Numerical Analysis of Indoor Air Characteristics and Window Screen Influence on Particulate Matter Dispersion in a Childcare Center Using Computational Fluid Dynamics.

Indoor exposure to outdoor pollutants adversely affects health, varying with building dimensions and particularly ventilation that have critical role on their indoor dispersion. This study assesses the impact of outdoor air on indoor air quality in a child care center. Computational fluid dynamics was utilized to analyze the dispersion of particulate matter, with a specific focus on window screens featuring 6 distinct pore sizes ranging from 0.8 mm to 2 mm and 2 different thicknesses of 0.5 mm and 0.1 mm. Results indicate that the presence of a window screen offers significant advantages in controlling particle infiltration compared to scenarios without a screen, as larger particles tend to pass directly through the window within the breathing zone. The scenario without window screens minimizes pressure drop but lacks enhanced particle capture capabilities. However, for effective particle reduction, the window screen with a pore size of 0.8 mm (R0.8T2) and a thickness of 0.5 mm proves to be the most beneficial, achieving the particle filtering efficiency of approximately 54.16%, while the larger window screen with a pore size of 2 mm and a thickness of 1 mm exhibits the lowest efficiency at about 23.85%. Nonetheless, screens with very small sizes are associated with a high-pressure drop, impacting energy efficiency, and overall window performance. Larger pores with smaller thicknesses (0.5 mm) reduced particle count by approximately 45.97%. Therefore, the significance of window screen thickness beyond pore size for particle reduction efficiency is highlighted, emphasizing screens' role in indoor air quality and health protection.

Ciprofloxacin Electrochemical Sensor Using Copper-Iron Mixed Metal Oxides Nanoparticles/Reduced Graphene Oxide Composite.

The harmful effects of antibiotic proliferation on the environment and its persistent nature are urgent global problems. Ciprofloxacin (CIP) is a fluoroquinolone-class antibiotic agent used widely to treat pathogen-related diseases in humans and animals. Its excretion into surface water causes antibiotic resistance in microbes, resulting in difficult-to-treat or untreatable infectious diseases. This study developed a simple and efficient electrochemical sensor to detect CIP. Hydrothermal chemistry was utilized to synthesize an electrophotocatalytic composite of copper-iron mixed metal oxides (CIMMO) on reduced graphene oxide (rGO) (CIMMO/rGO). The composite was employed in an electrochemical sensor and exhibited outstanding performance in detecting CIP. The sensor was operated in differential pulse voltammetry (DPV) mode under light source illumination. The sensor yielded a linear response in the concentration range of 0.75 × 10-9-1.0 × 10-7 mol L-1 CIP and showed a limit of detection (LOD) of 4.74 × 10-10 mol L-1. The excellent sensing performance of the composite is attributable to the synergic effects between CIMMO nanoparticles and rGO, which facilitate photoinduced electron-hole separation and assist in the indirect electrochemical reactions/interactions with CIP.

Microplastics in wastewater and sludge from centralized and decentralized wastewater treatment plants: Effects of treatment systems and microplastic characteristics.

Domestic wastewater treatment plants (WWTPs) play a vital role in limiting the release of microplastics (MP) into the environment. This study examined MP removal efficiency from five centralized and four decentralized domestic WWTPs in Bangkok, Thailand. MP concentrations in wastewater and sludge were comparable between centralized and decentralized WWTPs, despite these decentralized WWTPs serving smaller populations and having limited treatment capacity. The elimination of MPs ranged from 50 to 96.8% in centralized WWTPs and 14.2-53.6% in decentralized WWTPs. It is noted that the retained MPs concentrations in sludge ranged from 20,000 to 228,100 MP/kg dry weight. The prevalence of synthetic fibers and fragments could be attributed to their pathways from laundry or car tires, and the accidental release of a variety of plastic wastes ended up in investigated domestic WWTPs. Removal of MPs between the centralized and decentralized WWTPs was influenced by several impact factors including initial MP concentrations, longer retention times, MP fragmentation, and variations of MP concentrations in sludge leading to different activated sludge process configurations. Sewage sludge has become a primary location for the accumulation of incoming microplastics in WWTPs. The MPs entering and leaving each unit process were varied due to the unique characteristics of MPs, and their different treatment efficiencies. While the extended hydraulic retention period in decentralized WWTPs decreased the MP removal efficacy, the centralized WWTP with the two-stage activated sludge process achieved the highest MP removal efficiency.

Combo chloro-photosynthetic device and applications for greenhouse gas reduction campaign and smart agriculture.

The increasing carbon dioxide (CO2) levels in the air pose a direct threat to all living organisms and the environment. Leveraging the ability of plants to absorb CO2 is one of the most effective methods for countering these rising CO2 levels. The present study aimes to develop a combo photosynthetic and chlorophyll-a sensor based on Non-Dispersive Infrared (NDIR) spectroscopy and an optical method. This sensor enables simultaneous, intensive measurement of net photosynthesis and chlorophyll-a content and yields accurate information. Comparative analysis of the efficacy of the sensors to that of a commercial instrument demonstrated that the measurement values obtained from the developed photosynthetic and chlorophyll-a sensors were not significantly different from those acquired with the commercial instrument (portable photosynthesis system LI-6400) and chlorophyll metre (SPAD-502), with a 95 % confidence level. Furthermore, the developed photosynthetic sensor could be used as a new correlation unit for chlorophyll-a content and net photosynthesis. Therefore, the sensor can be used to propose effective plantation processes to reduce atmospheric CO2 levels and in smart farming systems to control the quality of yields.

Seasonal effects, spatial distribution, and possible sources of microplastics in the Chao Phraya River estuary, Thailand.

Microplastics (MPs) in estuaries are sources of plastic debris that enter the marine environment. However, there is limited information on the seasonal effect on the accumulation of MPs in the estuaries of Thailand. The abundance and spatial distribution of MPs in the dry and wet seasons were investigated in the Chao Phraya River estuary, and possible emission sources were traced. Dominant factors affecting the distribution patterns of MPs have also been reported. All collected water samples contained MPs, with a mean abundance of 4.0 ± 2.8 × 105 particles/km2 in the wet season and 5.2 ± 3.3 × 105 particles/km2 in the dry season. Fragments were mostly observed, with polypropylene and polyethylene being the dominant polymers. The findings also showed that accumulation of MPs was directly influenced by the river discharge rate into the estuary. Further, the spatial distribution of MPs was closely related to seasonal variations in sea surface currents. Microplastic pollution status with seasonal variations and possible emission sources could provide important information to the government and local environmental organizations for MP pollution prevention and future MP studies in estuarine environments.

Electrochemical Sensor Based on a Composite of Reduced Graphene Oxide and Molecularly Imprinted Copolymer of Polyaniline-Poly(o-phenylenediamine) for Ciprofloxacin Determination: Fabrication, Characterization, and Performance Evaluation.

Contamination of antibiotics in water is a major cause of antibiotic resistance (ABR) in pathogens that endangers human health and food security worldwide. Ciprofloxacin (CIP) is a synthetic fluoroquinolone (FQ) antibiotic and is reportedly present in surface water at a concentration exceeding the ecotoxicological predicted no-effect concentration in some areas. This study fabricated a CIP sensor using an electropolymerized molecularly imprinted polymer (MIP) of polyaniline (PANI) and poly(o-phenylenediamine) (o-PDA) with CIP recognition sites. The MIP was coated on a reduced graphene oxide (rGO)-modified glassy carbon electrode (rGO/GCE) and operated under a differential pulse voltammetry (DPV) mode for CIP detection. The sensor exhibited an excellent response from 1.0 × 10-9 to 5.0 × 10-7 mol L-1 CIP, showing a sensor detection limit and sensitivity of 5.28 × 10-11 mol L-1 and 5.78 µA mol-1 L, respectively. The sensor's sensitivity for CIP was 1.5 times higher than that of the other tested antibiotics, including enrofloxacin (ENR), ofloxacin (OFX), sulfamethoxazole (SMZ), and piperacillin sodium salt (PIP). The reproducibility and reusability of the sensor devices were also studied.

Rapid and efficient removal of organic matter from sewage sludge for extraction of microplastics.

Microplastic pollution is recognized as an emerging global issue; however, no standardized method for the extraction of these pollutants from the environment currently exists and existing methods are ineffective for specific environmental matrices. An appropriate organic matter removal method is essential for the extraction of microplastics from organic-rich sludge to minimize interference during their identification and enhance compatibility of the identification steps. The present study aimed to establish an effective technique for the digestion of organic matter-rich sludge using hydrogen peroxide and Fenton's reagent at varying temperatures, times, and concentrations of an iron catalyst. The organic matter removal efficiency of the five protocols utilized varied from 81.5 % to 87.1 %. Polymers such as polyvinyl chloride (PVC), high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), and polystyrene (PS) retained most of their physical and chemical properties after the treatments, with minor changes in the surface area, weight, and FTIR spectra properties. Polyethylene terephthalate (PET), PET fiber, polyamide (PA) fiber, and polymethyl methacrylate (PMMA) fiber were significantly degraded via treating with H2O2 at 50 °C for 24 h. Protocol 4, treating with Fenton's reagent (H2O2 (30 %) + (0.05 M) FeSO4.7H2O) at 50 °C for 1 h is proposed as a rapid and effective method for the removal of organic matter from sludge. In addition to its rapidity, this method minimally impacts most polymers, and its high organic matter removal efficiency is associated with a significant reduction of suspended solids in sludge. The present study provides a validated approach that facilitates as an effective organic removal step during the extraction of MPs in sludge.

Exposure, risk and predictors of hexabromocyclododecane and Tetrabromobisphenol-A in house dust from urban, rural and E-waste dismantling sites in Thailand.

In this study, for the first time, we determined concentrations of hexabromocyclododecane (HBCDD) and tetrabromobisphenol-A (TBBPA) in house dust and estimated human exposure to these substances in houses located in an e-waste dismantling site and in urban and rural residential areas of Thailand. The median HBCDD concentration in urban residential houses (2.10 ng g-1) was similar to that in houses in an e-waste dismantling site (2.05 ng g-1, p > 0.05) and slightly higher than that in rural residential houses (1.11 ng g-1, p > 0.05). In contrast, significantly higher TBBPA concentrations were present in house dust from an e-waste dismantling site (median = 720 ng g-1; range = 44-2300 ng g-1) compared to those in urban (68.6 ng g-1; 3.5-300 ng g-1, p < 0.001) and rural residential areas (17 ng g-1; 2.0-201 ng g-1, p < 0.001). TBBPA concentrations increased with the increasing presence of electronic devices and a decreasing distance to the e-waste dismantling site. These results suggest that e-waste dismantling activities may contribute to TBBPA contamination of house dust. The median estimated daily intake (EDI) of HBCDD and TBBPA through dust ingestion for toddlers exceeded that for children and adults. However, EDI values for HBCDD and TBBPA from all age groups were below the oral reference dose guideline value suggested by the US National Research Council and National Toxicology Program (NTP).

Horizontal variation of microplastics with tidal fluctuation in the Chao Phraya River Estuary, Thailand.

Microplastic (MP) pollution in estuarine environments is poorly characterized globally, although they are extensive buffer regions between terrestrial, freshwater and seawater environments. This research aims to investigate MP pollution levels and variations of MPs abundance with tidal fluctuation. Fourteen samples were collected from the surface water of the Chao Phraya River Estuary, Thailand using the Manta net at flood and ebb tides. The average abundance of microplastics at flood tide was 5.16 × 105 particles/km2 and at ebb tide was 3.11 × 105 particles/km2. The abundance of microplastics in the estuary was directly related to the tidal fluctuation, creating an accumulation of microplastics in the study area. Polypropylene, polyethylene, and polystyrene were the most common polymers. The findings provide important information on the pollution status of microplastics in the Chao Phraya River Estuary and the variation of suspended microplastics with tidal fluctuation should be considered in future estuarine microplastic studies.

Bioremoval and tolerance study of sulfamethoxazole using whole cell Trichoderma harzianum isolated from rotten tree bark.

Antibiotic contamination raises concerns over antibiotic resistance genes (ARGs), which can severely impact the human health and environment. Sulfamethoxazole (SMX) is a widely used antibiotic that is incompletely metabolized in the body. In this study, the research objectives were (1) to isolate the native strain of Trichoderma sp. from the environment and analyze the tolerance toward SMX concentration by evaluating fungal growth, and (2) to investigate the potential of SMX removal by fungi. The potential fungi isolated from rotten tree bark showed 97% similarity to Trichoderma harzianum (Accession no. MH707098.1). The whole cell of fungi was examined in vitro; the strain Trichoderma harzianum BGP115 eliminated 71% of SMX after 7 days, while the white rot fungi Trametes versicolor, demonstrated 90% removal after 10 days. Furthermore, the tolerance of fungal growth toward SMX concentration at 10 mg L-1 was analyzed, which indicated that Trichoderma harzianum BGP115 (the screened strain) exhibited more tolerance toward SMX than Trametes versicolor (the reference strain). The screened fungi isolated from rotted tree bark demonstrated the ability of SMX bioremoval and the potential to be tolerant to high concentrations of SMX.

Levels of perfluorinated compounds (PFCs) in groundwater around improper municipal and industrial waste disposal sites in Thailand and health risk assessment.

The aims of this study were to examine the levels of perfluorinated compounds (PFCs) in groundwater around improperly developed municipal and industrial waste disposal sites, including estimating non-cancer risk and cancer risk from ingestion of the groundwater. A total of 27 groundwater samples were collected from two cities in Thailand, Ayutthaya and Chonburi. Seven target compounds were extracted by solid phase extraction (SPE) and analyzed by high-performance liquid chromatography-tandem mass spectrometer (HPLC-MS/MS). The results showed that the total PFCs in groundwater around municipal waste disposal sites (MWDSs) varied from 1.68 to 7.75 ng/L. In groundwater around the industrial waste disposal site (IWDS), total PFCs varied from 2.64 to 42.01 ng/L, which were significantly different from those found in groundwater around the MWDSs at p < 0.01. PFOS and PFOA were ubiquitous in both areas, while perfluorohexane sulfonate (PFHxS) was frequently found in the samples around IWDS. The findings possibly suggest that PFHxS has been introduced for use as an alternative substance for most current C8 and higher due to it having shorter chain length and shorter half-lives. The results for both non-cancer risk and cancer risk in all samples were acceptable.

Study of hybrid membrane filtration and photocatalysis for removal of perfluorooctanoic acid (PFOA) in groundwater.

Groundwater contamination in Thailand from leaking of leachate due to improper solid waste disposal can cause contamination by PFOA (one of the perfluorinated compounds). This study proposed a new idea for the removal of PFOA from groundwater using a combination of membrane filtration and photocatalysis. Spiked groundwater samples were treated by nanofiltration and the rejected part was sent to a UV contact tank for photocatalysis. All samples were analyzed by high-performance liquid chromatography-tandem mass spectrometer (HPLC-MS/MS). The results showed that the removal efficiency of nanofiltration was 99.62%, and the rejected part was degraded by photocatalysis at an efficiency of 59.64%. Thus, the contaminants released to the environment were only 34.23%, which is around three times lower than nanofiltration alone. The results of this technical feasibility study proved that hybrid membrane filtration and photocatalysis are able to remove and degrade the contaminants in the rejected part significantly before being released to the environment, which has been the biggest gap in the processing of membrane filtration, and should be studied further in other aspects, such as fouling effects, energy consumption, and operating costs in a long-term pilot run.

Determination and health risk assessment of enrofloxacin, flumequine and sulfamethoxazole in imported Pangasius catfish products in Thailand.

The goals of this study were to determine the levels of three antibiotics - enrofloxacin, flumequine and sulfamethoxazole - in Pangasius catfish products imported into Thailand and to assess the health risks from consumption. To extract these antibiotic residues, acetonitrile, methanol and a small amount of formic acid were used as solvents. Determination of the antibiotics after extraction steps was carried out by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) technique. The results showed that 14 and 3 samples of Pangasius catfish products were contaminated with enrofloxacin and sulfamethoxazole, respectively. No flumequine residue was found. While the concentration levels of these antibiotics in most contaminated samples were lower than the European Union (EU) standard, one sample was found to contain sulfamethoxazole at 245.91 µg kg-1, which was higher than the EU standard (100 µg kg-1), indicating the likelihood that some contaminated freshwater fish products are widely distributed in Thai markets. Notably, the concentration levels of enrofloxacin in samples of Pangasius catfish with skin were higher than in non-skin products, suggesting that products with skin might retain more antibiotic residues than non-skin products. Although the hazard quotient showed that consuming imported Pangasius catfish products, based on the current consumption rate, will not adversely affect consumer health, antibiotic residues in Pangasius catfish products imported into Thailand should be continually monitored.

Removal of perfluorooctanoic acid (PFOA) in groundwater by nanofiltration membrane.

Perfluorooctanoic acid (PFOA) is very persistent in the environment and resistant to typical degradation processes. PFOA has been widely used in surface-active agents and as an emulsifier in several products and can contaminate groundwater. Groundwater is considered as an important source of water; hence removal of PFOA contamination in groundwater is needed. This study aimed to examine the removal of PFOA in spiked deionized water and spiked groundwater samples by nanofiltration (NF) membrane. PFOA removal efficiency was performed by using NF membrane and all samples were analysed by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). For groundwater concentration, solid phase extraction is needed before being analysed by HPLC-MS/MS. The results showed that at higher pressures and higher PFOA concentrations, the PFOA removal efficiencies were slightly higher. The PFOA removal efficiency of spiked deionized water and spiked groundwater sample were 99.78-99.87% and 99.49-99.54%, respectively, which were not significantly different.

Monitoring and determination of sulfonamide antibiotics (sulfamethoxydiazine, sulfamethazine, sulfamethoxazole and sulfadiazine) in imported Pangasius catfish products in Thailand using liquid chromatography coupled with tandem mass spectrometry.

This research aimed to monitor the concentrations of sulfamethoxydiazine (SMD), sulfamethazine (SMT), sulfamethoxazole (SMX) and sulfadiazine (SDZ) in imported Pangasius catfish products in Thailand. The residues of the four sulfonamides (SAs) were analyzed by extraction process and liquid chromatography coupled with tandem mass spectrometry. The highest concentrations found were 10.97ng/g for SMD, 6.23ng/g for SMT, 11.13ng/g for SDZ and 245.91ng/g for SMX, which was higher than the European Union (EU) standard (100ng/g). Moreover, all samples contaminated with SMX also contained SMT, indicating that more than one antibiotic was used for production in the country of origin. Because Thai standards for antibiotics in food have not been completely set, all contaminated discovered would not be considered to be an illegal food, in which antibiotic residues may affect human health in the long term. Therefore, antibiotic residues in Pangasius catfish products should be continually regulated and monitored.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination from textiles.

The goals of this study were to determine the concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in textiles and to determine PFOS and PFOA contamination in textile washing water. Quantification analysis was performed by high performance liquid chromatography coupled with tandem mass spectrometry. Analysis of 32 textile samples by methanol extraction revealed that the average concentrations of PFOS and PFOA were 0.18 µg m(-2) (0.02 to 0.61 µg m(-2)) and 2.74 µg m(-2) (0.31 to 14.14 µg m(-2)), respectively. Although the average concentration of PFOS found in textile samples was below European Union (EU) Commission regulations (<1 µg m(-2)), the average concentration of PFOA was 2.74 µg m(-2), and 68.75% of textile samples had PFOA concentrations exceeding 1 µg m(-2). Thus, based on these results, the concentration of PFOA in products should also be regulated. Experiments on PFOS and PFOA leaching into washing water were conducted. The maximum concentrations of PFOS and PFOA were measured after the first washing; the concentrations gradually decreased with each subsequent washing. PFOS and PFOA migrated from textiles and were released into the environment, with disappearance percentages of 29.8% for PFOS and 99% for PFOA. The data presented in this study showed that textiles could be a significant direct and indirect source of PFOS and PFOA exposure for both humans and the environment.

Evaluation of removal efficiency of human antibiotics in wastewater treatment plants in Bangkok, Thailand.

This study aimed to investigate the antibiotic concentration at each stage of treatment and to evaluate the removal efficiency of antibiotics in different types of secondary and advanced treatment, as well as the effects of the location of their discharge points on the occurrence of antibiotics in surface water. Eight target antibiotics and four hospital wastewater treatment plants in Bangkok with different conventional and advanced treatment options were investigated. Antibiotics were extracted by solid phase extraction and analysed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The antibiotic with the highest concentration at influent was cefazolin at 13,166 ng/L, while the antibiotic with the highest concentration at effluent was sulfamethoxazole at 1,499 ng/L. The removal efficiency of antibiotics from lowest to highest was sulfamethoxazole, piperacillin, clarithromycin, metronidazole, dicloxacillin, ciprofloxacin, cefazolin, and cefalexin. The adopted conventional treatment systems could not completely remove all antibiotics from wastewater. However, using advanced treatments or disinfection units such as chlorination and UV could increase the antibiotic removal efficiency. Chlorination was more effective than UV, ciprofloxacin and sulfamethoxazole concentration fluctuated during the treatment process, and sulfamethoxazole was the most difficult to remove. Both these antibiotics should be studied further regarding their contamination in sludge and suitable treatment options for their removal.

Determination of perfluorooctane sulfonate and perfluorooctanoic acid in food packaging using liquid chromatography coupled with tandem mass spectrometry.

This research aimed to monitor the amounts of PFOS and PFOA in food packaging and study the migration of PFOS and PFOA from food packaging, using a saliva simulant and pressurized liquid extraction (PLE) technique. Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) was employed to determine residues of PFOS and PFOA by using a gradient reversed-phase method with ammonium acetate/acetonitrile buffer. A good linearity was established for PFOS and PFOA in a range of 0.05-10 µgL(-1), with R2 ≥ 0.9998. Of the samples extracted by methanol, the highest concentration of PFOS was found in fast-food container samples, at a level of 92.48 ng dm(-2). For PFOA, the highest concentration in samples extracted by methanol was found in ice cream cup samples, at a level of 16.91 ng dm(-2). The amounts of PFOS and PFOA that migrated from food packaging samples through contact with saliva simulant were 4.80 and 4.55 ng dm(-2), respectively. Saliva simulant could leach PFOS and PFOA from the group of the thickest paper samples (≤1 dm2 g(-1)) at levels of 7.01 and 6.41 ng dm(-2), respectively, indicating that paper with greater thickness and less area might release larger quantities of coated/added PFOS or PFOA.

Isotopic composition of nitrogenous compounds with emphasis on anthropogenic loading in river ecosystems.

Nitrogenous compounds with high delta(15)N values were recently found in human-dominated small rivers in the Lake Biwa area. A detailed survey was performed to determine the distribution and variation of delta(15)N values in nitrogenous compounds in a representative small river (Hebisuna River) that flows into Lake Nishinoko, an inner bay of Lake Biwa. A high delta(15)N value was detected in the lower reaches of the river and the inner bay, most likely due to denitrification. These results strongly suggest that denitrification in small river systems such as the Hebisuna watershed has contributed to (15)N enrichment in the Lake Biwa ecosystem during the past 40 years. We also observed a clear, stepwise, positive correlation between population density and delta(15)N values for particulate organic matter or sediments. These results demonstrate that delta(15)N (POM) and delta(15)N (sediment) are helpful indicators for assessing nitrogen loading from domestic sewage. Moreover, they will aid in the development of new concepts in the environmental capacity of river ecosystems and its relationship to redox conditions. Finally, our data suggest that a population density of 100-200 persons per km(2) is the upper limit for a watershed in which only simple conventional sewage treatment is in effect.

Estimation of pathways of the production of greenhouse gases in the tropical swamp forest in Thailand by stable isotope investigation.

Dynamics of greenhouse gases (N(2)O and CH(4)) with the dry-wet cycle along with the variation of oxidation-reduction boundaries were investigated in the tropical wetland in monsoon Asia. It was clarified that the production of N(2)O and CH(4) was closely related to the development of a redox boundary in the Bang Nara River systems. An intermittent increase in N(2)O was observed at the beginning of the rainy season, when a large amount of easily decomposable organic matter was introduced into the river. After 10 days, when dissolved oxygen was consumed completely at the middle reaches, the emission of CH(4) became maximal due to the possible occurrence of denitrification. The distribution of stable isotope ratios in N(2)O clearly demonstrated that nitrification is the major process for its production. Furthermore, the production of N(2)O in this study area was found to vary in time and space with changes in the redox boundary along the water flow.