱼胚胎的毒性显著增强。因此,在受重金属Cu2+污染的地区,如同时受到酸雨或酸性矿山排水等较低pH值和Cu2+的双重胁迫,较低浓度的Cu2+就能够对水生生物的生殖发育及水生生态系统产生严重的影响和危害。     

Adsorptive behaviors of humic acid onto freshly prepared hydrous manganese dioxides

This study focused on the adsorptive behaviors of humic acid onto freshly prepared hydrous MnO₂(s) (δMnO₂), and investigated the feasibility of employing δMnO₂ for humic acid removal from drinking water. Effects of such parameters as molecular mass of humic acid, kinds of divalent cations on adsorptive behaviors and possible mechanisms involved were investigated. This study indicated that humic acid with higher molecular mass exhibited more tendency of adsorbing onto δMnO₂ than that with lower molecular mass. Ca²⁺ facilitated more humic acid adsorption than Mg²⁺; UV-Vis spectra analysis indicated higher capabilities of Ca²⁺ coordinating with acidic functional groups of humic acid than that of Mg²⁺. Additionally, ζ potential characterization indicated that Ca²⁺ showed higher potential of increasing gz potential of δMnO₂ than Mg²⁺. Ca²⁺ of 1.0 mmol/L increased ζ potential of δMnO₂ from ?37 mV (pH 7.9) to +7 mV (pH 7.2), while 1.0 mmol/L Mg²⁺ increased to lower value as ?9 mV (pH 6.5), correspondingly. Fourier transform infrared (FTIR) spectra demonstrated the adsorption of humic acid onto δMnO₂, showing the important roles of-COO^? functional groups and surface Mn-OH in the adsorption of humic acid onto δMnO₂.     

Nano-titanium dioxide (TiO2)-induced changes affecting Cu2+-mediated alterations in bacterium Bacillus subtilis and α-amylase

Titanium dioxide (TiO₂) nanoparticles possess the potential to coexist with Copper (Cu²⁺) in soil. The individual and combined toxicity of these two chemicals was evaluated using the bacterium Bacillus subtilis, a known soil model bacterium. Cu²⁺ (6.25–50?µg?mL^?1) alone produced toxicity to bacteria as evidenced by the decreased cell viability and deceased α-amylase production. The addition of TiO₂ (50?mg?mL^?1) enhanced the Cu²⁺-induced decrease in cell viability but elevated amylase activity. TiO₂ did not markedly affect the growth rate and lag period. A primary cause of TiO₂ increasing Cu²⁺ toxicity is presumed to be associated with hydroxyl radical formation, while increased amylase activity is considered to arise from Cu²⁺ facilitating TiO₂ degradation ability.     

Molecular dynamics of stability and structures in phytochelatin complexes with Zn,Cu, Fe,Mg, and Ca: Implications for metal detoxification

Phytochelatins, or (γ-glutamyl-cysteine) _n -glycine, are specialized peptides produced by plants and algae to mitigate toxic metal exposure, for instance in response to high levels of metals such as Cu, Cd, and Zn. Stability constants and structural characterization of metal–phytochelatin complexes are lacking. This information is required to gain mechanistic insights on the metal selectivity of phytochelatins. Here, we studied structural coordination and thermodynamic stability by performing molecular dynamics simulations of a fully hydrated phytochelatin molecule complexed with Ca²⁺, Mg²⁺, Fe²⁺, Zn²⁺, and Cu²⁺. Our results predict the following decreasing order for the thermodynamic stability of the phytochelatin complexes: Zn²⁺ ≥ Cu²⁺ ≥ Fe²⁺ > Mg²⁺ > Ca²⁺. The favorable binding energies with Zn²⁺ and Cu²⁺ over the other metal cations can be explained by shorter binding distances and greater coordination from carboxylate and keto O atoms. Conformational rearrangement of phytochelatin following metal chelation was captured by monitoring changes in the solvent-accessible volume. Accessibility of solvent molecules to the phytochelatin structure was inversely proportional to the distance between the coordinated ligands and the chelated metal. These new findings demonstrate the influence of the metal–phytochelatin structure on the metal-binding thermodynamics and the phytochelatin conformation, both of which are important to evaluate the intracellular role of phytochelatin in mediating algal response to toxic heavy metal exposure.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Effects of three different nanoparticles on bioaccumulation,oxidative stress,osmoregulatory, and immune responses of Carcinus aestuarii

Abstract

In this study, the toxicity of CuO (40?nm), α-Al₂O₃ (40?nm), and α-Fe₂O₃ (20–40?nm) nanoparticles was comparatively investigated on Carcinus aestuarii. Crabs were semi-statically exposed to 1?mg/L of each for 14?days and their accumulation and distribution in tissue and hemolymph, potential oxidative stress mechanism, total hemocyte counts and types, and the osmoregulatory and ionoregulatory responses were determined. The tissue distribution of CuO nanoparticles was hepatopancreas?>?hemolymph?≥?gill?> muscle, for α-Fe₂O₃ gill?>?hepatopancreas?>?muscle?> hemolymph, and for α-Al₂O₃ gill?>?muscle?≥?hemolymph?> hepatopancreas. While α-Al₂O₃ and α-Fe₂O₃ NPs, induced lipid peroxidation and changes in antioxidant enzyme activity in the hepatopancreas tissue, the oxidative damage caused by the CuO nanoparticles was minimal. All three nanoparticles, copper in particular, elicit osmoregulatory and ionoregulatory toxicity at this concentration, due to the inhibition of Na⁺, K⁺-ATPase activity in the gill and depletion of hemolymph and carcass ion concentrations.     

Diuron herbicide degradation catalyzed by low molecular weight humic acid-like compounds

Phenylureas such as diuron are major herbicides used worldwide to control undesirable weeds. The environmental fate of phenylureas is of great interest because massive amounts of those herbicides are used. It is known that abiotic degradation of phenylureas in soil–water systems is catalyzed by humic acids. However, due to the chemical heterogeneity and large molecular sizes of humic acids, the specific effects of functional groups during catalysis have not been elucidated. Therefore, we studied here for the first time the kinetics of diuron degradation in the presence of low molecular weight humic acid-like compounds such as benzoic acid derivatives. Experiments were carried out at various pH and temperature, and monitored by high-performance liquid chromatography. Results show that all benzoic acid derivatives efficiently catalyzed diuron hydrolysis. The catalytic efficiency decreased in the following order: 0.88 M^?1 day^?1 for 3,4-dihydroxybenzoic acid, 0.72 M^?1 day^?1 for 4-hydroxybenzoic acid, 0.23 M^?1 day^?1 for phthalic acid, 0.11 M^?1 day^?1 for 2-hydroxybenzoic acid, and 0.09 M^?1 day^?1 for 2,4-dihydroxybenzoic acid. These differences in the catalytic efficiency are explained by steric hindrance affecting the accessibility of reactive sites and hence influencing the rate of the overall process. Steric factors are therefore expected to control the catalytic activity of humic acids because of the chemical similarities between humic acids and low molecular weight humic acid-like compound. Our results should help predict more accurately the fate and abiotic degradation mechanism of phenylureas in the environment.     

Effects of vanadate supply on plant growth, Cu accumulation, and antioxidant capacities in Triticum aestivum L.

The effects of normal vanadate (V) supply (40 μM) on copper (Cu) accumulation, plant growth and reduction in Cu toxicity in wheat seedlings (Triticum aestivum L.) were investigated. The results showed Cu accumulation (mg g^?1 dw) in the applied V treatment was about 10.2 % in shoots and 16.7 % in roots higher up on exposure to excess Cu (300 μM) than that observed only in excess Cu plants. Compared with the treatment of the normal concentration used in Hoagland’s culture solution Cu (0.6 μM), excess Cu significantly induced lipid peroxidation indicated by accumulation of thiobarbituric acid reactive substances (MDA). The seedlings showed apparent symptoms of Cu toxicity and plant growth were significantly inhibited by excess Cu. The applied V significantly decreased lipid peroxidation in roots caused by excess Cu and inhibited the appearance of Cu toxicity symptoms. Moreover, the applied V effectively improved the antioxidant defense system to alleviate the oxidative damage induced by Cu. Although the addition of V could promote superoxide dismutase in both shoots and roots to reduce superoxide radicals, peroxidase and catalase in shoots and ascorbate peroxidase and dehydroascorbate reductase in roots were major enzymes to eliminate H₂O₂ in wheat seedlings.     

Oxidized multiwalled carbon nanotubes modified with 2-(2-hydroxy-5-nitrophenyl)-4,5-diphenyl imidazole for solid phase extraction and preconcentration of some metal ions

In this work, a new procedure for the enrichment of the trace amount of Cu²⁺, Ni²⁺, Co²⁺, Pb²⁺, Fe²⁺, and Zn²⁺ ions based on the utilization of multiwalled carbon nanotubes (MWCNT) modified with 2-(2-hydroxy-5-nitrophenyl)-4,5-diphenyl imidazole as chelating agent prior to their determination by flame atomic absorption spectrometry has been described. The influence of effective parameters including pH, amount of ligand and MWCNT, composition of eluent, and coexisting ions on recoveries of understudy metal ions was examined. At the optimum pH of 5.0, all metal ions were quantitatively sorbed onto the proposed solid phase and completely desorbed with 8?mL of 5.0?mol?L^?1 HNO₃. The detection limit of Cu²⁺, Co²⁺, Ni²⁺, Pb²⁺, Fe²⁺, and Zn²⁺ ions was 1.7, 2.4, 2.3, 2.9, 2.8, and 1.4?µg?L^?1, while the preconcentration factor was 63 for Cu²⁺ and 94 for the other metal ions and relative standard deviations between 1.8 less than 3.0%. The proposed procedure was applied for the analysis of various samples.     

Copper (II) adsorption studies using models of synthetic humic acids

A polymer with characteristics similar to those of humic acids was obtained by synthesis reactions from oxidative polymerization in an alkaline medium using para-benzoquinone, hydroquinone and 4-aminobenzoic acid as precursors. Samples of natural and synthetic humic acid were used to examine the adsorption behavior of Cu²⁺ ions on these substrates. The mathematical models described by Langmuir and Freundlich equations were applied, yielding the maximum adsorption intensity values K′ (Langmuir), maximum adsorption capacity, b (Langmuir) and the adsorbent adsorption capacity, m (Freundlich). Based on solubility studies, pH 3 was selected for the development of the adsorption experiment. The Cu²⁺ ion presented a favorable adsorption, with RL (equilibrium parameter) responses in Langmuir isotherms falling within the desirable ranges.     

Large-scale green synthesis of Cu nanoparticles

This article reports a novel, eco-friendly herbal method to synthesize Cu nanoparticles in large scales. Cu nanoparticles are an alternative to Ag and Au nanoparticles and have potential applications in many industrial areas. Many synthetic routes have been documented for the preparation of copper nanoparticles, but very few routes are eco-friendly and large-scale. We report here the preparation of Cu nanoparticles from aqueous CuSO₄ using non-toxic and inexpensive materials like curd, milk, and herbal extracts such as tamarind and lemon juice as capping agents. X-ray diffraction and transmission electron microscopy show that produced particles are nanocrystalline copper 20–50 nm in size with a face-centered cubic structure. Fourier-transformed infrared spectroscopy evidences the role of organic acids in the capping process. The novelty of this work is the synthesis of Cu nanoparticles from CuSO₄ without electricity and using non-toxic, cheap capping agents.     

Copper sulphate use in South African traditional medicine

Copper (Cu) is an essential element to humans; however, exposure to elevated concentrations through occupational hazard and/or environmental means may be detrimental. This paper provides results of a cross-sectional study aimed to determine the prevalence of copper sulphate (CuSO₄) use in South African traditional medicine by traditional health practitioners (THPs) and details the use thereof. A total of 201 THPs were enrolled from two main municipal areas of KwaZulu-Natal (South Africa). Information on demographic characteristics of THPs, reasons for using or not using CuSO₄ as well as administration methods and age groups of recipients were collected. Of the 201 THPs interviewed, 145 (72 %) use CuSO₄ for healing purposes. The use of CuSO₄ was strongly associated with gender (p = 0.009) where the proportion of CuSO₄ users was higher for female than male THPs. CuSO₄ was reportedly administered to individuals of all ages, including infants and children. The main routes of administration were enema (n = 110; 76 %), oral (n = 40; 28 %) and use in bath (n = 40; 28 %). The reasons cited for use are diverse and included skin rashes (n = 43; 30 %), aches, pains and swelling (n = 38; 28 %) as well as sexually transmitted diseases (n = 28; 19 %). This study identified a high prevalence of THPs using CuSO₄ for healing purposes. These findings support the need to regulate South African traditional medicine to safeguard the user.     

Determination of types of interactions exhibited by binary mixtures of heavy metals tested against the hermit crab,Clibanarius africanus

Single and joint action toxicity of heavy metal compounds (ZnCO₃, CuSO₄ and CdSO₄) were carried out against the hermit crab, Clibanarius africanus in laboratory bioassays. On the basis of 96?h LC₅₀ values, CuSO₄ (96?h LC₅₀?=?0.03?mM) was found to be the most toxic followed by CdSO₄ and ZnCO₃ (96?h LC₅₀?=?0.24?mM) in decreasing order of toxicity. The evaluation of the metal compounds in mixtures of ZnCO₃–CuSO₄, ZnCO₃–CdSO₄ and CdSO₄–CuSO₄ in pre-defined molar ratios revealed that interactions between Zn–Cu and Zn–Cd test mixtures were in conformity with the models of antagonism (reduction in toxicity of constituent metals). The synergistic ratios (S.R.s) and relationship between observed/predicted 96?h LC₅₀ values (relative toxic unit, RTU) were consistently below 1, indicating antagonistic interactions. Analysis using isobolograms also indicated the interactions between the mixture components to be antagonistic. However, with regards to CdSO₄–CuSO₄ test mixtures, the interactions between these metals were mainly in conformity with the model of synergism. The S.R. and RTU values were largely above 1, indicating synergistic interactions. The importance of the joint action evaluations for the management and protection of aquatic ecosystems, particularly in the setting up of water quality criteria was discussed.     

Attenuation of metal species in acidic solutions using bentonite clay: implications for acid mine drainage remediation

A laboratory batch experimental study has been carried out to evaluate the adsorption capacity of selected metal species in acid mine drainage (AMD) by bentonite clay. Bentonite clay was mixed with simulated AMD at specific solid–liquid (S/L) ratios and agitated in a reciprocating shaker and adsorption of selected toxic metals assessed over time. Cation exchange capacity varied from 1140 to 1290 meq kg^?1. Contact of AMD with bentonite leads to increase in pH and a possible reduction in electrical conductivity and total dissolved solids. At constant agitation time of 60 min, the pH increased with dosage of bentonite. Removal of Mn²⁺, Al ³⁺, and Fe³⁺ was observed to be greatest at 60 min of agitation. Bentonite clay exhibits high adsorption for Al³⁺ and Fe³⁺ at concentration less than 300 mg L^?1, while the capacity for Mn²⁺ was observed to be lower. Adsorption capacity for SO₄^2? was low with a great percentage of the SO₄^2? remaining in solution. Adsorption capacity of bentonite with more complex formulated AMD and gold tailing leachates was low for Fe³⁺, Al³⁺, and Mn²⁺. This indicates that optimum adsorption of bentonite clay is dependent on the chemistry of the AMD and its application might be site specific.     

Low-cost and efficient adsorbent derived from pyrolysis of Jatropha curcas seeds for the removal of Cu2+ from aqueous solutions

Biochar, is a low-cost material that can be used as an alternative adsorbent for the removal of heavy metals. In this study, a low-cost and efficient adsorbent synthesised from Jatropha curcas seeds was used for the uptake of Cu²⁺ from aqueous solutions. The as-prepared adsorbent was characterised by scanning electron microscopy and Brunauer–Emmett–Teller analysis post calcination at 500 °C, its BET surface area and total pore volume were 39.62?m²?g^?1 and 0.049?m³?g^?1, respectively. Subsequently, the effects of initial pH of the solution, contact time, and adsorbent material dosage on the adsorption of Cu²⁺ by the prepared adsorbent were investigated. The as-prepared adsorbent exhibited a high performance, with a maximum adsorption amount of 32.895?mg?g^?1 for Cu²⁺ at pH 5.0 and 25 °C, owing to the presence of ?OH, C=O, C–O, Si-O-Si, and O-Si-O on its surface. The predominant Cu²⁺ adsorption mechanism was assumed to be ion exchange. Notably, the Cu²⁺ adsorption could attain equilibrium within 90?min. In addition, the fact that the Langmuir model was a better fit than the Freundlich model for the isotherm data of Cu²⁺ adsorption by the as-prepared adsorbent suggested that the adsorption of Cu²⁺ was a monolayer adsorption process.     

腐殖酸作用下沉积物中纳米氧化铜对铜锈环棱螺生态毒性的影响

为了探讨不同水平腐殖酸作用下沉积物中纳米氧化铜(CuO-NPs)对底栖生物生态毒理学效应的影响,以铜锈环棱螺(Bellamya aeruginosa)为受试生物,通过腐殖酸和CuO-NPs加标沉积物的慢性(28 d)生物测试,研究了肝胰脏中Cu的生物积累、Na+K+-ATP酶(ATPase)、超氧化物歧化酶(SOD)以及过氧化氢酶(CAT)活性的变化规律.结果表明,在低浓度CuO-NPs处理组(60 μg·g1),沉积物中腐殖酸水平对Cu的生物积累以及ATPase、SOD和CAT活性均没有显著影响.在中、高浓度CuO-NPs处理组(≥180 μg·g-1),Cu的生物积累均随腐殖酸水平的增加而显著升高;肝胰脏ATPase活性随腐殖酸水平的增加而显著下降;当腐殖酸水平为0.05 g·g-1时,SOD活性显著高于未添加腐殖酸组,表现为显著诱导,当腐殖酸水平≥0.1g·g-1时,SOD活性开始下降,并具有浓度依赖性;随腐殖酸水平的增加,肝胰脏CAT活性总体上表现为浓度依赖性显著下降.由于沉积物中腐殖酸的存在,显著增加CuO-NPs在沉积物中的分散稳定性,更容易被铜锈环棱螺摄取,从而通过增加CuO-NPs的生物积累而增强对铜锈环棱螺的生态毒性.     

Geochemistry and quality of groundwater of the Yarmouk basin aquifer,north Jordan

Quality of groundwater in the Yarmouk basin, Jordan has been assessed through the study of hydrogeochemical characteristics and the water chemistry as it is considered the main source for drinking and agriculture activities in the region. The results of the relationship between Ca²⁺ + Mg²⁺ versus HCO₃^? + CO₃^2?, Ca²⁺ + Mg²⁺ versus total cations, Na⁺ + K⁺ versus total cations, Cl^? + SO₄^2? versus Na⁺ + K⁺, Na⁺ versus Cl^?, Na⁺ versus HCO₃^? + CO₃^2?, Na⁺ versus Ca²⁺, and Na⁺: Cl^? versus EC describe the mineral dissolution mechanism through the strong relationship between water with rocks in alkaline conditions with the release of Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃^?, CO₃^2?, SO₄^2?, and F^? ions in the groundwater for enrichment. Furthermore, evaporation processes, groundwater depletion, and ion exchange contribute to the increased concentration of Na⁺ and Cl^? ions in groundwater. Anthropogenic sources are one of the main reasons for contamination of groundwater in the study area and for increasing the concentration of Mg²⁺, Na⁺, Cl^?, SO₄^2?, and NO₃^? ions. Results show the quality of groundwater in the study area is categorized as follows: HCO₃^? + CO₃^2? > Cl^? > SO₄^2? > NO₃^? > F^? and Na⁺ > Ca²⁺ > Mg²⁺ > K⁺. In conclusion, the results of TDS, TH, and chemical composition showed that 26% of the groundwater samples were unsuitable for drinking. About 28% of groundwater samples in the study area have a high concentration of Mg²⁺, Na⁺, and NO₃^? above the acceptable limit. Also, based on high SAR, 10% of the groundwater samples were not suitable for irrigation purposes.     

Toxicity and bioaccumulation of heavy metals in mullet fish Liza klunzingeri (Mugilidae: Perciformes)

The mullet fish, Liza klunzingeri, commercially important and widely relished by Kuwaiti residents, and the stressed ecosystem in Kuwait Bay instigated us to conduct toxicity and bioaccumulation tests on heavy metals (Pb, Ni, V, Cu and Fe). Among five metals, Pb had the lowest observed effect concentration (LOEC) at 1 μg?l ^?1. Using multi-factor Probit analysis, toxicity tests (72 h) on L. klunzingeri reared in filtered sea water in the laboratory showed Pb with maximum effect at median lethal concentration (LC₅₀) followed by V, Ni, Cu and Fe. Their bioaccumulation factor (BAF) was in the sequence Pb>V>Fe>Cu and Ni. For fish exposed for 30 d, bioaccumulation exhibited increasing metal levels in liver followed by gills and muscles. These results suggest the potential use of L. klunzingeri as a bioindicator of metal pollution in the future.     

Geoenvironmental factors related to high incidence of human urinary calculi (kidney stones) in Central Highlands of Sri Lanka

An area with extremely high incidence of urinary calculi was investigated in the view of identifying the relationship between the disease prevalence and the drinking water geochemistry. The prevalence of the kidney stone disease in the selected Padiyapelella–Hanguranketa area in Central Highlands of Sri Lanka is significantly higher compared with neighboring regions. Drinking water samples were collected from water sources that used by clinically identified kidney stone patients and healthy people. A total of 83 samples were collected and analyzed for major anions and cations. The anions in the area varied in the order HCO₃ ^? > Cl^? > SO₄ ^2? > NO₃ ^? and cations varied in the order Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ > Fe²⁺. The dissolved silica that occurs as silicic acid (H₄SiO₄) in natural waters varied from 8.8 to 84 mg/L in prevalence samples, while it was between 9.7 and 65 mg/L for samples from non-prevalence locations. Hydrogeochemical data obtained from the two groups were compared using the Wilcoxon rank-sum test. It showed that pH, total hardness, Na⁺, Ca²⁺ and Fe²⁺ had significant difference (p < 0.005) between water sources used by patients and non-patients. Elemental ratio plots, Gibbs’ plot and factor analysis indicated that the chemical composition of water sources in this area is strongly influenced by rock–water interactions, particularly the weathering of carbonate and silicate minerals. This study reveals a kind of association between stone formation and drinking water geochemistry as evident by the high hardness/calcium contents in spring water used by patients.     

Evaluation of the toxicity of tetrabromobisphenol A and some of its oxidation products using a micro-scale algal growth inhibition test

A micro-scale algal growth inhibition (μ-AGI) test using a common micro-plate based fluorometric detection was used to demonstrate the effects of humic substances (HSs) on the toxicity of tetrabromobisphenol A (TBBPA) and its oxidative decomposition products 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), 2,5-dibromohydroquinone (2,5-DBHQ), 2,6-dibromobenzoquinone (2,6-DBBQ), and 2,6-dibromophenol (2,6-DBP) to Pseudokirchneriella subcapitata. The EC₅₀ values were: EC_50(TBBPA) = 7 mg L^?1, EC_50(2,5-DBHQ) = 7 mg L^?1, EC_50(2,5-DBBQ) = 19 mg L^?1, EC_50(2,6-DBP) = 49 mg L^?1, and EC_50(2,6-DBBQ) = 13 mg L^?1. The toxicity of the chemicals was slightly lower in the presence of HA. The toxicity of TBBPA decomposed by a biomimetic catalytic system consisting of iron (III) 5,10,15,20-tetrakis (p-sulfonatophenyl) porphyrin (Fe(III)-TPPS) and KHSO₅ was also evaluated using P. subcapitata and Chlamydomonas reinhardtii.