Surveillance of perchlorate level in wine, seafood, polished rice, milk, powdered milk and yogurt

Perchlorate, which may be naturally occurring or artificial in origin, inhibits iodide uptake into the thyroid gland and disturbs thyroid function. In order to investigate perchlorate contamination in foods in Japan, perchlorate levels in 28 wine samples, 20 seafood samples, 10 polished rice samples, 30 milk (include whole milk, composition modified milk, low fat milk, processed milk, milk drink) samples, 10 powdered milk samples and 10 yogurt samples were measured. Perchlorate was found in all wine, milk, powdered milk and yogurt samples tested. Perchlorate levels ranged from 0.2 ng/g to 103 ng/g in wine samples, from 2 ng/g to 11 ng/g in milk samples, from 3 ng/g to 35 ng/g in powdered milk samples, and from 2 ng/g to 11 ng/g in yogurt samples. Perchlorate levels in the seafood samples were under the LOQ (0.8 ng/g) in 8 samples and ranged from 0.8 ng/g to 72 ng/g in 12 samples. In all polished rice samples, perchlorate level was under the LOQ (1.0 ng/g).     

Trace analysis of bromate, chlorate, iodate, and perchlorate in natural and bottled waters

A simple and rapid method has been developed to simultaneously measure sub-microg/L quantities of the oxyhalide anions bromate, chlorate, iodate, and perchlorate in water samples. Water samples (10 mL) are passed through barium and hydronium cartridges to remove sulfate and carbonate, respectively. The method utilizes the direct injection of 10 microL volumes of water samples into a liquid chromatography-tandem triple-quadrupole mass spectrometry (LC-MS/MS) system. Ionization is accomplished using electrospray ionization in negative mode. The method detection limits were 0.021 microg/L for perchlorate, 0.045 microg/L for bromate, 0.070 microg/L for iodate, and 0.045 microg/L for chlorate anions in water. The LC-MS/MS method described here was compared to established EPA methods 300.1 and 317.1 for bromate analysis and EPA method 314.0 for perchlorate analysis. Samples collected from sites with known contamination were split and sent to certified laboratories utilizing EPA methods for bromate and perchlorate analysis. At concentrations above the reporting limits for EPA methods, the method described here was always within 20% of the established methods, and generally within 10%. Twenty-one commercially available bottled waters were analyzed for oxyhalides. The majority of bottled waters contained detectable levels of oxyhalides, with perchlorate < or = 0.74 microg/L, bromate < or = 76 microg/L, iodate < or = 25 microg/ L, and chlorate < or = 5.8 microg/L. Perchlorate, iodate, and chlorate were detectable in nearly all natural waters tested, while bromate was only detected in treated waters. Perchlorate was found in several rivers and reservoirs where itwas not found previously using EPA 314.0 (reporting limit of 4 microg/L). This method was also applied to common detergents used for cleaning laboratory glassware and equipmentto evaluate the potential for sample contamination. Only chlorate appeared as a major oxyhalide in the detergents evaluated, with concentrations up to 517 microg/g. Drinking water treatment plants were also evaluated using this method. Significant formations of chlorate and bromate are demonstrated from hypochlorite generation and ozonation. From the limited data set provided here, it appears that perchlorate is a ubiquitous contaminant of natural waters at trace levels.     

Perchlorate exposure and dose estimates in infants

Perchlorate is a naturally occurring inorganic anion used as a component of solid rocket fuel, explosives, and pyrotechnics. Sufficiently high perchlorate intakes can modify thyroid function by competitively inhibiting iodide uptake in adults; however, little is known about perchlorate exposure and health effects in infants. Food intake models predict that infants have higher perchlorate exposure doses than adults. For this reason, we measured perchlorate and related anions (nitrate, thiocyanate, and iodide) in 206 urine samples from 92 infants ages 1-377 days and calculated perchlorate intake dose for this sample of infants. The median estimated exposure dose for this sample of infants was 0.160 μg/kg/day. Of the 205 individual dose estimates, 9% exceeded the reference dose of 0.7 μg/kg/day; 6% of infants providing multiple samples had multiple perchlorate dose estimates above the reference dose. Estimated exposure dose differed by feeding method: breast-fed infants had a higher perchlorate exposure dose (geometric mean 0.220 μg/kg/day) than infants consuming cow milk-based formula (geometric mean 0.103 μg/kg/day, p < 0.0001) or soy-based formula (geometric mean 0.027 μg/kg/day, p < 0.0001), consistent with dose estimates based on dietary intake data. The ability of perchlorate to block adequate iodide uptake by the thyroid may have been reduced by the iodine-sufficient status of the infants studied (median urinary iodide 125 μg/L). Further research is needed to see whether these perchlorate intake doses lead to any health effects.     

Perchlorate and iodide in dairy and breast milk

Perchlorate inhibits iodide uptake and may impair thyroid and neurodevelopment in infants. Recently, we unambiguously identified the presence of perchlorate in all seven brands of dairy milk randomly purchased from grocery stores in Lubbock, TX. How widespread is perchlorate in milk? Perchlorate in 47 dairy milk samples from 11 states and in 36 human milk samples from 18 states were measured. Iodide was also measured in a number of the samples. Perchlorate was detectable in 81 of 82 samples. The dairy and breast milk means were, respectively, 2.0 and 10.5 microg/L with the corresponding maximum values of 11 and 92 microg/L. Perchlorate is present in virtually all milk samples, the average concentration in breast milk is five times higher than in dairy milk. Although the number of available measurements are few at this point, for breast milk samples with a perchlorate content greater than 10 microg/L, the iodide content is linearly correlated with the inverse of the perchlorate concentration with a r2 of >0.9 (n = 6). The presence of perchlorate in the milk lowers the iodide content and may impair thyroid development in infants. On the basis of limited available data, iodide levels in breast milk may be significantly lower than it was two decades ago. Recommended iodine intake by pregnant and lactating women may need to be revised upward.     

Perchlorate in milk

Perchlorate was unambiguously detected by ion chromatography-suppressed conductivity (IC-CD) and/or ion chromatography-electrospray mass spectrometry (IC-MS) in seven of seven supermarket milk samples bought randomly in Lubbock, TX. Quantitation by IC-MS and IC-suppressed conductivity detection in conjunction with a preconcentration-preelution method provided comparable results. With a sample cleanup procedure that involved protein removal by ethanol and sequential passage though activated alumina and C-18 silica, the limit of detection for perchlorate in milk was 0.5 microg/L. The levels found ranged from 1.7 to 6.4 microg/L. An evaporated milk sample contained perchlorate at 1.1 +/- 0.6 microg/L level, while we did not find detectable levels in a reconstituted powdered milk sample.     

Comparison of inductively coupled plasma-mass spectrometry and radiochemical techniques for total uranium in environmental water samples

Inductively coupled plasma-mass spectrometry (ICP-MS) method EPA 200.8 is gradually finding acceptance as an alternative to uranium analysis. A comparison of the ICP-MS with the accepted radiochemical method EPA 908.0 has been carried out based on data from laboratory control standards, national proficiency test samples, and environmental and drinking water samples from the State of Utah. The method detection limit (MDL) for ICP-MS was determined to be 0.017 microg/L or (0.011 pCi/L), and the minimum reporting limit (MRL) was 0.17 microg/L (MDL x 10) or (0.11 pCi/L). The minimum reporting limit for radiochemical 908.0 method is 1 pCi/L. Our spiked matrix recoveries, spiked blank samples, and reference materials deviate only a few percentage from the listed true values. Results demonstrate that the ICP-MS is a superior analytical tool for the determination of uranium in drinking and environmental waters at concentrations required by the United States Environmental Protection Agency.     

Perchlorate behavior in a municipal lake following fireworks displays

Perchlorate salts of potassium and ammonium are the primary oxidants in pyrotechnic mixtures, yet insufficient information is available regarding the relationship between fireworks displays and the environmental occurrence of perchlorate. Here we document changes in perchlorate concentrations in surface water adjacent to a site of fireworks displays from 2004 to 2006. Preceding fireworks displays, perchlorate concentrations in surface water ranged from 0.005 to 0.081 microg/L, with a mean value of 0.043 microg/L. Within 14 h after the fireworks, perchlorate concentrations spiked to values ranging from 24 to 1028x the mean baseline value. A maximum perchlorate concentration of 44.2 microg/L was determined following the July 4th event in 2006. After the fireworks displays, perchlorate concentrations decreased toward the background level within 20 to 80 days, with the rate of attenuation correlating to surface water temperature. Adsorption tests indicate that sediments underlying the water column have limited (< 100 nmol/g) capacity to remove perchlorate via chemical adsorption. Microcosms showed comparatively rapid intrinsic perchlorate degradation in the absence of nitrate consistent with the observed disappearance of perchlorate from the study site. This suggests that at sites with appropriate biogeochemical conditions, natural attenuation may be an important factor affecting the fate of perchlorate following fireworks displays.     

Perchlorate, nitrate, and iodide intake through tap water

Perchlorate is ubiquitous in the environment, leading to human exposure and potential impact on thyroid function. Nitrate can also competitively inhibit iodide uptake at the sodium-iodide symporter and thus reduce thyroid hormone production. This study investigates the intake of perchlorate, nitrate, and iodide attributable to direct and indirect tap water consumption. The National Health and Nutrition Examination Survey collected tap water samples and consumption data from 3262 U.S. residents during the years 2005-2006. The median perchlorate, nitrate, and iodide levels measured in tap water were 1.16, 758, and 4.55 μg/L, respectively. Measured perchlorate levels were below the United States Environmental Protection Agency (U.S. EPA) drinking water equivalent level for perchlorate (24.5 μg/L). Significant correlations were found between iodide and nitrate levels (r = 0.17, p < 0.0001) and perchlorate and nitrate levels (r = 0.25, p < 0.0001). On the basis of 24 h recall, 47% of the study participants reported drinking tap water; 89% reported either direct or indirect consumption of tap water. For the adult population (age ≥ 20 yrs) the median tap water consumption rate was 11.6 mL/kg-day. Using individual tap water consumption data and body weight, we estimated the median perchlorate, nitrate, and iodide dose attributable to tap water as 9.11, 11300, and 43.3 ng/kg-day, respectively, for U.S. adults. This perchlorate exposure dose from tap water is relatively small compared to the total perchlorate exposure dose previously characterized for the U.S. adults (median 64 ng/kg-day) and the U.S. EPA reference dose (700 ng/kg-day).     

The origin of naturally occurring perchlorate: the role of atmospheric processes

Perchlorate, an iodide uptake inhibitor, is increasingly being detected in new places and new matrices. Perchlorate contamination has been attributed largelyto the manufacture and use of ammonium perchlorate (the oxidizer in solid fuel rockets) and/or the earlier use of Chilean nitrate as fertilizer (approximately 0.1% perchlorate). However, there are regions such as the southern high plains (Texas Panhandle) where there is no clear historical or current evidence of the extensive presence of rocket fuel or Chilean fertilizer sources. The occurrence of easily measurable concentrations of perchlorate in such places is difficult to understand. In the southern high plains groundwater, perchlorate is better correlated with iodate, known to be of atmospheric origin, compared to any other species. We show that perchlorate is readily formed by a variety of simulated atmospheric processes. For example, it is formed from chloride aerosol by electrical discharge and by exposing aqueous chloride to high concentrations of ozone. We report that perchlorate is present in many rain and snow samples. This strongly suggests that some perchlorate is formed in the atmosphere and a natural perchlorate background of atmospheric origin should exist.     

Perchlorate in dairy milk. Comparison of Japan versus the United States

Perchlorate has been considered a potential threat to human health, especially to developing infants and children due to its ability to inhibit iodide uptake by the sodium iodide symporter (NIS) of the thyroid. Although the U.S. has been the prime focus of perchlorate contamination, at least some of the similar sources of perchlorate exist across the world, and it has been detected in many types of foods and beverages worldwide. We present here perchlorate data from cow's milk samples from Japan (mean 9.4 +/-2.7 microg/L, n = 54), which are higher on average than those found in U.S. dairy milk samples reported by a 2004 Food and Drug Administration (FDA) study (5.9+/-1.8 microg/L, n= 104).     

A bioassay for the detection of perchlorate in the ppb range

A bioassay for the determination of ppb (μg·L(-1)) concentrations of perchlorate has been developed and is described herein. The assay uses the enzyme perchlorate reductase (PR) from the perchlorate-reducing organism Dechloromonas agitata in purified and partially purified forms to detect perchlorate. The redox active dye phenazine methosulfate (PMS) is shown to efficiently shuttle electrons to PR from NADH. Perchlorate can be determined indirectly by monitoring NADH oxidization by PR. To lower the detection limit, we have shown that perchlorate can be concentrated on a solid-phase extraction (SPE) column that is pretreated with the cation decyltrimethylammonium bromide (DTAB). Perchlorate is eluted from these columns with a solution of 2 M NaCl and 200 mM morpholine propane sulfonic acid (MOPS, pH 12.5). By washing these columns with 15 mL of 2.5 mM DTAB and 15% acetone, contaminating ions, such as chlorate and nitrate, are removed without affecting the bioassay. Because of the effect of complex matrices on the SPE columns, the method of standard additions is used to analyze tap water and groundwater samples. The efficacy of the developed bioassay was demonstrated by analyzing samples from 2-17000 ppb in deionized lab water, tap water, and contaminated groundwater.     

Natural chlorate in the environment: application of a new IC-ESI/MS/MS method with a Cl¹⁸O₃-internal standard

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO??) in environmental samples. The method involves the electrochemical generation of isotopically labeled chlorate internal standard (Cl1?O??) using 1?O water (H?1?O) he standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO?? was 2 ng L?1 for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO?? in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO?? analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO??) occurrence were analyzed using the proposed method and ClO?? was found to co-occur with ClO?? at concentrations ranging from < 2 ng L?1 in precipitation from Texas and Puerto Rico to >500 mg kg?1 in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO?? in some natural groundwater samples (0.1 μg L?1) analyzed in this work may indicate lower stability when compared to ClO?? in the subsurface. The high concentrations ClO?? in caliches and soils (3-6 orders of magnitude greater) as compared to precipitation samples indicate that ClO??, like ClO??, may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.     

Thyrotoxicity of sodium arsenate, sodium perchlorate, and their mixture in zebrafish Danio rerio

Both perchlorate and arsenate are environmental contaminants. Perchlorate is a definitive thyroid disruptor, and arsenic may disrupt thyroid homeostasis via multiple pathways. To evaluate the effects of sodium perchlorate and sodium arsenate on thyroid function and possible interactions between them, zebrafish (Danio rerio) were exposed to sodium perchlorate (10 and 100 mg/L), sodium arsenate (1 and 10 mg/L), and the mixture sodium perchlorate + sodium arsenate (10 + 1 and 100 + 10 mg/ L) for up to 90 days. At day 10, 30, 60, and 90, fish were sampled and analyzed forthyroid histopathological end points including follicular cell height, follicle size, colloid size, colloid depletion, hyperplasia, and angiogenesis. Effects on epithelial cell height (hypertrophy) were seen as early as 10 days after exposure. Perchlorate induced changes in all parameters staring at 30 days of exposure. Prolonged perchlorate exposure induced angiogenesis, a relatively new marker of thyroid disruption. Sodium arsenate was less effective than sodium perchlorate in causing thyroid histopathologies, but transient responses were seen for hypertrophy, hyperplasia, and colloid depletion (% colloid). This is the first report of arsenate-induced effects on thyroid histopathology. However, because statistically significant effects were not consistently seen in all end points, evidence for arsenate as a thyroid disruptor remains equivocal. In general, the sensitivity of the following histopathological indicators for indicating thyroid perturbations is, in descending order: follicular cell height > percent of colloid area/follicle area > colloid area/follicular cell height > hyperplasia > angiogenesis > colloid area >follicle area = fish growth.     

Trace analysis of perchlorate anion in selected food products by reverse-phase liquid chromatography-tandem mass spectrometry.

An alternative, rapid, and reproducible method of analysis for perchlorate in selected food products (fruit and vegetable juice, milk, and bottled water) was developed and validated. Improvements over previous methods were achieved by the use of a rugged and inexpensive C18 column, a multi-mode OASIS HLB solid-phase extraction cartridge for sample clean-up, and acetic acid for pH adjustment and protein precipitation. The hydrophobicity of the perchlorate anion gives it good retention and separation characteristics on C18 chromatographic columns. The C18 column allowed for the use of 90% of acetonitrile at a low flow rate (0.3 ml min(-1)), without splitting, and could also be regenerated with organic solvents, unlike an ion-exchange column. Perchlorate levels in selected commercial food samples were: <1.0-2.1 ng g(-1) (fruit and vegetable juices, reported here for the first time), <1.0-5.0 ng g(-1) (milk), and <1.0 ng g(-1) (bottled water).     

Effects of genotype and transpiration rate on the uptake and accumulation of perchlorate (ClO4-) in lettuce

Although evidence of perchlorate accumulation in plants exists, there is a scarcity of information concerning the key factors and mechanisms involved. To ascertain whether genotypic variation in perchlorate accumulation occurs within lettuce, hydroponic plant uptake experiments were conducted with five types of lettuce (Lactuca sativa L.), which were grown to market size atthree perchlorate (ClO4-) concentrations (1, 5, or 10 microg/L). Perchlorate accumulated in the leafy tissues to varying amounts, ranging from 4 to 192 microg/kg fresh weight (FW), and the ranking of perchlorate accumulation was crisphead > butter head > romaine > red leaf > green leaf. The effect of transpiration rate on perchlorate accumulation was further examined using crisphead, butter head, and green leaf lettuce. By growing lettuce in controlled-environment chambers with two climatic regimes, "cloudy, humid, cool" (80% RH, 18/15 degrees C, 250 micromol/m2s photosynthetic photon flux density (PPFD)) and "sunny, dry, warm" (approximately 50% RH, 28/18 degrees C, 500 micromol/m2s PPFD), up to 2.7-fold differences in transpiration rates were achieved. Across all three genotypes, the plants that transpired more water accumulated more perchlorate on a whole-head basis; however, the effect of transpiration rate on perchlorate accumulation was not as great as expected. Despite 2.0-2.7-fold differences in transpiration rate, there were only 1.2-2.0-fold differences in perchlorate accumulation. In addition to whole-head analysis, plants were sectioned into inner, middle, and outer leaves and processed separately. Overall, the ranking of perchlorate accumulation was outer leaves > middle leaves > inner leaves. Transpiration rate has a clear effect on perchlorate accumulation in lettuce, but other factors are influential and deserve exploration.     

Rate and extent of aqueous perchlorate removal by iron surfaces

The rate and extent of perchlorate reduction on several types of iron metal was studied in batch and column reactors. Mass balances performed on the batch experiments indicate that perchlorate is initially sorbed to the iron surface, followed by a reduction to chloride. Perchlorate removal was proportional to the iron dosage in the batch reactors, with up to 66% removal in 336 h in the highest dosage system (1.25 g mL(-1)). Surface-normalized reaction rates among three commercial sources of iron filings were similar for acid-washed samples. The most significant perchlorate removal occurred in solutions with slightly acidic or near-neutral initial pH values. Surface mediation of the reaction is supported by the absence of reduction in batch experiments with soluble Fe2+ and also by the similarity in specific reaction rate constants (kSA) determined for three different iron types. Elevated soluble chloride concentrations significantly inhibited perchlorate reduction, and lower removal rates were observed for iron samples with higher amounts of background chloride contamination. Perchlorate reduction was not observed on electrolytic sources of iron or on a mixed-phase oxide (Fe3O4), suggesting that the reactive iron phase is neither pure zerovalent iron nor the mixed oxide alone. A mixed valence iron hydr(oxide) coating or a sorbed Fe2+ surface complex represent the most likely sites for the reaction. The observed reaction rates are too slow for immediate use in remediation system design, but the findings may provide a basis for future development of cost-effective abiotic perchlorate removal techniques.     

Uptake, elimination, and relative distribution of perchlorate in various tissues of channel catfish

This study was undertaken to determine the kinetics of uptake and elimination of perchlorate in channel catfish, Ictalurus punctatus. Perchlorate--an oxidizer used in solid fuel rockets, fireworks, and illuminating munitions--has been shown to effect thyroid function, causing hormone disruption and potential perturbations of metabolic activities. For the uptake study, catfish were exposed to 100 mg/L sodium perchlorate for 12 h to 5 d in the laboratory. Perchlorate in tissues was analyzed using ion chromatography. The highest perchlorate concentrations were found in the head and fillet, indicating that these tissues are the most important tissues to analyze when determining perchlorate uptake into large fish. To calculate uptake and elimination rate constants for fillet, gills, G-I tract, liver, and head, fish were exposed to 100 ppm sodium perchlorate for 5 days, and allowed to depurate in clean water for up to 20 days. The animals rapidly eliminated the perchlorate accumulated showing the highest elimination in fillet (Ke = 1.67 day(-1)) and lowest elimination in liver (Ke = 0.79 day(-1)).     

Comparison of haloacetic acids in the environment of the Northern and Southern Hemispheres

Haloacetic acids (HAAs) are a family of compounds whose environmental concentrations have been extensively studied, primarily in Europe. Depending on the compound, their sources are believed to be both natural and anthropogenic. To better understand possible sources and contribute to the knowledge of the global distribution of these compounds, especially between the Northern and Southern Hemispheres, samples of precipitation, soils, and conifer needles were collected from Canada, Malawi, Chile, and the U.K. Precipitation samples exhibited highest HAA concentrations in collections from Canada, and lowest in those from Malawi. Malawi samples contained measurable levels of monobromoacetic acid (MBA) (56 ng/ L) unlike those from most other locations (< 9 ng/L). Soil HAA concentration levels were highest in the U.K. (e.g., 7.3 ng/g average TCA) and lowest in Malawi (0.8 ng/g average TCA), with Chile having higher levels (4.8 ng/g average TCA) than Canada (3 ng/g average TCA). Malawi soils contained small amounts of MBA (2 ng/g), in common with the two most southern of the 11 Chilean sites. Analysis of soil cores (10-cm depth sliced at 1 cm) from sites in Malawi and Chile showed that trichloroacetic acid (TCA) generally declined with depth while mono- and dichloroacetic acid (MCA and DCA) showed no trend. MCA, DCA, and TCA concentrations in archived U.K. soil samples increased by factors of 2, 4, and 5-fold over 75 years while TFA showed no consistent trend. Monochloroacetic acid (MCA) was detected in pine needles collected from Malawi. U.K. needle samples had the highest concentrations of all chloroacetic acids (CAAs): MCA, 2-18 ng/g; dichloroacetic acid (DCA), 2-38 ng/g; and trichloroacetic acid (TCA), 28-190 ng/g. Conifer needles from Canada and Chile contained CAAs at levels ranging from < 2 to 16 ng/g wet wt. Trifluoroacetic acid concentrations generally declined with increasing elevation in the samples from the Rocky Mountains in western Canada. The results indicate that concentrations of HAAs are greatest in the industrialized Northern Hemisphere but there are significant amounts of these compounds in the less industrialized Southern Hemisphere.     

Ion chromatographic determination of perchlorate in foods consumed in Hatay region

Recently, the exposure to perchlorate was emphasised as an important risk factor for human and especially newborn health. A number of studies were focused on this matter. In this study, samples of soil, vegetable (cabbage, spinach, lettuce, carrot, tomato, red cabbage), fruit (orange, mandarin, lemon, grapefruit), water, milk and fish were taken from 8 different regions of Hatay (Samanda?, K?r?khan, Reyhanl?, Amik Plain, Dörtyol, Yaylada??, Alt?nözü, Erzin). An ion chromatography system (Shimadzu C196-E039A model) was used to determine the concentrations of perchlorate in the samples. 2.5 mM Phthalic acid and 2.4 mM tris (hydroxymethyl)aminomethane solutions (pH = 4) were used as the mobile phase. A flow rate of 1.5 ml min⁻¹ and oven temperature of 40 °C were used during the analysis. The foods had perchlorate concentrations in the range of 0.236–1.218 μg kg⁻¹. The perchlorate concentration varied from 0.30 ± 0.01 to 0.94 ± 0.02 μg l⁻¹ in milk samples. Perchlorate concentrations were determined to be lower in the drinking waters (0.44 ± 0.03 μg l⁻¹) compared to irrigation waters (0.59 ± 0.03 μg l⁻¹). Perchlorate concentrations of the fish samples were ranged from 0.38 ± 0.01 to 0.61 ± 0.01 μg kg⁻¹.     

A steady-state biofilm model for simultaneous reduction of nitrate and perchlorate, part 2: parameter optimization and results and discussion

Part 1 of this work developed a steady-state, multispecies biofilm model for simultaneous reduction of nitrate and perchlorate in the H(2)-based membrane biofilm reactor (MBfR) and presented a novel method to solve it. In Part 2, the half-maximum-rate concentrations and inhibition coefficients of nitrate and perchlorate are optimized by fitting data from experiments with different combinations of influent nitrate and perchlorate concentrations. The model with optimized parameters is used to quantitatively and systematically explain how three important operating conditions (nitrate loading, perchlorate loading, and H(2) pressure) affect nitrate and perchlorate reduction and biomass distribution in these reducing biofilms. Perchlorate reduction and accumulation of perchlorate-reducing bacteria (PRB) in the biofilm are affected by four promotion or inhibition mechanisms: simultaneous use of nitrate and perchlorate by PRB and competition for H(2), the same resources in PRB, and space in a biofilm. For the hydrogen pressure evaluated experimentally, a low nitrate loading (<0.1 g N/m(2)-d) slightly promotes perchlorate removal, because of the beneficial effect from PRB using both acceptors. However, a nitrate loading of >0.6 g N/m(2)-d begins to inhibit perchlorate removal, as the competition effects become dominant.