Deficiency and excess of groundwater iodine and their health associations.

More than two billion people worldwide have suffered thyroid disorders from either iodine deficiency or excess. By creating the national map of groundwater iodine throughout China, we reveal the spatial responses of diverse health risks to iodine in continental groundwater. Greater non-carcinogenic risks relevant to lower iodine more likely occur in the areas of higher altitude, while those associated with high groundwater iodine are concentrated in the areas suffered from transgressions enhanced by land over-use and intensive anthropogenic overexploitation. The potential roles of groundwater iodine species are also explored: iodide might be associated with subclinical hypothyroidism particularly in higher iodine regions, whereas iodate impacts on thyroid risks in presence of universal salt iodization exhibit high uncertainties in lower iodine regions. This implies that accurate iodine supply depending on spatial heterogeneity and dietary iodine structure optimization are highly needed to mitigate thyroid risks in iodine-deficient and -excess areas globally.

Bioaccumulation of 35 metal(loid)s in organs of a freshwater mussel (Hyriopsis cumingii) and environmental implications in Poyang Lake, China.

Benthic bioaccumulation of hazardous materials has been a great challenge to the health of lake ecosystems. As representative benthic macroinvertebrates, freshwater mussels and their accumulation characteristics have been regarded as effective indicators for assessing potential risks induced by sedimentary metal(loid)s in lakes. Here we profile organ-specific accumulation of 35 metal(loid)s in a freshwater mussel (Hyriopsis cumingii) and their correlations to metal speciation in sediments of Poyang Lake, the largest lake of China. Significant organ-specific characteristics of metal accumulation were found in gills, though higher thallium (Tl) and selenium (Se) were found in the hepatopancreas, and greater arsenic (As) mostly accumulated in gonads. Pearson correlation analysis revealed that the bioaccumulation of silver (Ag), cobalt (Co), and rare earth elements (ΣREE) in gills and As in gonads were closely associated with those in bioavailable fraction of sediments. Based on the biochemical analysis in the major organs, gills exhibited the highest enzymatic activity compared with hepatopancreas and gonads. Sedimentary metals, particularly for available Ag, Co, and ΣREE, play key roles in causing lipid peroxidation in gills and significantly promote the activities of superoxide dismutase (SOD)/glutathione reductase (GR), while many metals (e.g., cadmium, manganese, Se) inhibit the glutathione (GSH) content in gonads and hepatopancreas. Our study indicates a high physiological sensitivity of mussels to these target metals, which highlights the significance of organ-specific accumulation of metal(loid)s in understanding the potential ecological risks of sedimentary metal(loid)s in lake ecosystems.

Interpreting main features of the differential absorbance spectra of chlorinated natural organic matter: Comparison of the experimental and theoretical spectra of model compounds.

This study compared chlorination-induced changes of the properties of natural organic matter (NOM) represented by standard humic substances and NOM present in pristine and anthropogenically-affect reservoirs, rivers, groundwater and seawater. The chlorination-induced changes of NOM properties were quantified using the differential absorbance spectra (DAS) which were processed via numeric deconvolution. Six Gaussian bands were found to comprise the DAS of all examined waters. These bands (denoted as A0, A1, A2, A3, A4 and A5, respectively) have maxima located at ca. 200, 240, 276, 316, 385 and 547 nm. The bands A1-A4 were observed in the DAS of representative model chlorinated compounds. Quantum chemical (QC) calculations were carried out to examine the intrinsic nature of these bands and electronic transitions associated with them. QC data demonstrate that bands A1 and A2 are present in almost all aromatic organic species, A3 is likely to be associated with acetophenone- and/or styrene-like groups. A4 can be attributed to the engagement of m-hydroxyaromatic and flavone-type groups typical for the polyphenolic moiety in NOM and known to be the key precursors of disinfection by-product (DBP) formation. Thus, the intensity of band A4 is predicted to be an especially strong predictor of DBP formation.

Simultaneous nitrification, denitrification and phosphorus removal in a sequencing batch reactor (SBR) under low temperature.

Simultaneous nitrogen and phosphorus removal in winter is one of the great challenges in wastewater treatment processes due to the poor bioactivity of microbial communities. In this study, excellent performance of simultaneous nitrification, denitrification and phosphorus removal (SNDPR) was achieved at low temperature of 10 °C and COD/N ratio of 6 in a lab-scale sequencing batch reactor. Total nitrogen (TN) and phosphorus (TP) removal efficiency reached 89.6% and 97.5%, respectively, accompanied with N2O emission of 7.46% TN due to the primary contribution (70%) of nitrifier denitrification. It was further confirmed that polyphosphate accumulating organisms (PAOs) were dominant in microbial communities revealed by fluorescence in situ hybridization and 16S rRNA amplicon sequencing. Moreover, denitrifying phosphorus removal by PAOs through nitrite pathway was found to be the main reason for the high efficiency of this SNDPR process. Denitrifying PAOs, especially the subgroup PAOII capable of utilizing nitrite to take up phosphorus, played a significant role in highly efficient TN and TP removal at low temperature. Furthermore, genus Propionivibrio was enriched (48.9%) in the bacterial community based on the 16S rRNA analysis, which was proposed to be a crucial member involved in the nitrogen and phosphorus removal simultaneously at low temperature in this system.

Genomic insights into metabolic potentials of two simultaneous aerobic denitrification and phosphorus removal bacteria, Achromobacter sp. GAD3 and Agrobacterium sp. LAD9.

Bacteria capable of simultaneous aerobic denitrification and phosphorus removal (SADPR) are promising for the establishment of novel one-stage wastewater treatment systems. Nevertheless, insights into the metabolic potential of SADPR-related bacteria are limited. Here, comprehensive metabolic models of two efficient SADPR bacteria, Achromobacter sp. GAD3 and Agrobacterium sp. LAD9, were obtained for the first time by high-throughput genome sequencing. With succinate as the preferred carbon source, both strains employed a complete TCA cycle as the major carbon metabolism for potentials of various organic acids and complex carbon oxidation. Complete and truncated aerobic denitrification routes were confirmed in GAD3 and LAD9, respectively, facilitated by all the major components of the electron transfer chain via oxidative phosphorylation. Comparative genome analysis revealed distinctive ecological niches involved in denitrification among different phylogenetic clades within Achromobacter and Agrobacterium. Excellent phosphorus removal capacities were contributed by inorganic phosphate uptake, polyphosphate synthesis and phosphonate metabolism. Additionally, the physiology of GAD3/LAD9 is different from that displayed by most available polyphosphate accumulating organisms, and reveals both strains to be more versatile, carrying out potentials for diverse organics degradation and outstanding SADPR capacity within a single organism. The functional exploration of SADPR bacteria broadens their significant prospects for application in concurrent aerobic carbon and nutrient removal.

Potential application of aerobic denitrifying bacterium Pseudomonas aeruginosa PCN-2 in nitrogen oxides (NOx) removal from flue gas.

Conventional biological removal of nitrogen oxides (NOx) from flue gas has been severely restricted by the presence of oxygen. This paper presents an efficient alternative for NOx removal at varying oxygen levels using the newly isolated bacterial strain Pseudomonas aeruginosa PCN-2 which was capable of aerobic and anoxic denitrification. Interestingly, nitric oxide (NO), as the obligatory intermediate, was negligibly accumulated during nitrate and nitrite reduction. Moreover, normal nitrate reduction with decreasing NO accumulation was realized under O2 concentration ranging from 0 to 100%. Reverse transcription and real-time quantitative polymerase chain reaction (RT-qPCR) analysis revealed that high efficient NO removal was attributed to the coordinate regulation of gene expressions including napA (for periplasmic nitrate reductase), nirS (for cytochrome cd1 nitrite reductase) and cnorB (for NO reductase). Further batch experiments demonstrated the immobilized strain PCN-2 possessed high capability of removing NO and nitrogen dioxide (NO2) at O2 concentration of 0-10%. A biotrickling filter established with present strain achieved high NOx removal efficiencies of 91.94-96.74% at inlet NO concentration of 100-500ppm and O2 concentration of 0-10%, which implied promising potential applications in purifying NOx contaminated flue gas.

Simultaneous denitrification and phosphorus removal by Agrobacterium sp. LAD9 under varying oxygen concentration.

Although efficient aerobic denitrification has received increasing attention, few studies have been made on simultaneous denitrification and phosphorus removal (SDPR) under aerobic condition. In this study, SDPR by an efficient aerobic denitrifier, Agrobacterium sp. LAD9, was firstly demonstrated. High nitrate and phosphorus removal rates of 7.50 and 1.02 mg L(-1) h(-1) were achieved in wide range of O2 concentration from 5.92 to 20.02 mg L(-1). The N2O production would be inhibited as O2 concentration exceeded 11.06 mg L(-1), while the phosphorus removal efficiency would be generally improved with increasing O2 concentration. (15)N mass spectrometry revealed that nitrogen removal accorded with the typical aerobic denitrification pathway, while (31)P nuclear magnetic resonance spectroscopy ((31)P NMR) indicated the fate of phosphorus to cells, extracellular polymeric substances (EPS), and polyphosphate (poly-P) of the denitrifier. EPS acted as a reservoir of phosphorus and the transformation of poly-P was dynamic and depended on initial orthophosphate (ortho-P) content. The aerobic SDPR would greatly simplify the conventional wastewater treatment processes which required separated considerations of nitrogen and phosphorus removal.

Nitrite interference and elimination in diphenylcarbazide (DPCI) spectrophotometric determination of hexavalent chromium.

Cr(VI) is highly noted as a carcinogenic, mutagenic, and teratogenic pollutant. However, accurate determination of Cr(VI) in aqueous samples is difficult using the conventional diphenylcarbazide (DPCI) spectrophotometric method upon being interfered by co-existed nitrite. This paper illustrates how to eliminate the nitrite influence in a simple but efficient method based on a detailed analysis of interference mechanism. High-performance liquid chromatography analysis revealed that under acidic condition, DPCI was oxidized by nitrite to other substrates, which could not react with Cr(VI). The final oxidation product of DPCI was further purified by thin-layer chromatography and identified as diaryl carbodiazone by Fourier Transform Ion Cyclotron Resonance-Mass Spectrometry (FTICR-MS) and nuclear magnetic resonance. Consequently, an improved method was proposed by simply adding sulfamic acid for eliminating the nitrite interference in Cr(VI) determination. The proposed method was successfully confirmed by the accurate recovery of Cr(VI) from spiked water samples and further proven with inductively coupled plasma-atomic emission spectroscopy, which demonstrated a great potential for determining Cr(VI) concentration in aqueous samples containing nitrite.

Effect of inorganic nanoparticles on 17ß-estradiol and 17α-ethynylestradiol adsorption by multi-walled carbon nanotubes.

With extensive application of diverse engineered nanoparticles (NPs), multiple NPs would inevitably be released into the environment. However, much emphasis in most previous studies on the interactions of pollutants with NPs has been placed on only one type of NPs at a time. This study investigated the impact of inorganic NPs (I-NPs) on the adsorption of 17ß-estradiol (E2) and 17α-ethynylestradiol (EE2) by multi-walled carbon nanotubes (CNTs). The presence of I-NPs inhibited the adsorption and increased the equilibrium time of E2 and EE2 by CNTs. Moreover, the effect of Al2O3 was stronger than that of SiO2, because electrostatic attraction enhanced the interaction between oppositely charged Al2O3 and CNTs. The addition sequence of I-NPs and pollutant also influences adsorption. This is among the first studies investigating the effect of I-NPs on pollutants adsorption by CNTs, which is useful for understanding the transport and fate of CNTs and contaminants in natural aquatic systems.

Influence of silicate on the transport of bacteria in quartz sand and iron mineral-coated sand.

The influence of silicate on the transport and deposition of bacteria (Escherichia coli) in packed porous media were examined at a constant 20 mM ionic strength with different silicate concentrations (from 0 to 1 mM) at pH 7. Transport experiments were performed in two types of representative porous media, both bare quartz sand and iron mineral-coated quartz sand. In bare quartz sand, the breakthrough plateaus in the presence of silicate in suspensions were lower and the corresponding retained profiles were higher than those without silicate ions, indicating that the presence of silicate in suspensions decreased cell transport in bare quartz sand. Moreover, the decrease of bacteria transport in quartz sand induced by silicate was more pronounced with increasing silicate concentrations from 0 to 1 mM. However, when EPS was removed from cell surfaces, the presence of silicate in cell suspensions (with different concentrations) did not affect the transport behavior of bacteria in quartz sand. The interaction of silicate with EPS on cell surfaces negatively decreased the zeta potentials of bacteria, resulting in the decreased cell transport in bare quartz sand when silicate was copresent in bacteria suspensions. In contrast, the presence of silicate in suspensions increased cell transport in iron mineral-coated sand. Silicate ions competed with bacteria for the adsorption sites on mineral-coated sand, contributing to the increased cell transport in mineral-coated sand with silicate present in cell suspensions.

Sludge granulation and performance of a low superficial gas velocity sequencing batch reactor (SBR) in the treatment of prepared sanitary wastewater.

A sequencing batch reactor (SBR) employing a low superficial gas velocity was used to produce aerobic granular sludge for wastewater treatment. At a gas velocity of 0.0056 m s(-1) sludge containing a mixture of light yellow and black granules with similar functional groups was quickly formed. The black granules contained crystals of CaCO(3), FeS, and Fe(2)O(3) as well as filamentous bacteria that strengthened the particles and reduced the mass transfer resistance. No inorganic crystals were detected in the yellow sludge granules, and their structure was maintained through cohesion mediated by extracellular polymeric substances (EPS). The light yellow granules were denser and offered better settling performance than the black granules, enhancing the settling properties of the mixed sludge. During a 12-h cycle, the maximum reductions in chemical oxygen demand (COD), NH(3)-N, and total nitrogen (TN) occurred at 240, 480, and 360 min with removal efficiencies of 90%, 90%, and 54%. When the cycle time was limited to 480 min, self-dissolution of the granules was avoided while sill maintaining removal efficiencies for COD, NH(3)-N, and TN of 88%, 90%, and 53%.

Palm oil mill effluent treatment using a two-stage microbial fuel cells system integrated with immobilized biological aerated filters.

An integrated system of two-stage microbial fuel cells (MFCs) and immobilized biological aerated filters (I-BAFs) was used to treat palm oil mill effluent (POME) at laboratory scale. By replacing the conventional two-stage up-flow anaerobic sludge blanket (UASB) with a newly proposed upflow membrane-less microbial fuel cell (UML-MFC) in the integrated system, significant improvements on NH(3)-N removal were observed and direct electricity generation implemented in both MFC1 and MFC2. Moreover, the coupled iron-carbon micro-electrolysis in the cathode of MFC2 further enhanced treatment efficiency of organic compounds. The I-BAFs played a major role in further removal of NH(3)-N and COD. For influent COD and NH(3)-N of 10,000 and 125 mg/L, respectively, the final effluents COD and NH(3)-N were below 350 and 8 mg/L, with removal rates higher than 96.5% and 93.6%. The GC-MS analysis indicated that most of the contaminants were satisfactorily biodegraded by the integrated system.

Washing of field weathered crude oil contaminated soil with an environmentally compatible surfactant, alkyl polyglucoside.

Weathered crude oil contaminated soils (COCSs), which are much more difficult to remediate than those freshly contaminated, are widespread especially at the sites of oil fields and industries. Surfactant enhanced ex situ soil washing could be used to remediate COCSs, but surfactant toxicity becomes one of the major concerns. In this study, a class of green surfactants, alkyl polyglucosides (APGs), were tested in washing the field weathered COCS with relatively high oil concentration (123 mgg(-1) dry soil) from Jilin Oilfield, Northeastern China. APG1214, characterized with longer alkyl chain, was more effective than APG0810 in crude oil removal. Adding inorganic sodium salts into APG1214 solution further improved the crude oil removal efficiency (CORE). Washing parameters (temperature, washing time, agitation speed and solution/soil ratio) were investigated and further optimized integratedly with an orthogonal design. At the optimum conditions, the CORE reached 97%. GC/MS analysis showed that the proportion of small n-alkanes (C(16)-C(23)) in residual crude oil gradually increased, which was helpful to interpret the oil removal mechanism. Moreover, eminent effect on removal of large n-alkanes was achieved from the synergy between APG1214 and inorganic salts, which was opposite to the effect when they were added separately. This study demonstrated a promising way to remediate COCS with ecologically compatible surfactant and provided guidelines for its practical application.

Study on treatment of coking wastewater by biofilm reactors combined with zero-valent iron process.

Experiments were conducted to investigate the behavior of the integrated system with biofilm reactors and zero-valent iron (ZVI) process for coking wastewater treatment. Particular attention was paid to the performance of the integrated system for removal of organic and inorganic nitrogen compounds. Maximal removal efficiencies of chemical oxygen demand (COD), ammonia nitrogen (NH(3)-N) and total inorganic nitrogen (TIN) were up to 96.1, 99.2 and 92.3%, respectively. Moreover, it was found that some phenolic compounds were effectively removed. The refractory organic compounds were primarily removed in ZVI process of the integrated system. These compounds, with molecular weights either ranged 10,000-30,000 Da or 0-2000 Da, were mainly the humic acid (HA) and hydrophilic (HyI) compounds. Oxidation-reduction and coagulation were the main removal mechanisms in ZVI process, which could enhance the biodegradability of the system effluent. Furthermore, the integrated system showed a rapid recovery performance against the sudden loading shock and remained high efficiencies for pollutants removal. Overall, the integrated system was proved feasible for coking wastewater treatment in practical applications.

Titanium dioxide mediated photocatalytic degradation of 17beta-estradiol in aqueous solution.

Photocatalytic degradation of 17beta-estradiol (E2) in aqueous medium mediated with titanium dioxide (TiO2) was studied. Moreover, effect of TiO2 dosage on the degradation efficiency was investigated. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of E2 under neutral and alkaline conditions. The degradation efficiency of E2 increased with increasing concentration of TiO2 but decreased due to light scattering as TiO2 concentration was greater than 0.5mgml(-1). Several intermediates were formed during photocatalytic degradation of E2. However, only a few of the compounds could be identified and confirmed by LC-MS and LC-MS/MS. Six intermediates were observed by photocatalytic oxidation under alkaline conditions, namely 2-hydroxyestradiol, 10epsilon-17beta-dihydroxy-1,4-estradien-3-one (DEO), 10epsilon-hydroperoxide-17beta-hydroxy-1,4-estradien-3-one and three kinds of dicarboxylic acids formed by the opening of aromatic ring. In addition to the six intermediates mentioned above, 17beta-hydroxy-1,4-estradien-3-one (EO) was observed under neutral conditions and in the presence of methanol. Based on these intermediates, which were hardly degraded even after E2 was fully degraded, the mechanism of E2 degradation by TiO2 photocatalysis was elucidated.

Advanced treatment of coking wastewater by coagulation and zero-valent iron processes.

Advanced treatment of coking wastewater was investigated experimentally with coagulation and zero-valent iron (ZVI) processes. Particular attention was paid to the effect of dosage and pH on the removal of chemical oxygen demand (COD) in the two processes. The results showed that ZVI was more effective than coagulation for advanced treatment of coking wastewater. The jar tests revealed that maximal COD removal efficiency of 27.5-31.8% could be achieved under the optimal condition of coagulation, i.e. 400mg/L of Fe(2)(SO(4))3 as coagulant at pH 3.0-5.0. On the other hand, the COD removal efficiency could be up to 43.6% under the idealized condition of ZVI upon 10 g/L active carbon and 30 g/L iron being dosed at pH 4.0. The mechanisms for COD removal in ZVI were dominated by coagulation, precipitation and oxidation-reduction. ZVI would also enhance the biodegradability of effluent by increasing BOD5/COD from 0.07 to 0.53. Moreover, some ester compounds could be produced in the reaction. Although ZVI was found more efficient than coagulation in eliminating low molecular weight (<2000 Da) compounds in the wastewater, there were still a few residual contaminants which could hardly be eliminated by either of the process.

[Biodegradation of oil field wastewater in biological aerated filter (BAF) by immobilization].

A special kind of carrier was used to immobilize effective microorganisms B350M in a biological aerated filter (BAF) react system for treatment of oil field wastewater, which is of salinity > 0.5%, lack of N and P, and contains low organic matter. Through the biodegradation system operated for 142d, the react system can achieve average degradation efficiency 90.5%, 74.4%, 85.6%, 100% for oil, TOC, COD and H2S, when HRT was 4h and COD volumetric load was 1.07 kg/(m3 x d). GC-MS results show that the organic substance in wastewater contain 27 different kind substances, a majority (23) of alkane and a minority (4) of aromatic substances. C14H30 to C28H58 in influent could be decomposed into small molecular substance efficiently, especially the C18H38 to C28H58, and also polycyclic aromatic hydrocarbons (PAHs) such as Phenanthrene. The react system had a good diversity, because the carriers provide agreeable air and water condition for microorganisms, to resist high salinity and toxic pollutant. Filamentous microorganisms were observed in a great deal and will not cause foaming and bulking in BAF reactor by immobilization.