Monitoring of Phenol in Wastewater Bioremediation by HPLC

Bioremediation emphasizes the detoxification and destruction of toxic substances by microorganisms. Wastewater obtained from an industrial concern was solvent extracted with methyl alcohol and dichloromethane and analysed by GC/MS. Besides phenol, a large variety of organic compounds were detected. Under controlled laboratory conditions, the wastewater was innoculated with a mixed culture of microorganisms specially selected for their abilities to degrade phenol. Samples were collected at regular intervals from the stirred tank bioreactor and analysed for phenol by reverse phase HPLC with a C18 column. Results shows that from an initial phenol concentration of 987 ppm, slightly more than 50% was destroyed within 163 hours. The dry weight of the microorganisms and the plate count (CFU/ml) shows a steady increase from 0.5238 gms to 0.5355 gms and from 1.1E+9 to 1.94E+13 respectively over the same period. This suggested that the phenol was consumed by the microorganisms as the sole carbon source.     

Probability of intellectual disability is associated with soil concentrations of arsenic and lead

Background

The association between metals in water and soil and adverse child neurologic outcomes has focused on the singular effect of lead (Pb), mercury (Hg), and arsenic (As). This study describes the complex association between soil concentrations of As combined with Pb and the probability of intellectual disability (ID) in children.

Methods

We used a retrospective cohort design with 3988 mother child pairs who were insured by Medicaid and lived during pregnancy and early childhood in South Carolina between 1/1/97 and 12/31/02. The children were followed until 6/1/08, using computerized service files, to identify the diagnosis of ID in medical records and verified by either school placement or disability service records. The soil was sampled using a uniform grid and analyzed for eight metals. The metal concentrations were interpolated using Bayesian Kriging to estimate concentration at individual residences.

Results

The probability of ID increased for increasing concentrations of As and Pb in the soil. The Odds Ratio for ID, for one unit change in As was 1.130 (95% confidence interval 1.048-1.218) for Pb was 1.002 (95% confidence interval 1.000-1.004). We identified effect modification for the infants based on their birth weight for gestational age status and only infants who were normal size for their gestational age had increased probability of ID based on the As and Pb soil concentrations (OR for As at normal weight for gestational age = 1.151 (95% CI: 1.061-1.249) and OR for Pb at normal for gestational age = 1.002 (95% CI: 1.002-1.004)). For normal weight for gestational age children when As = 22 mg kg⁻¹ and Pb = 200 mg kg⁻¹ the risk for ID was 11% and when As = 22 mg kg⁻¹and Pb = 400 mg kg⁻¹ the probability of ID was 65%.

Conclusion

The probability of ID is significantly associated with the interaction between Pb and As for normal weight for gestational age infants.     

Identifying natural and anthropogenic sources of metals in urban and rural soils using GIS-based data,PCA, and spatial interpolation

Determining sources of neurotoxic metals in rural and urban soils is important for mitigating human exposure. Surface soil from four areas with significant clusters of mental retardation and developmental delay (MR/DD) in children, and one control site were analyzed for nine metals and characterized by soil type, climate, ecological region, land use and industrial facilities using readily available GIS-based data. Kriging, principal component analysis (PCA) and cluster analysis (CA) were used to identify commonalities of metal distribution. Three MR/DD areas (one rural and two urban) had similar soil types and significantly higher soil metal concentrations. PCA and CA results suggested that Ba, Be and Mn were consistently from natural sources; Pb and Hg from anthropogenic sources; and As, Cr, Cu, and Ni from both sources. Arsenic had low commonality estimates, was highly associated with a third PCA factor, and had a complex distribution, complicating mitigation strategies to minimize concentrations and exposures.     

Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using delta13C and 14C measurements

Few techniques exist to measure the biodegradation of recalcitrant organic compounds such as chlorinated hydrocarbons (CHC) in situ, yet predictions of biodegradation rates are needed for assessing monitored natural attenuation. Traditional techniques measuring O2, CO2, or chemical concentrations (in situ respiration, metabolite and soil air monitoring) may not be sufficiently sensitive to estimate biodegradation rates for these compounds. This study combined isotopic measurements (14C and delta13C of CO2 and delta13C of CHCs) in conjunction with traditional methods to assess in situ biodegradation of perchloroethylene (PCE) and its metabolites in PCE-contaminated vadose zone sediments. CHC, ethene, ethane, methane, O2, and CO2 concentrations were measured over 56 days using gas chromatography (GC). delta13C of PCE, trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE), delta13C and 14C of vadose zone CO2 and sediment organic matter, and delta13C, 14C, and deltaD of methane were measured using a GC-isotope ratio mass spectrometer or accelerator mass spectrometer. PCE metabolites accounted for 0.2% to 18% of CHC concentration suggesting limited reductive dechlorination. Metabolites TCE and DCE were significantly enriched in (13)C with respect to PCE indicating metabolite biodegradation. Average delta13C-CO2 in source area wells (-23.5 per thousand) was significantly lower compared to background wells (-18.4 per thousand) indicating CHC mineralization. Calculated CHC mineralization rates were 0.003 to 0.01 mg DCE/kg soil/day based on lower 14C values of CO2 in the contaminated wells (63% to 107% modern carbon (pMC)) relative to the control well (117 pMC). Approximately 74% of the methane was calculated to be derived from in situ CHC biodegradation based on the 14C measurement of methane (29 pMC). 14C-CO2 analyses was a sensitive measurement for quantifying in situ recalcitrant organic compound mineralization in vadose zone sediments for which limited methodological tools exist.     

Does the metal content in soil around a pregnant woman’s home increase the risk of low birth weight for her infant?

Low birth weight (LBW) is associated with a number of maternal environmental exposures during pregnancy. This study explored the association between soil metal concentrations around the home where the mother lived during pregnancy and the outcome of LBW. We used a retrospective cohort of 9,920 mother–child pairs who were insured by Medicaid during pregnancy and lived in ten residential areas, where we conducted soil sampling. We used a grid that overlaid the residential areas and collected soil samples at the grid intersections. The soil was analyzed for the concentration of eight metals [arsenic (As), barium (Ba), chromium (Cr), copper (Cu), lead (Pb), manganese (Mn), nickel (Ni), and mercury (Hg)], and we then used Bayesian Kriging to estimate the concentration at the actual maternal addresses, since we had the GIS coordinates of the homes. We used generalized additive modeling, because the metal concentrations had nonlinear associations with LBW, to develop the best fitting multivariable model for estimating the risk of LBW. The final model showed significant associations for female infants, maternal smoking during pregnancy, non-white mothers, Cu, and As with LBW. The As variable was nonlinear in relation to LBW, and the association between higher concentrations of As with LBW was strong (p = 0.002). We identified a statistically significant association between soil concentrations of arsenic around the home of pregnant women and an increased risk of LBW for her infant.     

Associations between soil lead concentrations and populations by race/ethnicity and income-to-poverty ratio in urban and rural areas

Lead (Pb) is a well-studied environmental contaminant that has many negative health effects, especially for children. Both racial/ethnic and income disparities have been documented with respect to exposure to Pb in soils. The objectives of this study were to assess whether soil Pb concentrations in rural and urban areas of South Carolina USA, previously identified as having clusters of intellectual disabilities (ID) in children, were positively associated with populations of minority and low-income individuals and children (≤6 years of age). Surface soils from two rural and two urban areas with identified clusters of ID were analyzed for Pb and concentrations were spatially interpolated using inverse distance weighted analysis. Population race/ethnicity and income-to-poverty ratio (ITPR) from United States Census 2000 block group data were aerially interpolated by block group within each area. Urban areas had significantly higher concentrations of Pb than rural areas. Significant positive associations between black, non-Hispanic Latino, individuals and children ≤6 years of age and mean estimated Pb concentrations were observed in both urban (r = 0.38, p = 0.0007) and rural (r = 0.53, p = 0.04) areas. Significant positive associations also were observed between individuals and children with an ITPR < 1.00 and Pb concentrations, though primarily in urban areas. Racial/ethnic minorities and low ITPR individuals, including children, may be at elevated risk for exposure to Pb in soils.     

Application of encapsulation (pH-sensitive polymer and phosphate buffer macrocapsules): a novel approach to remediation of acidic ground water

Macrocapsules, composed of a pH-sensitive polymer and phosphate buffer, offer a novel remediation alternative for acidic ground waters. To test their potential effectiveness, laboratory experiments were carried out followed by a field trial within a coal pile runoff (CPR) acidic contaminant plume. Results of traditional limestone and macrocapsule treatments were compared in both laboratory and field experiments. Macrocapsules were more effective than limestone as a passive treatment for raising pH in well water from 2.5 to 6 in both laboratory and field experiments. The limestone treatments had limited impact on pH, only increasing pH as high as 3.3, and armoring by iron was evident in the field trial. Aluminum, iron and sulfate concentrations remained relatively constant throughout the experiments, but phosphate increased (0.15-32 mg/L), indicating macrocapsule release. This research confirmed that macrocapsules may be an effective alternative to limestone to treat highly acidic ground water.     

Biological and chemical transformation of atrazine in coastal aquatic sediments

The degradation and distribution potential of atrazine, a persistent triazine herbicide, into three chemical fractions were measured in coastal aquatic sediments in the laboratory over time. Sediments with varying organic carbon contents were extracted with an organic solvent followed by an alkali hydrolysis reaction, and atrazine, deethylatrazine (DEA) and deisopropylatrazine (DIA) were quantified in the aqueous, solvent, and basic fractions using gas chromatography-mass spectrometry. The total amount of atrazine and its metabolites recovered after 95 days varied by site and ranged from 5% to 30% in which 95% was atrazine found primarily in the solvent fraction. Sediment organic carbon was positively correlated with the distribution of atrazine into the basic fraction and the decline in the total amount recovered. No DIA was detected in laboratory spiked sediments and transformation to DEA was limited in all sediments and made up less than 1% of the mass balance. The production and persistence of DEA were inversely correlated to organic carbon; sediments with less carbon and limited binding sites had increased formation and persistence of DEA. A secondary metabolite, methylated atrazine (M-ATR) not previously documented to be derived from atrazine, was chemically produced, detected in all sediments and time points, and concentrations were an order of magnitude higher than DEA. Based on results from spiked estuarine sediments, atrazine and M-ATR may have the potential to persist in the environment while DEA and DIA may not be an ecological threat due to their limited formation.     

Bayesian importance parameter modeling of misaligned predictors: soil metal measures related to residential history and intellectual disability in children

In this paper, we propose a novel spatial importance parameter hierarchical logistic regression modeling approach that includes measurement error from misalignment. We apply this model to study the relationship between the estimated concentration of soil metals at the residence of mothers and the development of intellectual disability (ID) in their children. The data consist of monthly computerized claims data about the prenatal experience of pregnant women living in nine areas within South Carolina and insured by Medicaid during January 1, 1996 and December 31, 2001 and the outcome of ID in their children during early childhood. We excluded mother-child pairs if the mother moved to an unknown location during pregnancy. We identified an association of the ID outcome with arsenic (As) and mercury (Hg) concentration in soil during pregnancy, controlling for infant sex, maternal race, mother’s age, and gestational weeks at delivery. There is some indication that Hg has a slightly higher importance in the third and fourth months of pregnancy, while As has a more uniform effect over all the months with a suggestion of a slight increase in risk in later months.     

Use of a general toxicity test to predict heavy metal concentrations in residential soils

Significant clusters of developmental delay and mental retardation (DD/MR) were identified in children born in South Carolina. Although it is difficult to identify one factor that causes DD/MR, environmental insult including exposure of pregnant women to heavy metals can induce DD/MR in their children. Because it is expensive to measure the concentrations of individual metals in large numbers of environmental samples, the general Microtox toxicity test was used to identify highly toxic soil samples. Approximately 100 soil samples were collected from residential areas and analyzed to determine an effective concentration (EC(50)) of soil required to inhibit 50% light emission of the luminescent bacterial test organism (Vibrio fischeri). The EC(50) values were then transformed to relative toxicity units (RTU). A subset of 56 high and low toxicity soil samples was then analyzed by inductively coupled plasma-atomic emission spectrometry (EPA method 6010) for arsenic, lead, and chromium, which are known neurotoxins. The highest measured arsenic concentration was 30 times higher than the South Carolina residential soil limit. Significant correlations were found between the RTU and soil arsenic and chromium concentrations. Microtox also identified some low arsenic and chromium samples as toxic, presumably because additional unidentified toxicants were present in the soil. In general, however, the Microtox test was effective in identifying soils with elevated concentrations of arsenic and chromium, even in residential neighborhoods where limited soil toxicity was expected.