Characteristics and practical treatment technologies of winery wastewater: A review for wastewater management at small wineries.

The wine-making industry drives tourism and rural revitalization in several countries. Meanwhile, winemaking generates wastewater at all production stages, mainly from cleaning of equipment, floors, vessels, and bottles. This review presents a comprehensive analysis with statistical characteristics on the overall quality and generation rate of winery wastewater since 2007, identifies the technologies used by wineries in pilot- and full-scale wastewater treatment systems, and offers insights on practical wastewater treatment at small wineries. The median wastewater generation rate has been reduced to 1.58 L/L-wine, with a weekly peaking factor of 1.6-3.4 and monthly peaking factor of 2.1-2.7. Winery wastewater is acidic and of high organic strength. The organic substances are largely biodegradable and constituent concentrations do not exceed 50% inhibitory levels for biological treatment. However, the small ratios of nitrogen and phosphorus to biochemical oxygen demand indicate substantial needs to supplement nutrients for aerobic biological treatment. The frequency of processes used to pretreat winery wastewater was in the order of sedimentation > coarse screening > equalization > neutralization. The most frequently reported treatment methods were constructed wetland, activated sludge process, membrane bioreactor, and anaerobic digestion. Advanced oxidation processes have been pilot tested for polishing. The best wastewater management practice at small wineries is physical pretreatment, followed by land-based treatment systems. Covered anaerobic lagoons and underground digesters are practicable anaerobic digestion designs to reduce organic loading to land-based treatment systems. Research is needed to develop sufficient design criteria for the best practicable treatment processes and compare land-based treatment systems at pilot and full scales.

Enhanced degradation of organic contaminants using catalytic activity of carbonaceous structures: A strategy for the reuse of exhausted sorbents.

Generation of hydroxyl radicals (⋅OH) is the basis of advanced oxidation process (AOP). This study investigates the catalytic activity of microporous carbonaceous structure for in-situ generation of ⋅OH radicals. Biochar (BC) was selected as a representative of carbon materials with a graphitic structure. The work aims at assessing the impact of BC structure on the activation of H2O2, the reinforcement of the persistent free radicals (PFRs) in BC using heavy metal complexes, and the subsequent AOP. Accordingly, three different biochars (raw, chemically- and physiochemically-activated BCs) were used for adsorption of two metal ions (nickel and lead) and the degradation of phenol (100 mg/L) through AOP. The results demonstrated four outcomes: (1) The structure of carbon material, the identity and the quantity of the metal complexes in the structure play the key roles in the AOP process. (2) the quantity of PFRs on BC significantly increased (by 200%) with structural activation and metal loading. (3) Though the Pb-loaded BC contained a larger quantity of PFRs, Ni-loaded BC exhibited a higher catalytic activity. (4) The degradation efficiency values for phenol by modified biochar in the presence of H2O2 was 80.3%, while the removal efficiency was found to be 17% and 22% in the two control tests, with H2O2 (no BC) and with BC (no H2O2), respectively. Overall, the work proposes a new approach for dual applications of carbonaceous structures; adsorption of metal ions and treatment of organic contaminants through in-situ chemical oxidation (ISCO).

Microbial community similarity and dissimilarity inside and across full-scale activated sludge processes for simultaneous nitrification and denitrification.

Simultaneous nitrification and denitrification under low dissolved oxygen conditions is an energy-saving modification of the activated sludge process to achieve efficient nitrogen removal. Geographically distinct full-scale treatment plants are excellent platforms to address the links of microbial community with operating parameters. Mixed liquor samples were collected from a sequencing batch reactor plant, oxidation ditch plant, and step-feed activated sludge plant. Next-Generation Sequencing of the samples showed that the microbial communities were similar at the phylum level among the plants, being dominated by Proteobacteria. Microbial composition of functional groups was similar between the react fill and react phases of the sequencing batch reactors, among four sequencing batch reactors, and among four oxidation ditches. Nitrospira was the only identified genus of autotropic nitrifying bacteria with a relative abundance of 2.2-2.5% in the oxidation ditches and 0.4-0.7% at the other plants. Heterotrophic nitrifying-aerobic denitrifying bacteria were dominated by Dechloromonas with a relative abundance of 0.4-1.0%. Microbial community composition and nitrogen removal mechanisms were related to overall level and local zonation of dissolved oxygen, mixed liquor suspended solids concentration, nitrogen and organic loadings, and solids retention time. Low dissolved oxygen and low organic and nitrogen loadings favored growth of Nitrospira.

Three-stage treatment for nitrogen and phosphorus recovery from human urine: Hydrolysis, precipitation and vacuum stripping.

Source separation of human urine has not been widely adopted because of scaling on urine collecting fixtures and lack of verified technologies for on-site utilization of waterless urine. This study investigated the effects of flushing liquid, temperature and urease amendment on hydrolysis of urea to ammonia, explored ammonia recovery via vacuum stripping in connection with phosphorus recovery via struvite precipitation in different sequences, and performed economic analysis of a proposed nutrient recovery strategy. It was found that acetic acid could be dosed at 0.05-0.07 N to flush urine-diverting toilets and urinals for hygiene and prevention of scaling. However, a high dosage of 0.56 N completely inhibited urea hydrolysis. Source-separated urine could be stored at 25 °C with ample urease for complete urea hydrolysis within approximately 20 h. Fully hydrolyzed waterless urine contained 9.0-11.6 g/L ammonia-N, 0.53-0.95 g/L phosphate-P and only 2.3-9.1 mg/L magnesium. When magnesium was supplemented to attain the optimum Mg2+: PO43- molar concentration ratio of 1.0 in hydrolyzed urine, batch operation of a pilot-scale air-lift crystallizer removed 93-95% of phosphate and produced 3.65-4.93 g/L struvite in 1-5 h. Batch operation of a pilot-scale vacuum stripping - acid absorption system for 12 h stripped 72-77% of ammonia and produced 37.6-39.7 g/L (NH4)2SO4. Compared with the ammonia → phosphorus recovery sequence, the struvite precipitation → vacuum stripping sequence produced more struvite and ammonium sulfate. The strategy of urea hydrolysis → struvite precipitation → vacuum stripping of ammonia is a sustainable alternative to the conventional phosphorus fertilizer production and ammonia synthesis processes.

Anaerobic co-digestion of foodwaste with liquid dairy manure or manure digestate: Co-substrate limitation and inhibition.

Process instability has been a challenge to anaerobic digestion of foodwaste at higher organic loading rates. Co-digestion is one of the measures to improve stability. This study conducted batch experiments to compare liquid dairy manure and dairy manure digestate as a co-substrate for anaerobic digestion of foodwaste. The batch co-digestion experiments showed a two-stage biogas production process, which could be simulated with a modification of the Gompertz model. The specific biogas yields derived with the two-stage biogas production model was further simulated against the co-substrate ratios with substrate limitation - inhibition models for identifying the optimal co-substrate ratio. The Haldane model was the best to simulate co-substrate limitation - inhibition kinetics in anaerobic co-digestion of foodwaste. A higher ratio of dairy manure could result in co-substrate inhibition to biogas production due to recalcitrance of cellulose and toxicity of lignin and lignin derivatives. Kinetic modeling shows that the optimal volatile solids (VS) ratio of liquid dairy manure is 16.6%, at which the maximum specific methane yield is 0.54 L/g VS. Semi-continuous co-digestion of 88% foodwaste and 12% liquid dairy manure at a hydraulic retention time of 14 d attained 94% of the simulated maximum methane yield. Although co-digestion of foodwaste and manure digestate resulted in lower biogas yields than co-digestion with liquid dairy manure, manure digestate is still an attractive co-substrate that has several operational advantages compared with liquid dairy manure.

Recovery of ammonia in anaerobic digestate using vacuum thermal stripping - acid absorption process: scale-up considerations.

A vacuum thermal stripping process coupled with acid absorption has been developed at laboratory scale to recover ammonia in anaerobic digestate. To make this ammonia recovery process scalable, this study investigated the effects of feed depth on vacuum thermal stripping in a pilot system, developed sodium hydroxide dosages required to raise feed pH for stripping, and simulated the dynamics of ammonia reduction in batch stripping tests. As feed depth was increased from 8.5 to 34.0 cm, the ammonia mass transfer coefficient and ammonia stripping efficiency decreased while the mass of stripped ammonia increased. Digested municipal sludge had a greater ammonia mass transfer coefficient than digested dairy manure at each feed depth, which could be attributed to the difference in suspended and dissolved solids concentrations. The optimum feed depth was 18 cm of the digested sludge and 14 cm of the digested manure. Sodium hydroxide dosage for the digested manure was higher than that for the digested sludge and co-digested foodwaste. The dosages were correlated to concentrations of total dissolved solids and ammonia. Total ammonia concentration decreased exponentially in batch stripping of the digested sludge at 25.5 cm deep, with a first-order stripping rate coefficient of 0.087-0.144 h-1.

Investigating into composition, distribution, sources and health risk of phthalic acid esters in street dust of Xi'an City, Northwest China.

Phthalic acid esters (PAEs) are widely used as plasticizers and in consumer products, which may enter the environment and present risks to human health. U.S. EPA classifies six PAEs as priority pollutants, which could be accumulated in street dust at the interface of atmosphere, biosphere and geosphere. This study collected a total of 58 street dust samples from Xi'an City in Northwest China and analyzed for concentrations of the priority PAEs. Composition, distribution, sources and health risk of the PAEs were further examined. All the priority PAEs were detected in the street dust. The concentrations of individual PAEs varied between not detected and 183.19 mg/kg. The sum of the 6 priority PAEs (∑6PAEs) ranged from 0.87 to 250.30 mg/kg with a mean of 40.48 mg/kg. The most abundant PAEs in the street dust were di-n-butyl phthalate and di (2-ethylhexyl) phthalate (DEHP). Higher concentrations of ∑6PAEs in the street dust were found in the south and west parts of Xi'an City as well as its urban center, which were possibly attributed to the prevailing northerly Asian winter monsoon. The PAEs in the street dust originated mainly from wide application of plasticizers as well as cosmetics and personal care products. The main pathways of human exposure to PAEs in the street dust were ingestion and dermal adsorption of dust particles. The non-cancer risk of human exposure to PAEs in the street dust was relatively low, while the risk to children was higher than that to adults. The cancer risk of human exposure to DEHP in the street dust was lower than the standard limit value of 10-6.

Struvite recovery from anaerobically digested dairy manure: A review of application potential and hindrances.

Anaerobically digested dairy manure is rich in ammonium, orthophosphates, and magnesium, indicating a high potential for struvite recovery. Continuous generation of large amounts of dairy manure plus increasing global interest in anaerobic digestion of dairy manure suggest a huge market for struvite production with anaerobically digested dairy manure. However, the complex chemical composition of digested dairy manure presents hindrances to struvite recovery. This review paper assesses the significance and potential of struvite recovery from anaerobically digested dairy manure, identifies the factors hindering struvite recovery, and discusses the methods to overcome hindrances and the measures to improve phosphorus speciation of dairy manure for struvite formation. This paper proposes using "struvite recovery potential" or Pstruvite based on the least molar activity of struvite component ions in addition to "supersaturation ratio" to identify the potential for struvite recovery. The probable hindrances mainly include high Ca(2+) concentration and molar activity ratios of Ca(2+): Mg(2+) and Ca(2+): PO4(3-), high ionic strength, and high alkalinity. Struvite formation and purity is likely a function of all the interfering variables, rather than just a single factor with digested dairy manure. Potential enhancement measures need to be tested for technical and economic feasibility and applicability to various sources of digested dairy manure. This review paper provides guidance to overcoming the hindrances of digested dairy manure to struvite formation.

Investigation into ammonia stress on Cyperus alternifolius and its impact on nutrient removal in microcosm experiments.

Ammonia stress on plants has been investigated at discrete ammonia concentrations in constructed wetlands. This study introduced a Gaussian model to simulate the kinetics of ammonia stress and investigated reversible and irreversible ammonia stress on Cyperus alternifolius in wetland-like microcosms. Ammonia stress on plant weight increase and oxygen release potential started at weekly ammonia concentrations of 27 and 28 mg N/L, reached 50% inhibition at 178 and 158 mg N/L, and resulted in lethal effects at 311 and 303 mg N/L, respectively. The stress of one-time ammonia concentrations up to 400 mg N/L could be reversible. Ammonia concentrations constantly above 219 mg N/L exerted irreversible stress. In the microcosms with ammonia concentrations above the 50% inhibition levels, plants played a minor role in nitrogen removal. Nitrogen removal performance was not affected considerably by ammonia stress. Orthophosphate removal was suppressed by ammonia stress due to less plant uptake. Design and operation of constructed wetlands should consider wastewater ammonia concentration so that the integrity of constructed wetland ecosystems can be maintained.

Anaerobic co-digestion of food waste and dairy manure: effects of food waste particle size and organic loading rate.

This study was to comprehensively evaluate the effects of food waste particle size on co-digestion of food waste and dairy manure at organic loading rates increased stepwise from 0.67 to 3 g/L/d of volatile solids (VS). Three anaerobic digesters were fed semi-continuously with equal VS amounts of food waste and dairy manure. Food waste was ground to 2.5 mm (fine), 4 mm (medium), and 8 mm (coarse) for the three digesters, respectively. Methane production rate and specific methane yield were significantly higher in the digester with fine food waste. Digestate dewaterability was improved significantly by reducing food waste particle size. Specific methane yield was highest at the organic loading rate of 2g VS/L/d, being 0.63, 0.56, and 0.47 L CH4/g VS with fine, medium, and coarse food waste, respectively. Methane production rate was highest (1.40-1.53 L CH4/L/d) at the organic loading rate of 3 g VS/L/d. The energy used to grind food waste was minor compared with the heating value of the methane produced.

Field leaching of alkaline copper quaternary-treated red pine lumber over 3 years: long-term dynamics.

Alkaline copper quaternary (ACQ), a wood preservative, consists of copper oxide and quaternary ammonium compounds. Three red pine piles were monitored over 3 years to evaluate the dynamics of contaminant leaching from ACQ-treated and untreated lumber. There were small temporal changes in the volumetric leachate/rain ratio with the ACQ-treated lumber, while the volumetric ratio decreased across the 3 years with the untreated lumber, most likely due to considerable weathering that increased the capacity of the untreated lumber to absorb rain water. The average copper (Cu) concentration in leachate from the ACQ-treated lumber (4,033 µg/L) was much higher than that in leachate from the untreated lumber (87 µg/L) and rain (48 µg/L) in the first leaching year. Cu concentration in leachate from the ACQ-treated lumber in the second and third years decreased to 46-51% of that in the first year. There were significant seasonal decreases of Cu concentration in leachate from the ACQ-treated lumber, which were correlated to exposure time and meteorological parameters. ACQ-treatment did not affect leachate pH and concentrations of quaternary ammonium compounds and chemical oxygen demand. There were insignificant temporal changes of leachate pH and concentrations of chemical oxygen demand and total dissolved solids in leachate from both ACQ-treated and untreated lumber piles.

Activation of sawdust biochar with water and wastewater treatment residuals for sorption of perfluorooctanesulfonic acid in water.

Recent research has found biochar to be a cost-effective adsorbent for removal of perfluoroalkyl substances in water. To promote cleaner production and sustainable waste management, this study explored the potential to produce activated biochars by co-pyrolyzing sawdust with iron-rich biosolids and polyaluminum sludge. The maximum capacity to adsorb perfluorooctanesulfonic acid (PFOS) reached 27.2 mg g-1 with biosolids-activated biochar and 19.2 mg g-1 with aluminum sludge-activated biochar, compared to 6.2 mg g-1 with sawdust biochar. The increased adsorption capacities were attributed to electrostatic interactions between the anionic PFOS and metal functionalities on the biochar surface. In contrast, hydrophobic interaction was the dominant adsorption mechanism of sawdust biochar. The presence of dissolved organic matter at 5-50 mg L-1 was found to inhibit adsorption of PFOS in water, while pH as low as 3.0 and sodium chloride concentrations up to 100 mM enhanced removal of PFOS by all the three adsorbents. In batch adsorption tests at environmentally relevant PFOS dosages and adsorbent dosage of 0.25 g L-1, the biosolids-sawdust biochar and Al sludge-sawdust biochar removed 71.4% and 66.9% of PFOS from drinking water and 77.9% and 87.9% of PFOS from filtrate of sludge digestate, respectively. The biosolids-sawdust biochar additionally removed Fe, although the Al sludge-sawdust biochar released Al into the alkaline drinking water and filtrate. Overall, this study proved co-pyrolyzing sawdust and Fe-rich biosolids to be an effective approach to activate sawdust biochar for enhanced removal of PFOS while recycling wastewater treatment residuals and sawdust.

Numerical modeling of nitrogen removal processes in biofilters with simultaneous nitritation and anammox.

This study developed a simple numerical model for nitrogen removal in biofilters, which was designed to enhance simultaneous nitritation and anaerobic ammonium oxidation (anammox). It is the first attempt to simulate anammox together with two-step nitrification in natural treatment systems, which may have different kinetic parameters and temperature effects from conventional bioreactors. Prediction accuracy was improved by adjusting kinetic coefficients over the startup period of the biofilters. The maximum rates of nitritation and nitrite oxidation increased linearly over time during the startup period. Simulations confirmed successful enhancement of simultaneous nitritation and anammox (SNA) in the biofilters, with anammox contributing 35% of ammonium removal. Effluent ammonium concentration was affected by influent ammonium concentration and the maximum nitritation rate, and was insensitive to the maximum nitrite oxidation rate and anammox substrate factor. Ammonium removal via SNA was likely limited by biomass of aerobic ammonia oxidizing bacteria in the biofilters. The developed model is a promising tool for studying the dynamics of nitrogen removal processes including SNA in natural treatment systems.

A spatial distribution - Principal component analysis (SD-PCA) model to assess pollution of heavy metals in soil.

With the rapid development of urbanization, heavy metal pollution of soil has received great attention. Over-enrichment of heavy metals in soil may endanger human health. Assessing soil pollution and identifying potential sources of heavy metals are crucial for prevention and control of soil heavy metal pollution. This study introduced a spatial distribution - principal component analysis (SD-PCA) model that couples the spatial attributes of soil pollution with linear data transformation by the eigenvector-based principal component analysis. By evaluating soil pollution in the spatial dimension it identifies the potential sources of heavy metals more easily. In this study, soil contamination by eight heavy metals was investigated in the Lintong District, a typical multi-source urban area in Northwest China. In general, the soils in the study area were lightly contaminated by Cr and Pb. Pearson correlation analysis showed that Cr was negatively correlated with other heavy metals, whereas the spatial autocorrelation analysis revealed that there was strong association in the spatial distribution of eight heavy metals. The aggregation forms were more varied and the correlation between Cr contamination and other heavy metals was lower. The aggregation forms of Mn and Cu, Zn and Pb, on the other hand, were remarkably comparable. Agriculture was the largest pollution source, contributing 65.5 % to soil pollution, which was caused by the superposition of multiple heavy metals. Additionally, traffic and natural pollution sources contributed 17.9 % and 11.1 %, respectively. The ability of this model to track pollution of heavy metals has important practical significance for the assessment and control of multi-source soil pollution.

Overcoming challenges to struvite recovery from anaerobically digested dairy manure.

Recovering struvite from dairy manure has consistently posed problems for researchers. This study separated solids from anaerobically digested dairy manure using a filtration system. Filtrate was rich in free magnesium (160 to 423 mg/L), ammonium (320 to 1800 mg N/L) and orthophosphate (93 to 332 mg P/L). High concentrations of free calcium (128 to 361 mg/L) and alkalinity (3309 to 6567 mg/L as CaCO3), however, may hinder struvite precipitation. Batch precipitation tests were conducted to identify and overcome factors that interfere with struvite formation. Precipitation tests at pH 9 identified calcium and ionic strength as most probable interferences. Calcium addition did not significantly change phosphorus removal efficiency, but decreased struvite purity because of formation of calcium phosphates when Ca:P activity ratio was greater than 0.5 to 1. Batch tests demonstrated effective calcium removal from anaerobically digested dairy manure through precipitation of calcium carbonate at pH 9 to 10 while retaining magnesium and orthophosphate, lessening hindrance to struvite formation.

Nitrogen removal in constructed wetlands using nitritation/anammox and nitrification/ denitrification: effects of influent nitrogen concentration.

Simultaneous nitritation/anammox and nitrification/denitrification (SNAND) is a promising method to increase nitrogen removal from ammonium- and nitrate-rich wastewater. This study examined the effects of influent nitrogen concentrations on plant assimilation and microbial nitrogen removal via SNAND in three free water surface wetlands. Anammox and denitrification contributed 78 and 22%, respectively, of microbial removal of total inorganic nitrogen (TIN). Nitrogen removal rates increased with influent concentrations in the low ranges of 17 to 105 mg N/L ammonium and 51 to 179 mg N/L TIN. However, nitrogen removal rates appeared to decrease with influent concentrations in the high ranges of 248 to 293 mg N/L ammonium and 348 to 391 mg N/L TIN. Plant growth was negatively affected when influent ammonium concentration exceeded 46 to 76 mg N/L. Plant assimilation contributed 11 to 47% toward TIN removal at low influent ammonium concentrations (42 to 76 mg N/L) and 4% at high influent ammonium concentrations (mean 264 mg N/L).

Effects of pH and seasonal temperature variation on simultaneous partial nitrification and anammox in free-water surface wetlands.

Design considerations to enhance simultaneous partial nitrification and anammox in constructed wetlands are largely unknown. This study examined the effects of pH and seasonal temperature variation on simultaneous partial nitrification and anammox in two free-water surface wetlands. In order to enhance partial nitrification and inhibit nitrite oxidation, furnace slag was placed on the rooting substrate to maintain different pH levels in the wetland water. The wetlands were batch operated for dairy wastewater treatment under oxygen-limited conditions at a cycle time of 7 d. Fluorescence in situ hybridization analysis found that aerobic ammonium oxidizing bacteria and anammox bacteria accounted for 42-73% of the bacterial populations in the wetlands, which was the highest relative abundance of ammonium oxidizing and anammox bacteria in constructed wetlands enhancing simultaneous partial nitrification and anammox. The two wetlands removed total inorganic nitrogen efficiently, 3.36-3.38 g/m(2)/d in the warm season with water temperatures at 18.9-24.9 °C and 1.09-1.50 g/m(2)/d in the cool season at 13.8-18.9 °C. Plant uptake contributed 2-45% to the total inorganic nitrogen removal in the growing season. A seasonal temperature variation of more than 6 °C would affect simultaneous partial nitrification and anammox significantly. Significant pH effects were identified only when the temperatures were below 18.9 °C. Anammox was the limiting stage of simultaneous partial nitrification and anammox in the wetlands. Water pH should be controlled along with influent ammonium concentration and temperature to avoid toxicity of free ammonia to anammox bacteria.

Treatment of anaerobically digested dairy manure in a two-stage biofiltration system.

High concentrations of ammonium and phosphate present a challenge to cost-effective treatment of anaerobically digested dairy manure. This study investigated the efficacy of a two-stage biofiltration system for passive treatment of digested dairy manure. The first stage pebble filters were batch loaded. When the slurry-like digested dairy manure was retained on pebble beds, soluble contaminants were removed before liquid infiltrated over 8-17 days. The pebble filters removed 70% of soluble chemical oxygen demand, 71% of soluble biochemical oxygen demand, 75% of ammonium, and 68% of orthophosphate. Nitrogen removal was attributed to the conventional nitrification - denitrification process and novel nitritation - anammox process. Aerobic ammonium oxidizing and anammox bacteria accounted for 25 and 23% of all bacteria, respectively, in the filtrate of the pebble filters. The longer it took for filtration, the greater the removal efficiency of soluble contaminants. The second stage sand filters had removal efficiencies of 17% for soluble chemical oxygen demand, 45% for soluble biochemical oxygen demand, 43% for ammonium, and 16% for orthophosphate during batch operations at a hydraulic retention time of 7 days. Aerobic ammonium oxidation and anammox were primarily responsible for nitrogen removal in the sand filters. Vegetation made an insignificant difference in treatment performance of the sand filters.

Spatial and seasonal distribution of nitrogen in marsh soils of a typical floodplain wetland in Northeast China.

Horizontal and profile distributions of nitrogen in marsh soils in different seasons were studied in a typical site within the Erbaifangzi wetland in Northeast China. Results showed that there was higher spatial heterogeneity for nitrate nitrogen (NO[Formula: see text]N) and ammonium nitrogen (NH[Formula: see text]-N), as well as available nitrogen (AN), in surface soils in July compared to that in September. Relative to July, the mean nitrogen contents in surface soils were slightly higher in September; however, in November, soils contained significantly lower NO[Formula: see text]N and NH[Formula: see text]-N, higher AN, organic nitrogen (Org-N), and total nitrogen (TN). Except for mineral nitrogen, no significant differences were observed between Org-N and TN contents in September and November. Nitrogen contents generally declined exponentially with depth along soil profiles in three sampling dates (July, September, and November), except for a significant accumulation peak of NO[Formula: see text]N at the 20-30 cm depth in September. However, NH[Formula: see text]-N contents showed a vertical alternation of "increasing and decreasing" in both July and September, while nearly kept constant with depth in November. The depth ranking of nitrogen showed the shallowest distribution for AN, followed by Org-N and TN, while deeper distributions for NO[Formula: see text]N and NH[Formula: see text]-N. TN, Org-N, and AN were significantly correlated with soil organic matter and total phosphorus. Soil pH values were significantly correlated with TN and AN contents in surface soils. Clay contents showed significant correlations with nitrogen contents except for NO[Formula: see text]N in surface soils and NH[Formula: see text]-N in profile soils. However, soil moisture was not significantly correlated with nitrogen contents among all soil samples.

Occurrence and dietary exposure risks of phthalate esters in food in the typical valley city Xi'an, Northwest China.

Diet is an important exposure pathway of phthalate esters (PAEs) for humans. A total of 174 food samples covering 11 food groups were collected from Xi'an, a typical valley city in Northwest China, and analyzed to assess the occurrence and exposure risks for PAEs in the food. Twenty-two PAEs were detected. The sum of the 22 PAEs (∑22PAEs) varied between 0.0340 and 56.8 µg/g, with a mean of 3.94 µg/g. The major PAEs were di-iso-butyl phthalate (DiBP), di-n-butyl phthalate (DnBP), bis(2-ethylhexyl) phthalate (DEHP), di-iso-nonyl phthalate (DiNP), and di-iso-decyl phthalate (DiDP), which were associated mainly with the usage of plasticizers. Bio-availability of the PAEs in the combined gastro-intestinal fluid simulant of digestion was higher than that in the single gastric or intestinal fluid simulant. Bis(2-methoxyethyl) phthalate exhibited the highest bio-availability in each of the three simulants. Bio-availability of the PAEs was negatively correlated with the molecular weight and octanol-water partition coefficient of the PAEs and positively correlated with the solubility and vapor pressure of the PAEs. The estimated daily intake (EDI) of PAEs based on national and municipal food consumption data was lower than the reference dose (RfD) of the United States Environmental Protection Agency and the tolerable dairy intake (TDI) of European Food Safety Authority (EFSA), except for the EDI of DnBP and DiBP being higher than the TDI of EFSA. Grains and vegetables were the major sources of human dietary exposure to PAEs. The hazardous quotient for human dietary exposure to PAEs was less than the critical value of 1 and the cancer risk of butyl benzyl phthalate and DEHP was in the range of 10-11-10-6, suggesting relatively low health risks. The results indicated that human exposure to DnBP, DiBP, DEHP, DiNP, and DiDP in food is considerable and a health concern.