Molecular transformation of dissolved organic matter in refinery wastewaters: Characterized by FT-ICR MS coupled with electrospray ionization and atmospheric pressure photoionization

Dissolved organic matter(DOM)in refinery wastewater is an extremely complex mixture of various organic compounds.Using mass spectrometry,it is impossible to characterize all of the DOM molecules with only one ionization source.In this study,negative-ion,electrospray ionization(ESI),positive-ion ESI,and positive-ion atmospheric pressure photoionization(APPI)were coupled with Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS)to analyze the molecular composition of DOM in a refinery wastewater stream during the treatment process.There were obvious differences in the heteroatom composition,number of DOM constituents,and chemical properties in refinery wastewater under the three ionization modes.Acidic CHO and CHOS compounds detected by(+)ESI,basic CHN and CHON compounds detected by(þ)ESI,and hydrocarbons detected by(+)APPI were analyzed to determine the molecular transformations that occurred during treatment.In an anaerobic biological treatment process,acidic CHO and CHOS compounds with a high oxygen content were preferentially removed,and acidic CHO and CHOS compounds with a low oxygen content were produced.In an aerobic biological process,acidic CHO and CHOS compounds with a low oxygen content were preferentially removed,and acidic CHO and CHOS compounds with a high oxygen content were produced.The whole biological treatment process has a poor removal efficiency for CHN and CHON compounds,and hydrocarbons.An activated carbon(AC)adsorption process removed different heteroatom compounds mainly with a low oxygen content for acidic and basic compounds.The transformation mechanism of CHO and CHOS compounds in the biological treatment process was analyzed by the Kendrick mass defect(KMD)theory and a mass difference network analysis.In the anaerobic process,large amounts of oxygenated CHO and CHOS compounds were degraded by decarboxylation,deoxydation,demethoxylation,and dehydration reactions,and converted to lower oxygen content compounds.In the aerobic processes,these low oxygen CHO and CHOS compounds mainly underwent carboxylation and oxidation reactions.This study determined the transformation characteristics and mechanisms of different types of organic compounds in refinery wastewater during the treatment process.The results provide guidance for the design and optimization of technologies for refinery wastewater treatment.

Treatment of Slightly Polluted Wastewater in an Oil Refinery Using a Biological Aerated Filter Process

The slightly polluted wastewater from oil refinery contains some COD, oil pollutants and suspended solids （SS）. A small-scale fixed film biological aerated filter （BAF） process was used to treat the wastewater. The influences of hydraulic retention time （HRT）, air/water volume flow ratio and backwashing cycle on treatment efficiencies were investigated. The wastewater was treated by the BAF process under optimal conditions： the HRT of 1.0 h, the air/water volume flow ratio of about 5 ： 1 and the backwashing cycle of every 4-7 days. The results showed that the average removal efficiency of COD, oil pollutants and SS was 84.5%, 94.0% and 83.4%, respectively. And the average effluent concentration of COD, oil pollutants and SS was 12.5, 0.27, 14.5 mg·L^-1, respectively. The experimental results demonstrated that the BAF process is a suitable and highly efficient method to treat the wastewater.

Pretreatment of super viscous oil wastewater and its application in refinery

Wastewater from super viscous oil processing cannot be effectively treated by conventional wastewater treatment plants in refineries because of its high concentration of various organic pollutants. In order to resolve this problem, a number of investigations were conducted in our work to understand the physicochemical properties, sedimentation, demulsification and pretreatment of such super viscous oil refinery wastewater. The results showed that the key issues for pretreatment of this wastewater were： （1） Optimized process parameters were used in the sedimentation and demulsification processes for oil removal to effectively recover oil and remove scum from wastewater; （2） A suitable flocculation process was selected to minimize oil, suspended solids （SS） and chemical oxygen demand （CODcr）. A pretreatment process including three continuous steps： oil removal by sedimentation, oil removal by demulsification, and flotation separation, was proposed and applied in Liaohe Petrochemical Company, PetroChina and the oil content in effluents was less than 200 mg/L and CODcr less than 2,500 mg/L, which completely met the requirement for influent of the conventional wastewater treatment plant, and the recovered super viscous oil reached 5,873 tons in the initial year in Liaohe Petrochemical Company, PetroChina.

Efficient ozonation of reverse osmosis concentrates from petroleum refinery wastewater using composite metal oxideloaded alumina

Novel Mn–Fe–Mg-and Mn–Fe–Ce-loaded alumina（Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3） were developed to catalytically ozonate reverse osmosis concentrates generated from petroleum refinery wastewaters（PRW-ROC）. Highly dispersed 100–300-nm deposits of composite multivalent metal oxides of Mn（Mn^2＋）, Mn^3＋,and Mn^4＋, Fe（Fe^2＋）and Fe^3＋ and Mg（Mg^2＋）, or Ce（Ce^4＋） were achieved on Al2O3 supports. The developed Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3 exhibited higher catalytic activity during the ozonation of PRW-ROC than Mn–Fe/Al2O3, Mn/Al2O-3, Fe/Al2O3, and Al2O3. Chemical oxygen demand removal by Mn–Fe–Mg/Al2O3-or Mn–Fe–Ce/Al2O3-catalyzed ozonation increased by 23.9% and23.2%, respectively, in comparison with single ozonation.Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3 notably promoted áOH generation and áOH-mediated oxidation. This study demonstrated the potential use of composite metal oxide-loaded Al2O3 in advanced treatment of bio-recalcitrant wastewaters.

Rapid aerobic granulation using biochar for the treatment of petroleum refinery wastewater

Aerobic granular sludge technology has great potential for the treatment of petroleum refinery wastewater.However,strategies to shorten the granulation time and improvement the stability still need to be developed.In this work,biochar was prepared from waste petroleum activated sludge(biochar-WPS) and used in a sequencing batch reactor for the treatment of petroleum refinery wastewater.Biochar-WPS presented the surface area of 229.77 m2/g,pore volume of 0.28 cm3/g,H/C and O/C atomic ratios of 0.42 and 0.21,respectively.The porous structure and a high degree of hydrophilicity were found to facilitate microbial colonization and adhesion as well as particle aggregation.Application of biochar-WPS resulted in the formation of more substantial and stable aerobic granules(~66% of granules> 0.46 mm diameter) 15 days earlier compared with the control.The addition of biochar-WPS enhanced the average removal efficiency of chemical organic demand(~3%),oil(~4%)and total nitrogen(~10%) over the control.Increased microbial richness and diversity were observed within the formed granules and had an increased(~4%) proportion of denitrifying bacteria.These results indicate that an aerobic granulation mechanism using biochar-WPS is a feasible option for the treatment of petroleum refinery wastewater.

Removal of Heavy Metals （Copper, Manganese and Zinc） from Industrial Wastewater of Baiji Refinery by Granular Activated Carbon

The aim of the present work is to remove heavy metals （copper, manganese, and zinc） from industrial wastewater of Baiji refinery using GAC （granular activated carbon）. The most important factors affecting adsorption process have been studied, which are granular activated carbon thickness, H, inlet pollutant concentration, Cv, and liquid hourly space velocity, LHSV. All experiments were performed under constant temperature at 25℃ and pH = 7. The experimental apparatus was designed and constructed to enable controlling of the operating conditions. Employing five levels for each of H and LHSV and three levels for Co required 75 runs for each metal. Box-Wilson method was used to reduce the number of experiments to 15 for each metal. The results indicated that copper, manganese, and zinc can be completely removed from wastewater using activated carbon. However, breakthrough time for zinc is low. It is also shown that breakthrough time （TB） and exhaustion time （TE） are inversely proportional with pollutant concentration and LHSV （liquid hour space velocity） while it is directly proportional with the thickness of activated carbon column.

An alternative treatment process for upgrade of petroleum refinery wastewater using electrocoagulation

An electrocoagulation treatment process was developed for treatment and upgrade of petroleum refinery effluent （wastewater）, instead of the conventional methods, which can consume higher amounts of chemicals and produce larger amounts of sludge. The effect of the operation parameters, such as current density, initial pH, anode material, anode dissolution, energy consumption and electrolysis time, on treatment efficiency was investigated. The experimental results showed that the effluent can be effectively treated under optimal conditions. Fourier transform infrared （FTIR） analysis of the effluent, and scanning electron microscopy （SEM） coupled with energy dispersive analysis of X-rays （EDAX） of the sludge produced, revealed that the unwanted pollutants can be eliminated. The electrocoagulation treatment process was assessed by using the removal efficiency of chemical oxygen demand （COD）, total suspended solids （TSS）, and the general physicochemical characteristics of wastewater, and the results showed that the electrocoagulation is an efficient process for recycling of petroleum wastewater; it is faster and provides better quality of treated water than the conventional methods.

Study on Immobilized Algal Cells for Treatment and Recycle of Refinery Wastewater

Compared to the algal oxidation pond, treatment of wastewater using the immobilized algal cell technology has excellent effect, which not only can effectively avoid the disadvantage of oxidation pond, but can also remarkably improve the efficiency of treating system and the effluent quality. When the treating system operates umder an optimal control conditions, such as a 55% loading rate, an illumination intensity of 2500-3500 lux and a hydraulic residence time of 4 hours, the COD and ammonia nitrogen removal can reach 90%. Water after deep treatment can comply with the requirement of the refinery for the quality of recycled water.

The Treatment of Polymer-bearing Wastewater from Refinery by Fenton Oxidation - Activated Carbon Adsorption

To solve the problem of polymer-bearing effluent of crude oil not reaching the standard,deep treatment system of Fenton oxidation-activated carbon adsorption is established in one refinery,and the most suitable condition of Fenton oxidation reaction is determined.Operation results show that CODCrconcentration of effluent treated by the system could be lower than 50 mg/L,and ammonia nitrogen content is less than 3 mg/L,which meets design requirement.

Study on Application of Novel Flocculating Agent in Treating Refinery Wastewater with High Concentration of Pollutants

After conducting a lot of screening experiments the appropriate flocculating formulations for treating high-concentration wastewater discharged from a certain refinery were selected. The oil removal rate and COD removal achieved by these flocculating formulations were better than that achieved by the conventional compound formulation consisting of polyaluminium chloride(PAC) and polyacrylamide(PAA) . Addition of an oil/water separating agent to the formulation could improve its oil removal performance to facilitate the oil/water separation of the oil-in-water emulsion in the high-concentration wastewater along with improved adaptability of the formulation to the wastewater containing high concentration of pollutants. This flocculating agent has promising prospects for commercial application.

Efficiency and effectiveness of systems for the treatment of domestic wastewater based on subsurface flow constructed wetlands in Jarabacoa, Dominican Republic

Constructed wetlands(CwW)are well known nature-based systems for water treatment.This study evaluated the efficiency and effectiveness of seven domestic wastewater treatment systems based on horizontal flow CWs in Jarabacoa,the Dominican Republic.The results showed that the CWs were efficient in reducing the degree of contamination of wastewater to levels below the Dominican wastewater discharge standards for parameters such as the 5-day biochemical oxygen demand(BOD5)and chemical oxygen demand,but not for the removal of phosphorus and fecal coliforms.In addition,a horizontal flow subsurface wetland in the peri-urban area El Dorado was evaluated in terms of the performance of wastewater treatment in tropical climatic conditions.The concentrations of heavy metals,such as zinc,copper,chromium,and iron,were found to decrease in the effluent of the wetland,and the concentrations for nickel and manganese tended to increase.The levels of heavy metals in the effluent were lower than the limit values of the Dominican wastewater discharge standards.The construction cost of these facilities was around 200 USD per population equivalent,similar to the cost in other countries in the same region.This study suggested some solutions to the improved performance of CWs:selection of a microbial flora that guarantees the reduction of nitrates and nitrites to molecular nitrogen,use of endemic plants that bioaccumulate heavy metals,combination of constructed wetlands with filtration on activated carbon,and inclusion of water purification processes that allow to evaluate the reuse of treated water.

Molecular investigation into the transformation of recalcitrant dissolved organic sulfur in refinery sour water during stripping process

Refinery sour water primarily originates from the tops of towers in various units and coker condensate,and cannot be discharged directly to a wastewater treatment plant due to high levels of chemical oxygen demand(COD)and organic sulfur contents.Even after the recovery of H_(2)S from the sour water by the stripping process,the effluent still contains a high concentration of dissolved organic sulfur(DOS),which can have a huge bad influence.While chemical composition of dissolved organic matter(DOM)in refinery wastewater has been extensively studied,the investigation of recalcitrant DOS from sour waters remains unclear.In the present study,chemical composition of sour water DOMs(especially DOS)was investigated using fluorescence spectroscopy(excitation-emission matrix,EEM)and mass spectrometry,including gas chromatography-mass spectrometry(GC-MS)and high-resolution Orbitrap MS.The GC-MS and EEM results showed that volatile and low-aromaticity compounds were effectively removed during the stripping process,while compounds with high hydrophilicity and humification degree were found to be more recalcitrant.The Orbitrap MS results showed that weak-polar oxygenated sulfur compounds were easier to be removed than oxygenated compounds.However,the effluent still contained significant amounts of sulfur-containing compounds with multiple sulfur atoms,particularly in the form of highly unsaturated and aromatic compounds.The Orbitrap MS/MS results of CHOS-containing compounds from the effluent indicate that the sulfur atoms may exist as sulfonates,disulfide bonds,thioethers.Understanding the composition and structure of sour water DOS is crucial for the development of effective treatment processes that can target polysulfide compounds and minimize their impact on the environment.

Textile dyeing wastewater negatively influences the hematological profile and reproductive health of male Swiss albino mice

Objective:To determine the effects of textile dyeing industrial wastewater on the hematological parameters and reproductive health including histoarchitecture of male gonad(testes)of mice.Methods:Twenty-four Swiss albino mice at 4-weeks old were divided into four groups(n=6 per group).Mice of group 1 supplied with normal drinking water were served as the control group.Mice of group 2,3 and 4 were supplied normal drinking water mixed with textile dyeing wastewater at 5%,10% and 20% concentration,respectively.After completing 24 weeks of treatment,different hematological profile,weight of testes,gonadosomatic index(GSI),sperm concentration and morphology were measured.Moreover,histopathological changes in testes were examined.Results:Hematocrit value and hemoglobin concentrations were decreased in all groups of wastewater-treated mice compared to the control group.Likewise,weight of testes,GSI and sperm concentration were decreased significantly in wastewater-treated mice in comparison to the control group.The percentage of morphologically healthy epididymal sperm was significantly reduced in wastewater-treated mice.Histopathological examination revealed degenerative changes in seminiferous tubules,a smaller number of spermatogenic cells,elongation of seminiferous tubules and degenerative changes of seminiferous tubules in wastewater-treated mice.Conclusions:Textile dyeing wastewater has harmful effects on hematological profile and reproductive health of male mice.

Metagenomic Insight Reveals the Microbial Structure and Function of the Full-Scale Coking Wastewater Treatment System:Gene-Based Nitrogen Removal

Microbial communities play crucial roles in pollutant removal and system stability in biological systems for coking wastewater(CWW)treatment,but a comprehensive understanding of their structure and functions is still lacking.A five month survey of four sequential bioreactors,anoxic 1/oxic 1/anoxic 2/oxic 2(A1/O1/A2/O2),was carried out in a full-scale CWW treatment system in China to elucidate operational performance and microbial ecology.The results showed that A1/O1/A2/O2 had excellent and stable performance for nitrogen removal.Both total nitrogen(TN;(17.38±6.89)mgL1)and ammonium-nitrogen(NH4 t-N;(2.10±1.34)mg·L^(-1))in the final biological effluent satisfied the Chinese national standards for CWW.Integrated analysis of 16S ribosome RNA(rRNA)sequencing and metagenomic sequencing showed that the bacterial communities and metagenomic function profiles of A1 and O1 shared similar functional structures,while those of A2 significantly varied from those of other bioreactors(p<0.05).The results indicated that microbial activity was strongly connected with activated sludge function.Nitrosospira,Nitrosomonas,and SM1A02 were responsible for nitrification during the primary anoxic-oxic(AO)stage and Azoarcus and Thauera acted as important denitrifiers in A2.Nitrogen cycling-related enzymes and genes work in the A1/O1/A2/O2 system.Moreover,the hao genes catalyzing hydroxylamine dehydrogenase(EC 1.7.2.6)and the napA and napB genes catalyzing nitrate reductase(EC 1.9.6.1)played important roles in the nitrification and denitrification processes in the primary and secondary AO stages,respectively.The mixed liquor suspended solids(MLSS)/total solids(TS),TN removal rate(RR),total organic carbon(TOC)(RR),and NH_(4)^(+)t-N(RR)were the most important environmental factors for regulating the structure of core bacterial genera and nitrogen-cycling genes.Proteobacteria were the potential main participants in nitrogen metabolism in the A1/O1/A2/O2 system for CWW treatment.This study provides an original and comprehensive understanding of the microbial community and functions at the gene level,which is crucial for the efficient and stable operation of the full-scale biological process for CWW treatment.

Performance Evaluation of the Halophilic Crude Oildegrading Bacterial Consortium XH-1 for Oilfield Wastewater Treatment

A total of 14 halophilic hydrocarbon-degrading strains were isolated from crude oil-contaminated sites,using petroleum as the sole carbon and energy source.Among these,four highly efficient strains were selected to create the mixed bacterial agent XH-1.These four strains were identified through 16S rRNA gene-based sequencing as belonging to Acinetobacter,Bacillus paramycoides,Rhodococcus sp.,and Enterobacter sp.,respectively.The optimal cultivation time for the mixed consortium XH-1 was found to be 48 h,and a nitrogen-phosphorus molar ratio of 10:1 was determined to be beneficial for crude oil degradation.XH-1 showed notable crude oil degradation even at a salinity of up to 30 g/L,with little inhibition observed at sulfide concentrations as high as 150 mg/L and initial oil concentrations of 500 mg/L.Gas chromatography analysis revealed that XH-1 was able to efficiently degrade C9–C29 n-alkanes.Moreover,a bio-contact oxidation reactor enhanced by XH-1 showed promising results in treating oilfield wastewater.These findings suggest that XH-1 can be applied for the treatment of oilfield wastewater.

Facile synthesis of composite polyferric magnesium-silicate-sulfate coagulant with enhanced performance in water and wastewater

The coagulation process is a widely applied technology in water and wastewater treatment.Novel composite polyferric mag-nesium-silicate-sulfate(PFMS)coagulants were synthesized using Na_(2)SiO_(3)·9H_(2)O,Fe_(2)(SO_(4))_(3),and MgSO_(4) as raw materials in this paper.The effects of aging time,Fe:Si:Mg,and OH:M molar ratios(M represents the metal ions)on the coagulation performance of the as-pre-pared PFMS were systematically investigated to obtain optimum coagulants.The results showed that PFMS coagulant exhibited good co-agulation properties in the treatment of simulated humic acid-kaolin surface water and reactive dye wastewater.When the molar ratio was controlled at Fe:Si:Mg=2:2:1 and OH:M=0.32,the obtained PFMS presented excellent stability and a high coagulation efficiency.The removal efficiency of ultraviolet UV254 was 99.81%,and the residual turbidity of the surface water reached 0.56 NTU at a dosage of 30 mg·L^(-1).After standing the coagulant for 120 d in the laboratory,the removal efficiency of UV254 and residual turbidity of the surface wa-ter were 88.12%and 0.68 NTU,respectively,which accord with the surface water treatment requirements.In addition,the coagulation performance in the treatment of reactive dye wastewater was greatly improved by combining the advantages of magnesium and iron salts.Compared with polyferric silicate-sulfate(PFS)and polymagnesium silicate-sulfate(PMS),the PFMS coagulant played a better decolor-ization role within the pH range of 7-13.

Ultrahydrophobic melamine sponge via interfacial modification with reduced graphene oxide/titanium dioxide nanocomposite and polydimethylsiloxane for oily wastewater treatment

Three-dimensional(3D)porous absorbents have attracted significant attention in the oily wastewater treatment technology due to their high porosity and elasticity.Given their amphiphilic surface,they have a propensity to simultaneously absorb water and oil,which restricts their range of applications.In this study,a reduced graphene oxide and titanium dioxide nanocomposite(rGO/TiO_(2))was used to fabricate an ultra-hydrophobic melamine sponge(MS)through interfacial modification using a solution immersion technique.To further modify it,poly-dimethylsiloxane(PDMS)was grafted onto its surface to establish stronger covalent bonds with the composite.The water contact angle of the sponge(rGO/TiO_(2)/PDMS/MS)was 164.2°,which satisfies the condition for ultrahydrophobicity.The evidence of its water repellency was demonstrated by the Cassie-Baxter theory and the lotus leaf effect.As a result of the increased density of rGO/TiO_(2)/PDMS/MS,it recorded an initial capacity that was 2 g/g lower than the raw MS for crude oil absorption.The raw MS retained 53% of its initial absorption capacity after 20 cycles of absorption,while rGO/TiO_(2)/PDMS/MS retained 97%,suggesting good recyclability.Excellent oil and organic solvent recovery(90%-96%)was demonstrated by rGO/TiO_(2)/PDMS/MS in oil-water combinations.In a continuous separation system,it achieved a remarkable separation efficiency of 2.4×10^(6)L/(m^(3)·h),and in turbulent emulsion separation,it achieved a demulsification efficiency of 90%-91%.This study provides a practical substitute for massive oil spill cleaning.

Effects of Coagulation and Ozonation Pretreatments on Biochemical Treatment of Fluid Catalytic Cracking Wastewater

Fluid catalytic cracking (FCC) salty wastewaters, containing quaternary ammonium compounds (QACs), are very difficult to treat by biochemical process. Anoxic/oxic (A/O) biochemical system, based on nitrification and denitrification reactions, was used to assess their possible biodegradation. Because of the negative effects of high salt concentration (3%), heavy metals and toxic organic matter on microorganisms’ activities, some techniques consisting of dilution, coagulation and flocculation, and ozonation pretreatments, were gradually tested to evaluate chemical oxygen demand (COD), ammonia-nitrogen (ammonia-N) and total nitrogen (TN) removal rates. In this process of FCC wastewater, starting with university-domesticated sludge, the ammonia-N and TN removal rates were worst. However, when using domesticated SBR’s sludge and operating with five-fold daily diluted influent (thus reducing salt concentration), the ammonia-N removal reached about 57% while the TN removal rate was less than 37% meaning an amelioration of the nitrification process. However, by reducing the dilution factors, these results were inflected after some days of operation, with ammonia-N removal decreasing and TN barely removed meaning a poor nitrification. Even by reducing heavy metals concentration with coagulation/flocculation process, the results never changed. Thereafter, by using ozonation pre-treatment to degrade the detected organic matter of di-tert-butylphenol and certain isoparaffins, COD, ammonia-N and TN removal rates reached 92%, 62% and 61%, respectively. These results showed that the activities of the microorganisms were increased, thus indicating a net denitrification and nitrification reactions improvement.

Advances Treatment Technologies in Chemical Industry Wastewater

The main treatment methods of chemical wastewater were reviewed.Physical,chemical,and biochemical treatment technologies effective for removing those pollutants were presented with their applicability,effectiveness and advantages.The problems facing the wastewater treatment in the petroleum chemical industry and coal chemical industry were introduced.In the end,the new progress and trend of the processes were overviewed.

Progress of Electrocatalytic Technology in Treating Organic Chemical Wastewater

In recent years,extensive research has been conducted on the preparation of high catalytic performance electrodes and the development of electrocatalytic water treatment processes.This article introduces the basic principles of electrochemical water treatment,the preparation of electrode materials,and the research progress of electrocatalytic technology for degrading organic chemical wastewater.It analyzes the problems faced by electrocatalytic degradation of organic chemical wastewater and looks forward to the development trend of electrocatalytic technology in the field of organic chemical wastewater treatment.