Syam S. Andra

Analysis of phytochelatin complexes in the lead tolerant vetiver grass [Vetiveria zizanioides (L.)] using liquid chromatography and mass spectrometry.

Ethylenediamene tetraacetic acid (EDTA) has been used to mobilize soil lead (Pb) and enhance plant uptake for phytoremediation. Chelant bound Pb is considered less toxic compared to free Pb ions and hence might induce less stress on plants. Characterization of possible Pb complexes with phytochelatins (PCn, metal-binding peptides) and EDTA in plant tissues will enhance our understanding of Pb tolerance mechanisms. In a previous study, we showed that vetiver grass (Vetiveria zizanioides L.) can accumulate up to 19,800 and 3350 mg Pb kg(-1) dry weight in root and shoot tissues, respectively; in a hydroponics set-up. Following the basic incubation study, a greenhouse experiment was conducted to elucidate the efficiency of vetiver grass (with or without EDTA) in remediating Pb-contaminated soils from actual residential sites where Pb-based paints were used. The levels of total thiols, PCn, and catalase (an antioxidant enzyme) were measured in vetiver root and shoot following chelant-assisted phytostabilization. In the presence of 15 mM kg (-1) EDTA, vetiver accumulated 4460 and 480 mg Pb kg(-1) dry root and shoot tissue, respectively; that are 15- and 24-fold higher compared to those in untreated controls. Despite higher Pb concentrations in the plant tissues, the amount of total thiols and catalase activity in EDTA treated vetiver tissues was comparable to chelant unamended controls, indicating lowered Pb toxicity by chelation with EDTA. The identification of glutathione (referred as PC1) (m/z 308.2), along with chelated complexes like Pb-EDTA (m/z 498.8) and PC(1)-Pb-EDTA (m/z 805.3) in vetiver root tissue using electrospray tandem mass spectrometry (ES-MS) highlights the possible role of such species towards Pb tolerance in vetiver grass.

Induction of lead-binding phytochelatins in vetiver grass [Vetiveria zizanioides (L.)].

Elevated lead (Pb) concentrations in residential houseyards around house walls painted with Pb-based pigments pose serious human health risks, especially to children. Vetiver grass (Vetiveria zizanioides L.) has shown promise for use in in situ Pb phytoremediation efforts. However, little is known about the biochemical mechanisms responsible for the observed high Pb tolerance by vetiver. We hypothesized that vetiver exposure to Pb induced the synthesis of phytochelatins (PC(n)) and the formation of Pb-PC(n) complexes, alleviating the phytotoxic effects of free Pb ions. Our main objective was to identify PC(n) and Pb-PC(n) complexes in root and shoot compartments of vetiver grass using high-performance liquid chromatography coupled to electrospray mass spectrometry (HPLC-ES-MS). After 7 d of exposure to Pb, vetiver accumulated up to 3000 mg Pb kg(-1) in shoot tissues, but much higher Pb concentrations were measured in root ( approximately 20,000 mg kg(-1)), without phytotoxic symptoms. Scanning electron micrographs showed Pb deposition in the vascular tissues of root and shoot, suggesting Pb translocation to shoot. Collision-induced dissociation analyses in MS/ MS mode during HPLC-ES-MS analysis allowed for the confirmation of four unique PC(n) (n = 1-4) based on their respective amino acid sequence. The high tolerance of vetiver grass to Pb was attributed to the formation of PC(n) and Pb-PC(n) complexes within the plant tissues, using ES-MS and Pb mass isotopic patterns. These data illustrate the mechanism of high Pb tolerance by vetiver grass, suggesting its potential usefulness for the remediation of Pb-contaminated residential sites.

Controlling the fate of roxarsone and inorganic arsenic in poultry litter

A growing body of literature reports 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) degradation in poultry litter (PL) to the more toxic inorganic arsenic (As). Aluminum-based drinking-water treatment residuals (WTR) present a low-cost amendment technology to reduce As availability in PL, similar to the use of alum to reduce phosphorus availability. Batch experiments investigated the effectiveness of WTR in removing roxarsone and inorganic As species from PL aqueous suspensions. Incubation experiments with WTR-amended PL evaluated the effects of WTR application rates (2.5-15% by weight) and incubation time (up to 32 d) at two incubation temperatures (23 and 35 degrees C) on As availability in PL. Batch PL aqueous experiments showed the high affinity of As(V), As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and roxarsone for the WTR. The 10% WTR amendment rate decreased As availability in PL by half of that of the unamended (no WTR) PL-incubated samples. The reduction in dissolved As concentrations during incubation of WTR-amended PL samples was kinetically limited, being complete within 13 d. Parallel reductions in roxarsone, As(V), and DMA concentrations were observed with liquid chromatography-inductively coupled plasma mass spectrometry, whereas As(III) and MMA concentrations were always <5% of dissolved As. Incubation temperature did not significantly (p > 0.05) influence dissolved As concentrations in the WTR-amended PL. Potential formation of a copper-containing roxarsone metabolite was considered in PL aqueous suspensions with the aid of electrospray mass spectrometry. Further experiments in the field are necessary to ensure that sorbed As is stable in WTR-amended PL.

Biomonitoring of human exposures to chlorinated derivatives and structural analogs of bisphenol A

The high reactivity of bisphenol A (BPA) with disinfectant chlorine is evident in the instantaneous formation of chlorinated BPA derivatives (ClxBPA) in various environmental media that show increased estrogen-activity when compared with that of BPA. The documented health risks associated with BPA exposures have led to the gradual market entry of BPA structural analogs, such as bisphenol S (BPS), bisphenol F (BPF), bisphenol B (BPB), etc. A suite of exposure sources to ClxBPA and BPA analogs in the domestic environment is anticipated to drive the nature and range of halogenated BPA derivatives that can form when residual BPA comes in contact with disinfectant in tap water and/or consumer products. The primary objective of this review was to survey all available studies reporting biomonitoring protocols of ClxBPA and structural BPA analogs (BPS, BPF, BPB, etc.) in human matrices. Focus was paid on describing the analytical methodologies practiced for the analysis of ClxBPA and BPA analogs using hyphenated chromatography and mass spectrometry techniques, because current methodologies for human matrices are complex. During the last decade, an increasing number of ecotoxicological, cell-culture and animal-based and human studies dealing with ClxBPA exposure sources and routes of exposure, metabolism and toxicity have been published. Up to date findings indicated the association of ClxBPA with metabolic conditions, such as obesity, lipid accumulation, and type 2 diabetes mellitus, particularly in in-vitro and in-vivo studies. We critically discuss the limitations, research needs and future opportunities linked with the inclusion of ClxBPA and BPA analogs into exposure assessment protocols of relevant epidemiological studies.

Pipe Scales and Biofilms in Drinking-Water Distribution Systems: Undermining Finished Water Quality

Safety and security are two important features of urban drinking-water distribution systems (UDWDS), worldwide, that are often compromised by a suite of physical, hydraulic, and chemical factors adversely impacting quality of potable water reaching consumer taps. Growth of scales and biofilm conglomerates (SBC) coupled with sorption of water chemicals and planktonic microorganisms by SBC has been increasingly recognized as underestimated contaminant sources in aging pipe networks of UDWDS. The main objective of this study was to provide an updated review of factors and processes associated with the increasing frequency of deteriorated finished water quality incidences as a result of SBC effects in UDWDS. This critical review integrated scattered knowledge on the effects of either pipe scales or pipe-anchored biofilm systems on contaminant destabilization and subsequent release into water. It was emphasized that little information exists on combined or concomitantly studied effects of SBC on finished water quality. Important synergistic SBC effects on finished water quality were identified as: (i) those promoting chemical release from pipe scales due to biofilm-induced alterations at the pipe surface/water interface, (ii) the synergistic SBC action on promoting increased release rates of pathogens or toxic chemicals into water, and (iii) the microbially enhanced corrosive phenomena on pipe scales and their constituents. Substantial room for improvement is anticipated for the water and global health research agenda by formulating innovative hypotheses and research designs that water authorities could benefit from as they strive towards further securing access to safe water in urban settings.

Co-leaching of brominated compounds and antimony from bottled water

A fast-growing bottled water market is occasionally challenged by reports calling for contaminant leaching from water-contact materials (plastics). Our focus was on leaching of antimony (Sb) and brominated compounds expressed by total soluble bromine (Br) measurements, including those of polybrominated diphenyl ethers (PBDE). Studies are lacking on concomitant leaching of two or more inorganic plastic constituents from the same bottle. A market-representative basket survey of bottled water was initiated in Boston, USA supermarkets. Bottled water classes sampled were: i) non-carbonated (NCR), ii) carbonated (CR), and iii) non-carbonated and enriched (NCRE). Plastic bottle materials sampled were: polyethylene terephthalate (PET), high-density polyethylene (HDPE), polystyrene (PS), and polycarbonate (PC). Storage conditions for the 31 bottled water samples were: 23°C temperature, no-shaking and 12h/12h light/dark for 60days of equilibration. Average Br and Sb concentrations after 60-days of storage followed the order of NCR<CR=NCRE, and NCR<CR<NCRE, respectively, suggesting that the presence of dissolved carbon dioxide in CR samples coupled to additions of flavors and color to NCRE could explain the elevated leaching of Br and Sb. Combining all bottled water classes and plastic material types, a highly significant (p<0.001) correlation was observed between log-transformed soluble Br and Sb concentrations, suggesting similar leaching behavior. Among samples with the highest soluble Br concentrations, BDE-209 congener was qualitatively confirmed in three out of four bottled water samples. The PC, HDPE, and PS samples exhibited significantly (p<0.05) lower Sb and Br leaching than PET. Upon quantitative validation of PBDE leaching from certain plastic bottles into water, a revisit to existing PBDE exposure assessment reports will be deemed necessary.

Thyroid Disrupting Chemicals in Plastic Additives and Thyroid Health

The globally escalating thyroid nodule incidence rates may be only partially ascribed to better diagnostics, allowing for the assessment of environmental risk factors on thyroid disease. Endocrine disruptors or thyroid-disrupting chemicals (TDC) like bisphenol A, phthalates, and polybrominated diphenyl ethers are widely used as plastic additives in consumer products. This comprehensive review studied the magnitude and uncertainty of TDC exposures and their effects on thyroid hormones for sensitive subpopulation groups like pregnant women, infants, and children. Our findings qualitatively suggest the mixed, significant (α = 0.05) TDC associations with natural thyroid hormones (positive or negative sign). Future studies should undertake systematic meta-analyses to elucidate pooled TDC effect estimates on thyroid health indicators and outcomes.

Chelant-aided enhancement of lead mobilization in residential soils.

Chelation of metals is an important factor in enhancing solubility and hence, availability to plants to promote phytoremediation. We compared the effects of two chelants, namely, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS) in enhancing mobilized lead (Pb) in Pb-based paint contaminated residential soils collected from San Antonio, Texas and Baltimore, Maryland. Batch incubation studies were performed to investigate the effectiveness of the two chelants in enhancing mobilized Pb, at various concentrations and treatment durations. Over a period of 1 month, the mobilized Pb pool in the San Antonio study soils increased from 52 mg kg(-1) to 287 and 114 mg kg(-1) in the presence of 15 mM kg(-1) EDTA and EDDS, respectively. Stepwise linear regression analysis demonstrated that pH and organic matter content significantly affected the mobilized Pb fraction. The regression models explained a large percentage, from 83 to 99%, of the total variation in mobilized Pb concentrations.

Household cleaning activities as noningestion exposure determinants of urinary trihalomethanes.

Previous epidemiological studies linking drinking water total trihalomethanes (THM) with pregnancy disorders or bladder cancer have not accounted for specific household cleaning activities that could enhance THM exposures. We examined the relation between household cleaning activities (washing dishes/clothes, mopping, toilet cleaning, and washing windows/surfaces) and urinary THM concentrations accounting for water sources, uses, and demographics. A cross-sectional study (n = 326) was conducted during the summer in Nicosia, Cyprus, linking household addresses to the geocoded public water pipe network, individual household tap water, and urinary THM measurements. Household tap water THM concentrations ranged between 3-129 μg L(-1), while the median (Q1, Q3) creatinine-adjusted urinary THM concentration in females (669 ng g(-1) (353, 1377)) was significantly (p < 0.001) higher than that in males (399 ng g(-1), (256, 681)). Exposure assessment, based on THM exposure equivalency units, showed that hand dishwashing, mopping, and toilet cleaning significantly (p < 0.001) increased urinary THM levels. The effect of dishwashing by females ≥36 y of age remained significant, even after adjusting for potential confounders. No significant (p > 0.05) association was observed between ingestion-based THM exposure equivalency units and urinary THM. Noningestion routes of THM exposures during performance of routine household cleaning activities were shown for the first time to exert a major influence on urinary THM levels. It is warranted that future pregnancy-birth cohorts include monitoring of noningestion household THM exposures in their study design.

Association between Water Consumption from Polycarbonate Containers and Bisphenol A Intake during Harsh Environmental Conditions in Summer

With the exception of polycarbonate (PC) baby bottles, little attention has been paid to bisphenol A (BPA) intake from packaged water consumption (PC water dispensers), especially during summer weather conditions. We determined the magnitude and variability of urinary BPA concentrations during summer in 35 healthy individuals largely relying upon PC packaged water to satisfy their potable needs. We used liquid chromatography-tandem mass spectrometry to measure urinary BPA concentrations. A questionnaire was administered in July/August and a spot urine sample was collected on the same day and 7 days after the completion of the interview (without intervention). Linear regression was performed to assess the association of variables, such as water consumption from different sources, on urinary BPA levels for the average of the two urine samples. A significant positive association (p = 0.017) was observed between PC water consumption and urinary BPA levels in females, even after adjusting for covariates in a multivariate regression model. The geometric mean of daily BPA intake back-calculated from urinary BPA data was 118 ng · (kg bw)(-1) · day(-1), nearly double the average intake levels observed in biomonitoring studies worldwide. High urinary BPA levels were partially ascribed to summers high PC water consumption and weather characteristics (high temperatures, >40 °C; very high UV index values, >8), which could be causing BPA leaching from PC. It is suggested that PC-based water consumption could serve as a proxy for urinary BPA, although the magnitude of its relative contribution to overall daily intake requires further investigation.