Different chromatographic techniques for arsenic detection. |
However, SEC is very effective for analysis of arsenic interactions with large molecules. For instance, analysis of arsenic–protein binding commonly uses SEC to separate protein-bound arsenic from free arsenic. 12 García-Sevillano et al. used SEC to measure arsenic–biomolecule complexes from liver extracts of Mus musculus . 51 Chen et al. used SEC to separate and collect protein-bound arsenic from free arsenic, followed by hydrogen peroxide treatment to release the protein-bound arsenic. 52 Schmidt et al. simultaneously measured binding of phenylarsine oxide to five different peptides and proteins (glutathione, oxytocin, aprotinin, α-lactalbumin, thioredoxin) using SEC-ESI-MS. 53 Yang et al. investigated the roles of dissolved organic matter on arsenic mobilisation and speciation in environmental water using (SEC), combined with (ICP-MS), as well as three-dimensional excitation–emission matrix (3DEEM) fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC). Low LODs (0.014–0.041 ppb) were reported. 54 The relevant literature on the chromatographic technique is summarised in the Table 2 .
Techniques | Analyte | Column | LOD (ppb) | Reference |
---|---|---|---|---|
AE-HPLC | As(III), As(V), MMA, DMA, AsA | Shodex RSpak NN-614 column (150 × 6 mm) | 0.20–0.80 | |
CE-HPLC | AsB, DMA | Spheris S5SCX | 0.20–0.33 | and |
IPC | As(III), As(V), MMA, DMA, AsB, AsC, TMAO, TMA, arsenosugar X | Capcell pak C18 | 0.04–0.07 | |
RP-LC | Arsenolipids | Asahipak reversed-phase C-8 column (4.6 × 150 mm, particle size 5 μm) | 0.002 | |
HILIC | Rox, PAA, ASA, PAO, DMA, MMA, AsB, AsC, TMAO | SeQuant ZIC-HILIC | 10 | |
SEC (SEC -ICP-MS) | As(V), As(III), AsB, DOM–As(III), MMA, DMA | Shodex OHpak SB-802.5 HQ | 0.014–0.041 |
Hyphenated techniques have become more popular in recent times. Chromatographic methods such as liquid chromatography offer excellent possibility for the separation of all arsenic species because a variety of separation modes can be employed, followed by detection with different detection techniques, particularly in HPLC coupled in hyphenated techniques such as HPLC-hydride generation atomic absorption spectrometry (HG–AAS), hydride generation atomic emission spectrometry (HG-AES) and HPLC-ICP-MS. These methods are successfully and extensively used for the determination of the arsenic species at trace levels in environmental samples because of their low LODs.
HPLC methods for arsenic speciation are based on reversed phase chromatography with, usually, phosphate buffered mobile phases. This is relatively easy to set up, reasonably sensitive and provides the necessary chromatographic resolution of the target species. However, the need for a buffered, sometimes multi-component mobile phase leads to extra preparation work and more cost. In addition, the presence of phosphate in the mobile phase is not ideal for the ICP-MS instrument, as phosphates cause pitting of the interface cones, leading to more frequent replacement or necessitating the use of more robust (and much more expensive) Pt-tipped cones. Longer term operation of HPLC methods for arsenic speciation eventually leads to a drop off in sensitivity and peak retention time drift caused by other components in the sample, leading to the need to periodically change the HPLC column. For lower numbers of samples, HPLC is a cost-effective solution, but the less expensive instrument cost can eventually be offset by the higher column consumable costs in the longer term. 42 In contrast, IC offers the benefits of sharp peak shapes (even for late eluting species), retention time stability, column robustness, excellent long-term peak area/height reproducibility and simpler mobile phases; only dilute ammonium carbonate is required, which is easy to prepare. In addition, dilute ammonium carbonate is fully converted to gaseous species in the plasma (NO 2 , H 2 O and CO 2 ), so no damage or blocking of the interface cones occurs when using this mobile phase. Although not so much of an issue for arsenic speciation, IC also provides a metal-free sample path as standard, which provides lower backgrounds for other elements of speciation interest, such as chromium. Although IC instruments can be more expensive to purchase than HPLC systems, over time this can be offset by the lower consumables cost. Ponthieu et al. proposed a cation exchange IC-ICP-MS method for the simultaneous determination of eight arsenic species using mobile phases prepared from ammonium nitrate. 58 The relevant literature on the coupled/hyphenated chromatographic technique is summarised in the Table 3 .
Separation process | Column | Detector | Arsenic species | Ref. |
---|---|---|---|---|
Anion exchange | Hamilton PRP-X100 | ICP-MS | As(III), AsB, DMA, MMA, As(V), AsA, Rox | |
Hamilton PRP-X100S | ICP-MS/ESI-MS | As(III), AsB, DMA, MMA, methyl-3AHPAA, As(V) | ||
IonPac AS7 | ICP-MS | As(III), PAO, PAA, As(V), o-APAA, Rox, AsA | ||
Shodex RSpak NN-614 | ICP-MS | As(V), MMA, As(III), PhAs, Rox, PhAsO, TMAO | ||
Dionex AS15A | ICP-MS | iAs, DMA, MMA, 4NPAA | ||
Hamilton PRP-X100 | ICP-MS | As(III), As(V), DMA, MA, As-sug-PO , As-sug-SO , As-sug-SO | ||
Hamilton PRP-X100 | ICP-MS/ESI-MS | As-sug-PO , As-sug-SO , As-sug-SO , As-sug-OH aglycone-free sugar | ||
Hamilton PRP-X110S | ICP-MS/ESI-MS/MS | AsB, As(V), Rox, NAHAA, MMA, DMA, As(III) | ||
Hamilton PRP-X110S | ICP-MS/ESI-MS/MS | AsB, N-AHAA, 3-AHPAA, As(III), As(V), MMA, DMA, Rox | ||
Hamilton PRP-X110S | ICP-MS/ESI-MS/MS and ESI-TOF-MS | Rox, methyl-Rox, methyl-3-AHPAA, methyl-N-AHPAA, AsB, As(III), DMA, MMA, As(V), 3-AHPAA, N-AHPAA | ||
Cation exchange | Spheris S5SCX | ICP-MS | AsB, DMA | |
IonoSpher 5C | ICP-MS | As(V), As(III), DMA, TMAO | ||
Zorbax 300-SCX | ICP-QqQMS | AsB, TMAO, TMAP, AsC, TMA | ||
Reversed- phase | Asahipak C8 | ICP-MS/ESI-QqQ | AsFA (C H AsO , C H AsO ), AsHC (C H AsO) | |
ACE C18 | ICP-MS/ESI-MS | As-sug-OH, As-sug-PO , As-sug-SO , AsPL (C H AsO P, C H AsO P, C H AsO P, C H AsO P, C H AsO P, C H AsO P, etc.), AsHC (C H AsO, C H AsO, C H AsO, C H AsO, C H AsO, C H AsO), AsFA (C H AsO , C H AsO ) | ||
Atlantis dC18 | ICP-MS/ESI-qTOF-MS | AsFA (C H AsO , C H AsO , C H AsO , C H AsO ) | ||
Ion pair | Capcell pak C18 | ICP-MS/ESI-qTOF-MS | As(III), As(V), MMA, DMA, AsB | |
Shim-pack VP-ODS C18 | ICP-MS | As(III), As(III), MMA, DMA, TMAO, TMA, AsB, AsC | ||
Agilent ZORBAX SB-Aq | ICP-MS | As(III), As(V), MMA, DMA | ||
HILIC | Thermo Fisher Trinity P2 | ICP-MS/ESI-MS | Rox, As(V) | |
Phenomenex HILIC | ESI-MS/MS | AsB | ||
Size exclusion | Phenomenex | ICP-MS/ESI-MS/MS | As(III), As(V), MMA, DMA, TMAO, MMMTA, DMMTA | |
Shodex OHpak SB-802.5 HQ | ICP-MS | As(V), As(III), AsB, DOM-As(III), MMA, DMA | ||
Others | GO@SiO | ICP-MS | As(III), DMA, MMA, As(V) | |
Sigma-Aldrich Discovery HS F5 | ICP-MS | As(III), As(V), MMA, DMA | and |
Commercial colorimetric kit | Theoretical LOD (ppb) | Practical LOD (ppb) | Reliability (ppb) | Cost per sample (USD) | Time per sample (min) | Features | Data/signal type | Ref. |
---|---|---|---|---|---|---|---|---|
NIPSOM | 10 | >20 | Unreliable <70 | 0.4 | 5 | Colour sensitivity to yellow; working quickly | Colour change (range) | and |
Merck | 10 | >50 | Unreliable <70 | 0.5–1.00 | 30 | Colour sensitivity to yellow; working quickly | Colour change (range) | , and |
GPL | 10 | NA | Unreliable <70 | 0.4 | 20 | Colour sensitivity to yellow; working quickly | Colour change (range) | |
AAIH & PH | 50 | >50 | Unreliable <70 | 0.4 | NA | Colour sensitivity to yellow; working quickly | Colour change (binary) | and |
AAN | 10 | >20 | Unreliable <70 | 0.4 | 30 | Colour sensitivity to yellow; working quickly | Colour change (range) | , and |
Quick As | 5 | NA | Can identify samples > 15 | 1.00–2.00 | NA | Colour sensitivity to yellow; working quickly | Colour change (range) | |
Hach Ez | 10 | NA | Can identify samples > 15 | <1–2.00 | 20–40 | Colour sensitivity to yellow; working quickly | Colour change (range) | and |
Arsenator | 0.5–2 | NA | Found to be correct 85% of the time, more reliable at lower concentrations | 1.00 | 20 | Ability to make accurate dilutions | Digital readout | and |
As(V) + Mo(IV) → [AsMo O ] → [AsMo O ] | (1) |
To avoid human bias, digital colour processing can replace semi-quantification by visual comparison with a colour chart. Such an idea was adopted by a number of commercial products, for instances, the Arsenator by Wagtech and the DigiPAsS by Palintest. Parts used to remove interfering gas, such as hydrogen sulphide, are included in modern kits. A recent evaluation of 8 commercial arsenic field test kits for drinking water (Bangladesh) by comparing with HG-AAS showed a performance correlation with the product price. The two most expensive kits, LaMotte and Quick II kit, provided the best estimates while the cheapest were neither accurate nor precise. 78
Some of the relevant literature on the colorimetric arsenic detection technique is summarised in the Table 5 .
Techniques | Detection time | Portability | LOD (ppb) | Reference |
---|---|---|---|---|
Molybdenum blue | >30 min | Not portable, bulky instrument | 1–15 | |
Methylene dye | ∼6 min | Potentially portable | 10–100 | |
Sulfanilic acid – NEDA | ∼30 min | Portable | 18 | and |
Paper based | Very quick | Portable | 1 | and |
According to authors, the results reflect that different arsenic contamination produces different intensities of colour, thereby can be used to distinguish between different arsenic percentages. However, the method may not be fully reliable as it depends on visual colour comparison. 15
Silver nanoparticles (AgNPs) are reported to provide a rapid response to localised surface plasmon resonance compared to gold nanoparticles with enhanced sensitivity. 85 Polyethylene glycol (PEG)-functionalised silver nanoparticles are well-suited for detecting arsenic( III ) ions in an aqueous medium. 86 The PEG-modified silver nanoparticles are sufficient enough to detect arsenic( III ) in 1 ppb due to the addition of PEG. PEG-functionalised AgNPs have adjustable negative surface charges, responsible for the nanoparticle's stability and the electrostatic repulsion between negatively charged surfaces of AgNPs protects them from agglomeration. Interestingly, in the presence of As( III ), the functional AgNPs interacted with PEG hydroxyl groups, which led to the aggregation of AgNPs. As a result, the colour of functionalised nanoparticles changed from yellow to bluish ( Fig. 6 ). A silver nanoprisms (AgNPr) based assay has been designed and reported to achieve the wide range morphologically modified surface plasmon tuning–detuning for accurate colour-coded detection and sensing of As( III ) over other alkali, alkaline, and transition metals ( Fig. 7 ). 87 Plasmon tuning–detuning not only confirms the presence but also can detect As( III ) concentration up to a limit of 75 ppb. The authors have suggested that the assays ability to detect As( III ) in real water samples coupled with its cost effectiveness make it potentially useful for field applications. 87
Functionalised silver nanoparticles as an effective medium towards trace determination of arsenic(III) in aqueous solution (reprinted from ref. ; Copyright (2019), with permission from Elsevier). |
(A) Concentration-dependent colour-coded sensing of arsenic(III) between the concentration range of 10 to 10 M, (B) tuning of SPR as a result of morphological change of AgNPr (silver nanoprism) at different concentrations of arsenic(III) between 10 and 10 M where (B ) shows the variation of plasmon band at different lower concentrations of arsenic(III) in the range of 0.0–10.0 μM (0.0 μM (blank): black trace (λ = 704 nm), 1.0–2.0 μM: blue trace, 2.0–4.0 μM: orange trace, 5.0–7.0 μM: red-violet trace, 8.0–10.0 μM: blue-violet trace) and (B ) at different higher concentrations of arsenic(III). The plasmon band, and hence the colour of the nanomaterials, changes in a distinct manner, where a specific colour remains unchanged in a broader range of growing concentrations such as: 10.0–80.0 μM: yellow, 90.0–100.0 μM: orange, 110.0–200.0 μM: dark red, 250.0–500.0 μM: purple, 750.0 μM to 2 mM: different shades of blue, 3–10 mM: faded blue, and above 10 mM the colour becomes faint blue to grey or almost colourless (reprinted with permission from ref. . Copyright [2019] American Chemical Society). |
Biological detection methods developed for arsenic have mostly been based on the ars operon. An operon is a cluster of genes which are transcribed together giving a single messenger RNA (mRNA) molecule that encodes for multiple proteins. 92 Plasmid encoded ars operons found in bacterial species such as E . coli are known to confer a certain level of resistance to As( III ) and As( V ) through giving cells the ability to remove As species from within the cell, lowering the intracellular concentration of toxic arsenic species. 93 Upon encountering arsenite, a dedicated sensory protein in the bacterial cell called ArsR will undergo a conformational change that unleashes expression of the defence system. 94 This protein functions as a transcriptional repressor, attaching to a particular DNA sequence (the operator) that overlaps the binding site for RNA polymerase in the absence of arsenic (the promoter). However, when binding arsenite, ArsR will lose its affinity for the DNA and RNA polymerase can start transcription. 94 This detoxification system can be exploited for highly specific and sensitive arsenic detection. Modifications involve the coupling of the regulatory elements of the ars operon, including the transcriptional regulator and cognate promoters to reporter genes for Green fluorescent protein (GFP), luciferase, and β-galactosidase (lacZ). In response to the presence of arsenic, genetically modified bacterial species such E. coli , Bacillus subtilis , Staphylococcus aureus , and Rhodopseudomonas palustris , generate reporter proteins, the amount or activity of which is related to arsenic concentration. Such an approach has allowed for LODs in the order of 1 ppb. E. Diesel et al. ( Fig. 8 ) summarised the use of bacteria-based assays as an emerging method that is both robust and inexpensive for the detection of arsenic in groundwater for both in the field and laboratory. 95
Design principle of most bacteria sensor–reporters for arsenic: (a) when no arsenic enters the cell, the ArsR protein represses the transcription of the arsenic defence system genes (arsD, arsC, arsA, and arsB) from one particular DNA region upstream of the gene for itself (the operator–promoter site). In the presence of arsenite in the cell, ArsR loses affinity for the operator and RNA polymerase will transcribe the arsDCAB genes to produce the defence. ArsC is a reductase that reduces arsenate [As(V)] to arsenite [As(III)], whereas ArsAB constitute an efflux pump for arsenite. (b) In the sensor–reporter strain, an extra copy of the operator–promoter DNA fused to the arsR gene and a gene for a reporter protein is added to the cell. In this case, when arsenite or arsenate is sensed by the cell, transcription for the reporter gene will also be unleashed and the reporter protein will be formed. The presence or activity of the reporter protein is subsequently measured (reprinted by permission from Springer [ref. ] COPYRIGHT (2009)). |
Kaur et al. mentioned that the development of whole cell biosensors employing these metabolic processes for their design. 96 In case of arsenic, the well-established ability of As( III ) or As( V ) to bind the ArsR protein and undo its repressor function on the Ars promoter leads to subsequent synthesis of reporter genes. Thus, whole-cell-based biosensors devised using the above approach have been further subdivided, based on their signal transduction mechanisms like luciferase, lacZ and GFP whereby the signal relay is either in terms of fluorescence, luminescence or colorimetry as depicted in Fig. 9A . 96 Wang et al. developed a convenient analysis method for environmental monitoring, that intended to employ in vitro protein expression technology to detect toxic pollutants based on evolved genetically encoded biosensors ( Fig. 9B ). His team established a genetically encoded biosensor in vitro with ArsR and GFP reporter gene. Given that the wildtype ArsR did not respond to arsenic and activate GFP expression in vitro , they found, after screening, an evolved ArsR mutant ep3 could respond to arsenic and exhibited an approximately 3.4-fold fluorescence increase. 97
(A) Schematic representation of whole-cell-based biosensor for (a) arsenic [As(V) and As(III)] transport by phosphate channel, (b) working mechanism of signal transducer for arsenic biosensor, and (c) detection of As(III) by luminescence, fluorescence and colour change (for interpretation of the references to colour in this scheme legend, the reader is referred to the web version of this article) (reprinted from ref. ; Copyright (2015), with permission from Elsevier). (B) Arsenic detection with genetically encoded biosensors in vitro. Schematic of arsenic induction reaction (reprinted from ref. ; Copyright (2021), with permission from Elsevier). |
The engineered promoter modification approach is used to improve the performance of whole-cell biosensors to facilitate their practical application. A recent study, demonstrated how to design the core elements ( i.e. , RNA polymerase binding site and transcription factor binding site) of the promoters to obtain a significant gain in the signal-to-noise output ratio of the whole-cell biosensor circuits ( Fig. 10 , left). 88 The arsenite-regulated promoter from Escherichia coli K-12 genome was modified to lower background and higher expression and was achieved by balancing the relationship between the number of ArsR binding sites (ABS) and the activity of the promoter and adjusting the location of the auxiliary ABS. A promoter variant ParsD-ABS-8 was obtained with an induction ratio of 179 when induced with 1 μM arsenite (11-fold increase over the wild-type promoter). The reported biosensor exhibited good dose–response in the range of 0.1 to 4 μM ( R 2 = 0.9928) of arsenite with a detection limit of ca. 10 nM.
Left: Design and improvement of arsenic biosensors (engineered promotor modifications): construction of arsenic responsive biosensor genetic circuit (reprinted with permission from ref. . Copyright [2019] American Chemical Society). Right: Schematic of the arsenic WCBs with positive feedback (B) and without (A). (A) The typical arsenic WCB consists of the ArsR-regulated promoter Pars, the regulator arsR, and the reporter gene mCherry. (B) The positive feedback WCB consists of the arsR-Pars regulatory circuit and a positive feedback amplifier where LuxR produced in response to arsenite activates the expression of mCherry and LuxR from the PluxI promoter. The LuxR from the PluxI promoter activates its own expression and forms a positive feedback loop (reprinted with permission from ref. . Copyright [2019] American Society for Microbiology). |
An arsenic WCB with a positive feedback amplifier Escherichia coli DH5α was developed and reported ( Fig. 10 , right), 98 where the output signal from the reporter mCherry was significantly enhanced by the positive feedback amplifier. The sensitivity of the WCB with positive feedback was about 1 order of magnitude higher compared to without positive feedback when evaluated using a half As( III ) concentration (half-saturation). The LOD for As( III ) was reduced by 1 order of magnitude to 0.1 μM, lower than the WHO standard for the arsenic levels in drinking water (0.13 μM). The WCB with the positive feedback amplifier exhibited exceptionally high specificity toward As( III ) when compared with other metal ions. The importance of genetic circuit engineering in designing WCBs, and the use of genetic positive feedback amplifiers may be a good strategy to improve the performance of WCBs. The integration of WCBs for the field-ready electrochemical detection of arsenic (FRED-As) has been reported recently. 99 Sergio Sánchez et al. reported a WCB biosensor which was followed by electrochemical measurements and provided enhanced accuracy and signal intensity compared to traditional bacterial-detection approaches ( Fig. 11 ). FRED-As had a number of benefits including ease of use, potential for measuring a wide spectrum of metals, sensitivity etc. When integrated within a customised hardware system, the reported whole-cell biosensor demonstrated excellent specificity and sensitivity with an LOD 95% confidence, (FRED-As) of 2.2 ppb As( III ). 99 This sensitive and easy-to-use approach may be a viable alternative for on-site arsenic testing.
Process schematic of the bacterial biosensor system used for arsenic detection (reproduced from ref. ; Copyright (2021), with permission from IOP Publishing). |
Principles of representative fluorescence-based arsenic aptasensor: (A) DNA adsorption by magnetic iron oxide nanoparticles and its application for arsenate detection (reproduced from ref. with permission from Royal Society of Chemistry, copyright [2014]). (B) Fluorescence aptasensors of As(III) using silica nanoparticles (reprinted with permission from ref. . Copyright [2017] American Chemical Society). (C) The fluorescence quenching analysis (reprinted from ref. ; Copyright (2016), with permission from Elsevier). (D) The fluorescence enhancement analysis based QDs aptasensor for arsenite determination (reprinted from ref. ; Copyright (2017), with permission from Elsevier). Principles of representative colorimetry-based arsenic aptasensor techniques: (E) Cationic polymers and aptamers mediated aggregation of AuNPs for colorimetric detection of As(III) in aqueous solution (reproduced from ref. with permission from Royal Society of Chemistry, copyright [2012]). (F) Ultrasensitive aptamer biosensor for As(III) detection in aqueous solution based on surfactant-induced aggregation of AuNPs (reproduced from ref. with permission from Royal Society of Chemistry, copyright [2012]). (G) Aptasensor for As(III) detection in aqueous solution based on cationic salt-induced aggregation of AuNPs (reprinted from ref. ; Copyright [2014]; with permission from CSIRO Publishing). (H) Regulation of hemin peroxidase catalytic activity by As-binding aptamers for colorimetric detection of As(III) (reproduced from ref. with permission from Royal Society of Chemistry, copyright [2013]). |
Ensafi et al. , have developed a CdTe/ZnS QDs (quantum dots) aggregation-based fluorimeter aptasensor for As( III ) ( Fig. 12C ). 103 The aptamer was designed to aggregate cationic cysteamine-stabilised CdTe/ZnS QDs, which led to fluorescence quenching. When As( III ) was introduced, the complex between the aptamer and As( III ) prevented aggregation of the QDs. Therefore, depending upon the As( III ) concentration, the QDs fluorescence was enhanced due to de-aggregation. The fluorescence analysis held a promising LOD of 1.3 pM with a dynamic range of 10 −2 to 10 3 nM. The proposed QDs based aptasensor has advantages such as high sensitivity and selectivity, compared with conventional dyes based aptasensors. Zhang et al. ( Fig. 12D ), reported an arsenite detection strategy based on the fluorescence enhancement of DNA QDs. 104 In their work, they synthesised DNA QDs using G/T-rich ssDNA that showed special optical properties, and acquired the basic structure and biological activities of ssDNA precursors, making the QDs selectively bind with arsenite, driving the (GT) 29 region towards conformational switching and form a well-ordered assembly. They speculated that the strong inter-molecular interaction and efficient stacking of base pairs stiffened the assembly structure, blocked non-radiative relaxation channels, populated radiative decay, and thus made the assembly highly emissive as a new fluorescence center. The fluorescence enhancement induced by arsenite promoted QDs as light-up probes for determination of arsenite. A very good linear relationship was demonstrated between fluorescence intensity and logarithmic arsenite concentration from 1–150 ppb with an LOD of 0.2 ppb reported.
The first colorimetric arsenic aptasensor was reported by Wu and co-workers ( Fig. 12E ). In the presence of Arsenic, the aptamer selectively interacted with As( III ) forming an As–aptamer complex. The formation of this complex allowed the cationic polymer poly-diallyldimethylammonium (PDDA) to aggregate AuNPs, resulting in an obvious colour variance allowing for highly sensitive colorimetric arsenic detection. 105 In the same year, Wu and co-workers reported another aptasensor employing a different polymer (cetyltrimethylammonium bromide, CTAB) that also utilised AuNP induced aggregation for As( III ) detection ( Fig. 12F ). The dynamic range spanned from 1–1500 ppb with the LOD of 0.6 ppb for colour analysis and 40 ppb for naked-eye detection, respectively. 106 Following the same strategy, Nguyen et al. developed a novel biosensor based on CTAB and AuNPs for colorimetric detection of As( III ) with an LOD of 16.9 ppb in real samples. 14 Zhou's group ( Fig. 12G ) reported the salt-induced aggregation of AuNPs (classical aptamer-based AuNPs colorimetric method) for As( III ) detection. 107 In this study, an arsenic aptamer was employed as the probe with AuNPs as a colorimetric signal. When As( III ) was absent in the solution, AuNPs were wrapped by aptamer and therefore stable even when a high concentration of sodium chloride was in the solution, showing a red colour. When introduced to As( III ), the AuNPs were easy to aggregate due to the formation of the As–aptamer complex, showing a blue coloured solution. Through monitoring the coluor variance, the rapid colorimetric detection methods for As( III ) with a dynamic range from 1.26 to 200 ppb and a LOD of 1.26 ppb was demonstrated. However, AuNPs-based biosensors are dependent on salt-induced aggregation, which seems to make them more susceptible to interference by environmental matrices. Natural matrices are typically diluted in a buffer before sensing, but matrices with high salt concentrations must be handled carefully when performing this assay.
Divsar et al. , (2015) 109 prepared AgNPs modified by aptamer (Apt–AgNPs) and used it for colorimetric determination of As( III ). In their work, As( III ) could selectively interact with Apt–AgNPs resulting in the formation of an As( III )–Apt–AgNPs complex and cause an obvious decrease in peak intensity ( λ max 403 nm), which was proportional to As( III ) concentration. Additionally, a combination of a central composite design optimisation method and response surface methodology was applied to optimize the efficiency of As( III ) analysis. The linear range of the colorimetric biosensor held a wide scope of As( III ) concentration from 50 to 700 ppb with a LOD of 6 ppb. Wu et al. reported the development of a colorimetric aptasensor for As( III ) determination that was designed through the combination of aptamer and G-quadruplex DNAzyme (Wu et al. Fig. 12H ). 108 The catalytic activity of hemin peroxidase was temporarily inhibited by As–aptamer complex. In the presence of As( III ) an As–aptamer complex formed allowing hemin peroxidase catalyze TMB oxidation in the presence of H 2 O 2 resulting in an obvious increase of UV-vis spectra intensity (442 nm), LOD of 6 ppb was reported.
Recently, a highly sensitive fluorescence sensing platform for As( III ) detection based on target-triggered successive signal amplification strategy was demonstrated. As( III ) aptamer was used as the recognition unit and in the presence of As( III ), the blocking DNA is released to trigger the cascade signal amplification process. The integration of Exo III-assisted DNA recycling and DNAzyme-based catalytic cleavage with multiple turnovers results in the generation of amplified fluorescence signals (significantly) for highly sensitive quantification of trace levels of As( III ), and a detection limit of 2 pM was achieved ( Fig. 13 ). 110
(A) Highly sensitive aptasensor for trace arsenic(III) detection using DNAzyme as the biocatalytic amplifier. (B) Schematic illustration of the assay principle for As(III) detection based on target-triggered successive signal amplification strategy ( domain a is complementary to domain a*). The sequence of DNA1 corresponds to the Mg -dependent DNAzyme. MB, magnetic beads; HP, hairpin probe; Exo III, exonuclease III; F, fluorophore (FAM); Q, quencher (TAMRA) (reprinted with permission from ref. . Copyright [2019] American Chemical Society). |
Some of the biological sensors with their performances are summarised in Table 6 .
Biosensor specifications | Response time (min) | LOD (ppb) | As species detected | Reference |
---|---|---|---|---|
E. coli arsRp: luc | 120 | 3.75 | As(III) | |
E. coli DH5α (pASPW2–arsR–luxCDABE) | 120 | 0.74 | As(III) | |
E. coli DH5α (pPROBE′arsR–ABS–RBS–lacZ strain 2245) harboring arsR–lacZ fusion | 4.23 | 0.8 | As(III) | |
Magnetic nanoparticle based thermo-responsive biosensor | 0.08 | 1 | As(III) | |
Rhodopseudomonas palustris (crtIBS) | — | NA | As(III), As(V) | |
Aptamer–CTAB–AuNPs | 3 | 16.9 | As(III) | |
AuNPs DNA aptamer | 65 | 161 | As(III) | |
ssDNA–AuNPs | 15 | 0.18 | As(III) | |
Aptamers-AuNPs-surfactant | 35 | 0.6 | As(III) | |
S. cerevisiae pdr5Δ luxAB gene construct | 60 | 0.0007 | As(V) | |
A. niger harboring arsA–egfp fusion protein | 720 | 1.8 | As(V) | |
E. coli strain 1598 harboring plasmid pPROBE–ArsR–ABS | 72 | 10 | As(III) | |
DNA functionalised SWCNT hybrid biosensor | 180 | 0.05 | As(III) | |
Calf thymus DNA based SPR biosensor | 30 | 10 | As(III) |
(A) Different types of engineered nanomaterials divided into organic and inorganic nanomaterials (reproduced with permission from ref. . Copyright [2017] Walter de Gruyter). (B) Schematic illustration of electrochemical sensors and biosensors based on nanomaterials and nanostructures, in which electrochemical sensors for small molecular, enzyme-based biosensors, genosensors, immunosensors, and cytosensors are demonstrated (reprinted with permission from ref. . Copyright [2015] American Chemical Society). |
As mentioned above, electrode surface modification with metallic nanoparticles, carbonaceous nanomaterials ( e.g. carbon nanotubes, nanofibers and graphene) and even enzymes (arsenite oxidase) can improve detection sensitivity and selectivity, while circumventing interferences. Fig. 15 shows the schematic comparing the laboratory based electrochemical devices vs. portable electrochemical devices and classical electrodes vs. screen-printed electrodes. The commonly used materials (textile, paper based etc. ) and fabrication methods (inkjet, screen and 3D printing) are illustrated for the construction of flexible and wearable printed electrodes/sensors. 125 A low-cost plastic-based microfluidic arsenic sensor comprised of an ink-based three-electrode system used for rapid and point-of-use water quality monitoring. A water sample is applied to the sensing system and hand-held analyzer runs a voltammetric test on the sample to determine arsenic concentration. 126
Schematic overview comparing laboratory-scale based electrochemical device vs. portable electrochemical device, classical electrodes vs. screen-printed electrodes, and fabrication methods of printed electrodes (reprinted from ref. ; Copyright (2022), with permission from Elsevier). |
Electrode modifier | Electrode | Electrochemical technique | LOD (ppb) | References |
---|---|---|---|---|
Au(NPs)/AuNP: gold nanoparticles. Ru(NPs): ruthenium nanoparticles. MWCNT: multi-walled carbon nanotubes. GCE: glassy carbon electrode. CPE: carbon-paste electrode. SPE: screen-printed electrode. BDD: boron-doped diamond. UME: ultramicroelectrode. CV: cyclic voltammetry. ASV: anodic stripping voltammetry. CA: chronoamperometry. DPV: differential pulse voltammetry. SWV: square wave voltammetry. SWASV: square wave anodic stripping voltammetry. DPASV: differential pulse anodic stripping voltammetry. LSASV: linear sweep anodic stripping voltammetry. DPSV: differential pulse stripping voltammetry. | ||||
Au(NPs) | GCE | SWASV | 0.025 | |
Au(NPs) | Boron-doped diamond | DPASV | 0.005 | |
Au(NPs) | GCE | SWASV | 0.28 | |
Au(NPs) | Ultra-micro electrode | SWASV | 0.05 | |
Au(NPs) | Nanoelectrode ensemble | SWASV | 0.005 | |
Au(NPs) | GCE | LSV, SWV | 0.0096 | |
Au(NPs) | GCE | ASV | 0.25 | |
Au(NPs) | GCE | SWASV | 0.15 | |
Au(NPs)/MWCNT | GCE | LSV, SWASV | 0.1 | |
Pt(NPs) | GCE | CV, LSV | 2.1 | |
Ru(NPs) | GCE | DPV | 0.1 | |
Au–Cu bimetallic | GCE | SWASV | 2.09 | |
Au–Pd bimetallic | GCE | ASV | 0.25 | |
Au NP layer from Au/Si alloy | SPE | CV, DPASV | 0.22 | |
Au(NPs) | GCE | DPV, CV, ASV, LSV | 0.9 | |
Au–Pt bimetallic | GCE | LSASV | 0.28 | |
Oxides | ||||
MnOx/Au NP | GCE | LSASV | 0.057 | |
Mesoporous MnFe O | GCE | SWASV | 3.37 | |
Fe O /ionic liquids | GCE | SWASV | 0.0008 | |
SnO NP | Graphite pencil electrode | CV | 10 | |
Fe O /reduced graphene oxide nanocomposite | GCE | SWASV | 0.38 | |
CoO | GCE | CV, amperometry | 0.825 | |
Au NP/polyaniline | GCE | CV, ASV | 0.4 | |
Pt nanotube array | GCE | LSV | 0.1 | |
AuNPs/CeO –ZrO | GCE | CV, CA, SWASV | 0.137 | |
IrO | Boron-doped diamond | CV | 0.15 | |
Bismuth film electrode | Bismuth film electrode is formed in situ with arsenic | DPASV | 0.012 | |
Silane grafted bentonite modified CPE | CPE | ASV | 0.0036 | |
Graphene/PbO | GCE | SWASV | 0.01 | |
Pt–Fe(III)/MWCNT | GCE | ASV | 0.75 | |
Graphene oxide–Au NP | GCE | LSV | 0.2 | |
CNT–Au NP | SPE | LSV | 0.5 | |
Carbon black–Au NP nanocomposite | SPE | LSV | 0.4 | |
Other type of electrodes | ||||
Nafion–AuNP composite | GCE | SWASV | 0.047 | |
AuNP | SPE | CV, DPASV | 0.11 | |
Au film | Plastic electrode | DPSV | 5 | |
AuNP | Carbon microfibre electrode | CV, DPV | 0.9 | |
Carbon nanotube/Au (NPs) | Carbon nanotube flow-through membrane electrode membrane | ASV | 0.75 | |
DWCNT/graphene/cholesterol oxidase | SPE | CV, SWV | 0.287 |
Thakkar et al. made a detailed review of arsenic detection methodologies with LODs of <10 ppb (WHO guideline value). They have critically compared the methods in terms of their potential to detect different arsenic species e.g. As( III ) and As( V ) in drinking water in the presence of interference from other ions. 17 According to Duoc and colleagues, a novel electrochemical sensor containing double-walled carbon nanotubes (DWCNTs) and a graphene hybrid thin film was discussed for As( V ) detection. 128 The hybrid thin films based on DWCNTs and graphene have been prepared for electrochemical sensing applications. The hybrid films were synthesised on polycrystalline copper foil by thermal chemical vapor deposition under low pressure. This carbonaceous hybrid film has exhibited high transparency with a transmittance of 94.3%. The occurrence of this hybrid material on the electrode surface of screen-printed electrodes was found to increase electroactive surface area by 1.4 times, whereas electrochemical current was enhanced by 2.4 times. This highly transparent and conductive hybrid film was utilised as a transducing platform of an enzymatic electrochemical As( V ) biosensor and showed the linear range from 1–10 ppb, with an LOD as low as 0.287 ppb. 128
AuNPs–polyaniline nanosheet array on iron containing carbon nanofiber (Au–PANI–Fe–CNFs composite) was reported as sensing platform for the determination of As( III ). 129 The Au–PANI–Fe–CNFs composite was constructed by the formation of polyaniline (PANI) nanosheet array on the electrospun Fe-containing carbon nanofibers (Fe-CNFs) substrate and self-deposition of Au nanoparticles. PANI presents a uniform array structure on the fiber surfaces and Au nanoparticles (20 ± 6 nm) were deposited uniformly on the PANI nanosheet surface by means of the reducing property of PANI. The presence and role of Fe in the CNFs was mentioned to accelerate the growth of PANI nanosheet and improves the arsenic adsorption in the sensing process of As( III ). The Au–PANI–Fe–CNFs sensor exhibit excellent electrochemical performance for the detection of As( III ) in water (linear range 5–400 ppb with an LOD of 0.5 ppb, S/N ≥ 3) and attributed to the unique structure of PANI array and uniform AuNPs distribution. 129 According to Bu et al. , a new material of 3D porous graphitic carbon nitride (g-C 3 N 4 ) decorated by gold nanoparticles (AuNPs/g-C 3 N 4 ) was designed using a mesoporous molecular sieve (SBA-15) as the sacrificial template. 130 The reported AuNPs/g-C 3 N 4 /GCE electrode demonstrates superiorities compared to AuNPs/GCE prepared by electrochemical deposition, highlighting the specialties of g-C 3 N 4 in increasing activity and sensitivity with an extremely low LOD of 0.22 ppb. 130 Zhang and Compton recently reported the use of anodic stripping voltammetry (ASV) allowing sub 10 ppb measurement of total As and As( III ) in water using the gold macroelectrodes and based on the underpotential deposition (UPD) of As ad-atoms ( Fig. 16 ). 131 The detection of As( III ) or total arsenic can be selectively made by changing deposition potential (total As content by deposition at −1.3 V and As( III ) at −0.9 V, linear responses were observed in the range 0.01–0.1 μM). The analytical signals were recorded at concentrations as low as 0.01 μM (0.8 ppb) for both arsenic species which suggests that this method could be used to detect total arsenic concentrations in drinking water within the WHO threshold value of 10 ppb. The As( V ) concentration can be determined by subtraction from the total arsenic concentration of the As( III ) concentration.
The total arsenic concentration measured by deposition at −1.3 V while the As(III) measured at −0.9 V on gold macroelectrodes based on the underpotential deposition (UPD) of As ad-atoms (reprinted from ref. ; Copyright (2022), with permission from Elsevier). |
This review provides an overview of existing methods for analysis of arsenic (mainly As( III ) and As( V )) in water. Various chromatographic, spectroscopic, colorimetric, biological, electroanalytical and coupled techniques were discussed followed by evaluation of their performances towards arsenic detection and determination. Relevant images and informative data are presented throughout the manuscript by reviewing the concerned literature for various analytical technique and methods. Current challenges as well as potential avenues for future research, including the demands for enhanced analytical performance, rapid analysis and on-site technologies for water analysis are discussed. Currently the coupled or hyphenated analytical techniques and methods ( e.g. ICP-MS, LC-MS, HPLC/ICP-MS) are the most promising and realistic way of arsenic determination but the novel and on-site methods based on biosensors, nanomaterials and electroanalytical or electronic devices are the future hopes for sensitive, rapid and cost-effective arsenic detection and determination. The use of novel materials, biomaterials and advanced functional nanomaterials (including metallic nanoparticles, graphene, carbon nanotubes, QDs and polymer-based nanocomposites) have the potential to improve the sensitivity, selectivity, biocompatibility and overall performance, and could open up new opportunities in the future arsenic analysis. Overall, this review will be beneficial and enhance awareness and appreciation of the role of analytical techniques in arsenic determination and in protecting our environment and water resources.
Conflicts of interest, acknowledgements.
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Home > Books > Arsenic - Analytical and Toxicological Studies
Submitted: 21 November 2017 Reviewed: 16 February 2018 Published: 25 July 2018
DOI: 10.5772/intechopen.75531
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Depending on the physical, chemical and biogeochemical processes and condition of the environment, various arsenic species can be present in water. Water soluble arsenic species existing in natural water are inorganic arsenic (iAs) and organic arsenic (oAs) species. All acidic species, according to the chemical equilibrium, have well-recognized molecular and ionic forms in water. The distribution of iAs and oAs species is a function of pH value of water traces of arsenic that are found in groundwater, lakes, rivers and ocean. The WHO provisional guideline value for arsenic in drinking water is 10 μg L−1. The most selective and sensitive methods for determination of total arsenic and its species in water are coupled techniques including chromatography, optical methods and mass spectrometry. Determination of arsenic species is of crucial importance for selection of arsenic removal technology. Best available technologies are based on absorption, precipitation, membrane and hybrid membrane processes. Adsorption is considered to be relatively simple, efficient and low-cost removal technique, especially convenient for application in rural areas. Sorbents for arsenic removal are biological materials, mineral oxides, activated carbons and polymer resins.
Ljubinka rajakovic *.
*Address all correspondence to: [email protected]
Arsenic, As, belongs to the group of elements that are called metalloids. A metalloid is a chemical element that has properties of both metals and nonmetals. Arsenic is from all its features mostly recognized as a poison. Arsenic has a complex chemical behavior since it exists in four different oxidative states [ 1 ]. Depending on oxidative state and presence in environment, arsenic species exhibit different toxicity [ 2 ]. Arsenic species can be present in all types of environment and can originate from natural and anthropogenic sources [ 3 ]. Natural sources of arsenic are: rocks with incorporated arsenic compounds, activity of volcanoes and some biological processes. Anthropogenic sources are numerous, from mining to different types of production (pesticides, wood preservatives, and pigments). When the arsenic compounds reach groundwater, it is hard to distinguish the origin, both natural and anthropogenic arsenic species are released [ 3 ].
According to Science Direct, during the last decade, a significant number of scientific papers reporting the results from arsenic investigations are presented in Figure 1 . The focus of these researches was the development and improvement of methods for arsenic detection, extraction, separation and removal.
The number of publications with keyword arsenic, according to Science Direct.
The investigation of arsenic species and their behavior in various samples, especially in natural waters and environment is important for chemistry and environmental protection. The most common arsenic species are presented in Table 1
Arsenic species | Oxidation state | Chemical formula | Group | Presence in the environment |
---|---|---|---|---|
As(V) | +5 | AsO | iAs | Water |
As(III) | +3 | AsO | ||
MMA | +5 | CH AsO(OH) | oAs | |
DMA | +5 | (CH ) AsO(OH) | ||
TMAO | +5 | (CH ) AsO | Seafood (fish, mussels) | |
TETRA | +3 | (CH ) As | ||
AsB | +3 | (CH ) As CH COO | ||
AsC | +3 | (CH ) As CH CH OH |
Common inorganic and organic arsenic species [ 5 ].
Depending on the oxido-reduction conditions, microbiological environment, arsenic species can be present in water in solution or in a precipitated form, and they can also adsorb or desorb from the existing precipitates [ 1 , 2 ]. When arsenic species are soluble in water, they can be present in both inorganic and organic forms. For iAs species both As(III), arsenite, and As(V), arsenate, can be present. For oAs species, MMA and DMA are soluble forms of organic arsenic species. From the value of the chemical equilibrium constants for each molecular or ionic form of arsenic in water, the present species can be recognized [ 3 ]. When choosing and analyzing the most dominant form of arsenic in water, the most present is inorganic arsenic as As(V). If As(III) is present, there are two important things that need to be taken into account. As(III) is more poisonous (even at low concentrations) than As(V). Beside the severe toxic effect, As(III) is easily oxidized. In oxidized conditions, stable forms of arsenic are As(V), and MMA and DMA, from oAs species. Many water sources in the world containing high concentration of arsenic cause health problems or diseases such as cancer. The WHO provisional guideline value for arsenic in drinking water is 10 μg L −1 [ 4 ]. Water quality analysis usually do not include test on arsenic. Arsenic compounds are colorless and odorless.
Once the presence of arsenic is determined in water, the separation and removal is obligatory. Removal technologies that are efficient, but still need improvement include absorption, precipitation, different electrochemical processes, membrane and hybrid membrane processes [ 6 , 7 , 8 , 9 ].
Arsenic enters the water through the dissolution of minerals, ores soil, sediments, water, living organisms and rocks containing high concentrations of arsenic. Drinking water from surface water bodies usually does not contain high concentrations of arsenic. Higher concentrations have only been found in the groundwater. Human activities influence and change the content of arsenic in nature. When using arsenic compounds for different purposes, there is a direct influence. There is also indirect influence that affects the mobility of arsenic from different natural sources. Organic arsenic compounds such as AsB, AsC, TETRA, TMAO, arsenosugars and arsenic-containing lipids are mainly found in marine organisms although some of these compounds have also been found in terrestrial species.
Despite the fact that iAs species are predominant in natural waters, the presence of oAs has also been reported. Even though the main analytical interest is to determine total arsenic in water, it is also important to develop the procedures for As species determination, separation, and removal. The distribution of i As and oAs species is a function of pH value of water [ 2 ].
The distribution of arsenic species vs. pH values of water is presented in Figure 2 [ 2 ].
The distribution of iAs and oAs species as a function of pH values of water [ 2 ]. Copyright approved by publisher.
As(III) species: H 3 AsO 3 , H 2 AsO 3 − , HAsO 3 2− and AsO 3 3− , are stable under slightly reducing aqueous conditions. As(V) species: H 3 AsO 4 , H 2 AsO 4 − , HAsO 4 2− and AsO 4 3− , are stable in oxygenated waters [ 6 ]. Two valences of the same element, molecular (ortho, H 3 AsO 3 , H 3 AsO 4 and meta forms, HAsO 2 , HAsO 3 ) and ionic forms with different charges make the research of arsenic removal from water more challenging and indivisible of arsenic chemistry knowledge. Any arsenic removal technology strongly depends on the water conditions and the stability of arsenic forms in the water.
Bearing in mind the fact that arsenic occurs in water in molecular and ionic form depending on water pH, the main goal of many investigations is to select the most efficient exchanger, not only in terms of efficiency, but also in terms of applicability in the wide range of water pH values in real and environmentally friendly water treatment systems. In neutral conditions, As(V) species are completely in ionic form (H 2 AsO 4 − and HAsO 4 2− ), while As(III) is in molecular (H 3 AsO 3 or HAsO 2 ), as shown in Figure 2 [ 2 ].
There are a variety of chemical methods from classical to contemporary analytical techniques that are used for determination of arsenic and arsenic species in water.
There has been several review articles on the speciation of arsenic in a variety of samples [ 10 , 11 , 12 , 13 , 14 ]. These reviews focus on (1) determination of total content of arsenic and (2) speciation analysis.
A review of contemporary methods for arsenic and arsenic species in water is presented in Table 2 . The parameters, as detection limit, advantages and disadvantages are pointed out in order to have an insight into ability and application of available techniques.
Methodology | Detection | Detection limit (μg L ) | Advantages | Disadvantage | Ref. |
---|---|---|---|---|---|
ICP-AES | Total arsenic | ~30 | Minimal sample volume; no sample pretreatment and short measurement time | Expensive; needs lot of knowledge for operating and interpretation of data | [ ] |
ICP-MS | Total arsenic | ~0.1 | Approved by US EPA | Spectral and matrix interferences | [ , , ] |
GF-AAS | Total arsenic | ~0.025 | Approved by US EPA | — | [ , ] |
HG-AAS | Total arsenic and arsenic speciation | 0.6–6.0 | Approved by US EPA | — | [ ] |
HPLC-HG-AAS | Total arsenic and arsenic speciation | 1–47 | No need for sample pretreatment | — | [ , ] |
HPLC-HF-AAS | Arsenic speciation | 0.05–0.8 | Rapid, inexpensive. No need for sample pretreatment | — | [ , ] |
IC-ICP-MS | Arsenic speciation | 0.01 | No need for sample pretreatment | — | [ ] |
HPLC-ICP-MS | Total arsenic | 0.01 | No need for sample pretreatment | — | [ ] |
A review of contemporary methods for arsenic and arsenic species determination in water.
The total concentration of arsenic in drinking water (mostly traces of arsenic, level of μg L −1 or less) can be detected only by sophisticated analytical techniques as ICP-MS, GF-AAS and HG-AAS [ 3 , 14 ]. For As speciation analysis, well-established methods that involve the coupling of separation techniques, such as HPLC with a sensitive detection system, that is, ICP-MS, are recommended, and they are mostly used [ 13 ].
Historically, colorimetric/spectrophotometric methods have been used to determine total arsenic concentration. Several commercial field kits have been based on Marsh and Gutzeit reaction. All As species in a sample reduce to As (arsenic mirror) or arsine, AsH 3 , (it passes on to an HgBr 2 -impregnated filter, turning it to yellow to brown color, depending on the amount of arsenic present). These tests are obvious, visible proofs for arsenic detection, and they are popular and useful in the field of forensic toxicology. The colorimetric methods are easy to use and inexpensive in terms of equipment and operator cost. They are useful for the semi-quantitative determination of high concentrations of arsenic in water. Spectrophotometric methods are based on conversion of arsenic to the colored compound such as molybdenum blue, or silver diethyldithiocarbamate [ 15 , 16 ].
Electrochemical methods , particularly voltammetric methods, are affordable, sensitive and ease of fabrication, and they are noteworthy for arsenic determination. Much work has been done in this area [ 12 ]. The ASV methods using platinum and gold electrodes, and CSV method using a glassy-carbon electrode have very low detection limit for arsenic determination. Determination of total As is performed by reducing As(V) to As(III) using various chemicals, and the limits of detection achieved were in vicinity of 0.02 μg L −1 . Also, arsenic in drinking water can be measured with Cu(II) by differential pulse cathodic stripping voltammetry (DPCSV) using hanging mercury drop electrode (HMDE) as working electrode and Ag/AgCl as reference electrode [ 12 , 17 , 18 ].
At present , for total As concentration determination, laboratories often prefer more sensitive methods such as AAS, AES, MS or AFS. Usually, the total concentration of arsenic needs to be determined, then the speciation analysis follows.
To perform speciation analysis properly, the best option is coupling of two analytical techniques. One technique is used for the separation of all chemical forms of arsenic that are present in water, and the other is used for the detection of these species. Besides coupling analytical techniques, there are necessary steps for complete analysis of arsenic. The first one is the extraction of arsenic, which has to be both mild and effective, at the same time. The second step is separation of various forms of arsenic species. The final step is the measuring step which gives the answer to the quantification of each present arsenic compound.
Analytical methods for determining different arsenic species have become increasingly important due to different toxicity and chemical behavior of various arsenic forms. Methods that involve the coupling of separation techniques, such as IC and HPLC with a sensitive detection system, such as ICP-MS, HG-AFS, HG-AAS and GF-AAS [ 3 , 11 , 13 , 14 , 19 ]. HPLC has been a preferred technique used for separation of arsenic compounds. Coupled with ICP-MS for determination, as HPLC-ICP-MS system it is a method of choice for separation and measurements all arsenic species in water. In addition, applying IC coupled with ICP-MS, it is possible to separate and estimate arsenic species in water: iAs(III), iAs(V), DMA, MMA, AsBet. A representative result is presented in Figure 3 [ 19 ].
Determination of five arsenic species by IC-ICP-MS. Mobile phase: NaOH [ 19 ].
The evaluation of analytical method is based on defining: selectivity, repeatability, accuracy, specific features of the method and defining the limits of detection and quantification (LoD and LoQ). These limits, these numbers give the information on the smallest concentration that can be detected and quantified with certain accuracy that has been defined [ 10 ]. The LoD was discussed and determined for the induced coupled plasma-mass spectrometry (ICP-MS) measurements of arsenic [ 11 ]. Thorough analysis has shown that the best option for LoD would be experiments, which would include the repetition many times. If experiments would be repeated 100 times, it is expected that only five measurements would be inadequate. Although this is ideal, the time consumption for the repetitive measurements is not acceptable. The most important conclusions were that LoD is not permanent and constant value, and it has to be verified and adopted for each new case. LoD is a basic parameter for estimation of the LoQ. It was concluded in [ 11 ] that the traditional (IUPAC) method is the one that could be applied.
Different methods can be applied for arsenic removal from water. Arsenic (V) is more effectively removed than As(III) by both conventional and nonconventional methods. Pretreatmen (preoxidation) of As(III) to As(V) is an essential step for better removal [ 2 ]. Methods that have been successfully applied in water treatment plants are: precipitation and coprecipitation, electrochemical (such as electrocoagulation), ion exchange and MST (reverse osmosis, ultrafiltration and other membrane techniques) [ 6 , 7 , 8 , 9 , 20 , 21 ].
A wide range of sorbent materials for aqueous arsenic removal has been tested and used: biological materials, mineral oxides, activated carbons and polymer resins. Even some agricultural and industrial by-products such as red mud, fly ash, waste iron slag from steel production plant and waste filter sand from water treatment plant, have proved to be good and inexpensive arsenic sorbents [ 6 , 7 ]. The potential use and application of industrial wastes in water treatment is in favor of the eco-friendly concept that preserves natural resources and supports the reuse-recycle concept. The technology of arsenic adsorption is based on materials which have a high affinity for dissolved arsenic. Adsorption of arsenic by iron modified sorbents has been established by several authors [ 6 , 7 ]. There are numerous scientific and professional investigations with intention to develop a small and efficient system for arsenic removal based on natural and artificial sorption materials [ 20 , 21 ]. Large amount of chemicals used for precipitation and coprecipitation processes (alum sulfate or ferric chloride) produce sludge, which needs treatment before disposal. If not treated properly, leachate with high concentration of arsenic is emitted to soil, threatening to contaminate the aquifers.
A step forward has been made by investigations that were devoted to the evaluation of selective multifunctional sorbents including ion-exchange resins for SPE and chromatographic columns connected with a sensitive measurements system [ 2 ]. The need to determine As species in water resulted in developing new materials for arsenic separation and removal. A simple procedure for selective separation (in pretreatment) of arsenic species in water using chemically modified and unmodified ion-exchange resins is presented in Figure 4 [ 2 ].
Procedure for selective separation arsenic species in water using ion-exchange resins [ 2 ]. Copyright approved by publisher.
For separation of As species in water, two types of resins, strong base anion exchange resin (SBAE), hybrid resins (HY) and hybrid resin chemically modified (HY-Fe and HY-AgCl), were tested and used. The HY-Fe resin retained all arsenic species except DMAs(V). This is recognized as an advantage because this makes direct measurement of this species in the effluent possible. The HY-AgCl resin retained all iAs, which was convenient for direct determination of oAs species in the effluent. The selective bonding of arsenic species on three types of resins, as shown in Figure 4 , has been established as the procedure which enables the separation and calculation of all arsenic species in water [ 2 ].
EC comprises complex chemical and physical processes involving many surface and interfacial phenomena. Very effective and perspective EC process consists of three processes: electrochemical reactions (simultaneous anodic oxidation and cathodic reduction), flotation and coagulation [ 9 , 20 ]. The EC process relies on the generation of metal ions from electrodes. The electrodes can be made of iron, aluminum or zinc, depending on the most favorable reactions for arsenic removal. The reaction in reaction chamber starts after the application of direct current. The electrode (metallic anode) dissociates into valent metallic ions. The metallic ions migrate to oppositely charged ions and the precipitation of different insoluble salts occur (different sulfides, oxides, hydroxides, chromates or phosphates, depending on the presence of ions in water). EC has several advantages when compared to other methods. The construction of reaction chamber is compact, control of the process is simple, no additional chemicals are required, and the result is reduced amount of sludge. If the electrode is made of iron, ferric hydroxide is one of the main solid products, as shown in Eq. (1) [ 9 ]:
Arsenate co-precipitates or adsorbs to Fe(OH) 3 (s), as shown in Eq. (2) .
The potential of EC as an alternative water treatment technique to remove arsenic from water needs to be realized [ 8 , 9 , 20 ].
Ion-exchange, IE, processes with regeneration capability is a proven, efficient and low-cost treatment method for the exchange of arsenic in the As(V) form [ 1 , 2 ]. The ion-exchange reaction between As(V) and a bed of chloride-form SBAE resin (designated as R-Cl resin) occurs as presented by Eq. (3) :
When the regeneration of resins is needed, both HCl and NaCl can be applied. Still, with HCl solution, more efficient regeneration occurs because the ionic forms of arsenic (anions) transform to molecular form (H 3 AsO 4 ). Molecular forms do not affect the equilibrium of ion-exchange processes as illustrated by Eq. (4) :
Different sorption processes, from adsorption, to chemisorption and ion-exchange, have shown a potential being efficient and cheap (depending on the selected sorbent). With improved, more selective and chemically modified sorbents, the extraction technique can be replaced [ 17 , 18 , 19 ]. What has been specifically used as an advantage for arsenic species separation is different behavior of arsenic species at various pH values [ 3 , 22 ].
The hybrid resin (HY) that has successfully been applied uses the activity of the hydrated iron oxides (HFO) and anion exchange for selective separation of arsenic [ 2 ]. With integrated use of anion exchange and sorption, the separation of As(III) and As(V) species and removal of all species of arsenic can be accomplished. With application of HY resin, two separate things can be accomplished: the collection and preconcentration of low concentrated iAs or the removal of iAs species, if it is interfering the determination.
Membrane separation technologies, such as RO, NF, UF, MF, can be employed in the removal of arsenic from water. Depending on the removal efficiency, RO and NF are more efficient than UF and MF. Operating conditions, membrane material, water quality, temperature, pressure, pH value and chemical compatibility have to be considered during operation of a membrane plant. When MF and UF are applied, less amounts of chemicals are used, and therefore, less sludge is produced. When RO and NF are used, no chemicals are needed and the amount of sludge is neglectable [ 8 ].
The comparison and future perspective of different technologies for arsenic removal are presented in Table 3 .
Technology for arsenic removal | Advantage | Disadvantage | Some specific feature | Future perspective |
---|---|---|---|---|
Adsorption | Cheap materials, effective and efficient removal | Further treatment for regeneration and consumption of chemicals | Additional filter for removal of fine particles is required | Still attractive as an efficient and cheap technology for As removal. Finding new, environmentally friendly sorbent is still a challenging task |
Chemical coagulation | Effective for industrial wastewater treatment plants and efficient for As(V) removal | Chemical required. pH adjustment needed. Large volumes of sludge that needs further treatment | Arsenic leaching out from sludge | Not attractive as a solution, only if it coupled with electrochemical techniques |
Electrocoagulation | Efficient for arsenic removal. Low maintenance costs. No chemicals or pH adjustment. Low operating costs | Applicable only on batch scale. Passive oxide films for on the electrode. High energy consumption | No generation of secondary pollutants | Attractive for future investigations. Need to overcome the lack of application on a large scale |
Ion exchange | Efficient for As(V) removal. Exchange resins are available; the selective resins for removing arsenic are one of the most important requirements to provide high removal. Together with hybrid solution is an excellent technology | Interference with other ions. Easily blocked. Huge amount of chemicals | Using this kind of technique depends on the pH values of water | Attractive only if selective and sensitive chemical agents are included in ion-exchange process |
Membrane technologies | Efficient in arsenic removal. No chemical reagents. No sludge. Small dimensions for membrane treatment plant. Easy automation and control | Removal of arsenic depends on the pressure, pH value, solute concentration, temperature of feed solution | Arsenic is concentrated in the retentate | Attractive in future perspective. With decrease of investment the MST will prevail in arsenic removal technologies. Different membrane materials and processes need to be evaluated to select the optimum for each situation |
The comparison and future perspective of different technologies for arsenic removal.
Arsenic contamination of water has been reported as a critical issue in many articles, which reflects the latest state-of-the-art understanding of the behavior and toxicity of various arsenic species. Many water sources in the world contain low concentration of arsenic (mostly traces of arsenic, level of μg L −1 or less). If the concentration of arsenic in drinking water is higher than 10 μg L −1 , which is the WHO provisional guideline value for arsenic, it causes various health problems. All arsenic compounds dissolved in water are toxic. In natural waters, arsenic appears most often in inorganic forms and to a lesser extent in organic form. Inorganic species, arsenic acids (H 3 AsO 3 and H 3 AsO 4 ) and their ions are more toxic than organic forms. In addition, As(III) species are more toxic than As(V) ones. The valence (+III and +V), the type of arsenic species, ionic or molecular forms are dependent on the oxidation–reduction condition and pH of the water. Arsenic in water occurs in both inorganic and organic forms, but inorganic species are predominant in natural waters. In neutral conditions, As(V) species are completely in ionic form (H 2 AsO 4 − and HAsO 4 2− ), while As(III) is in molecular form (H 3 AsO 3 or HAsO 2 ).
Arsenic compounds are colorless and odorless, and testing water for arsenic is an important strategy for the health and well-being of people. Working with a water professional to monitor and maintain the quality of the well and water supply is an important responsibility.
In this work, methods for arsenic and arsenic speciation separation, determination and removal were reviewed. There are numerous methods for separation and determination of arsenic species in water. It is very important to recognize easy, simple and inexpensive methods to estimate the very low concentrations of arsenic.
The total concentration of arsenic in drinking water can be detected by simple Gutzeit method, and some similar colorimetric methods of comparing stains produced on treated paper strips. Although its minimum detectable concentration is 1.0·μ L −1 , these tests should be used when only a qualitative or semiqualitative detection is needed.
For precise, and reliable determination of arsenic in water, only sophisticated analytical techniques as ICP-MS, GF-AAS and HG-AAS can be applied. These methods are approved by US EPA. The features of these methods are high sensitivity, high accuracy, minimal sample volume; no sample pretreatment and short measurement time with minimum detectable concentration of 0.1 μ L −1 . They are expensive, need lot of knowledge for operating and interpretation of data.
For As speciation analysis, well-established methods that involve the coupling of separation techniques, such as HPLC with a sensitive detection system, that is, ICP-MS, are recommended, and they are mostly used. Through the limits, it is possible to define the smallest concentration of analyte that can be reliably detected and quantified. Limit of detection for the HPLC-ICP-MS system is 0.001 μ L −1 . This system is also expensive and needs lot of knowledge for operating and interpretation of data.
In all works, a special attention is paid to the preservation of arsenic species in environmental water samples for reliable speciation analysis. An appropriate procedure for the extraction of arsenic species from water should be accomplished without changing any original state of arsenic. This is still a challenging topic for research. The proposed system showed themselves to be accurate, precise and time efficient, as just a very simple sample treatment is required. Successful application of all methods required considerable practice.
Sorption processes (ion exchange, adsorption, chemisorption) with regeneration capability are proven as efficient and low-cost treatment methods for the removal of arsenic species from water. Separation of arsenic species using these new selective and chemically active sorbents recognize as a cost- and time-saving alternative to the traditional extraction techniques. The major drawback of all these techniques is that they are unable to remove As(III) efficiently.
Membrane separation technologies, such as RO, NF, UF, MF, are recommended for the removal of arsenic from water in water treatment plants.
Although there are numerous research papers focused on extraction techniques, yet it is not possible to set universal extraction procedures. These procedures depend on the presence of different species as well as on the type of matrices. For arsenic speciation, the choice of the most appropriate method is of great importance for obtaining reliable and accurate results.
The authors are grateful to the Ministry of Education and Science of the Republic of Serbia which supported our scientific work (projects no. TR37009, TR37010 and III43009).
As | arsenic |
iAs | inorganic arsenic |
oAs | organic arsenic |
As(III) | arsenite ion |
As(V) | arsenate ions |
MMA | monomethylarsenic acid |
DMA | dimethylarsenic acid |
TMAO | trimethylarsine oxide |
TETRA | tetramethylarsonium ion |
AsB | arsenobetaine |
AsC | arsenocholine |
IC | ion chromatography |
HPLC | high-performance liquid chromatography |
MS | mass spectrometry |
AES | atomic emission spectrometry |
ICP-MS | inductively coupled plasma-mass spectrometry |
ASV | anodic stripping voltammetry |
CSV | cathodic stripping voltammetry |
DPCSV | differential pulse cathodic stripping voltammetry |
GF-AAS | graphite furnace absorption spectrometry |
HG-AAS | hydride generation atomic absorption spectrometry |
HPLC-HG-AAS | high-performance liquid chromatography-hydride generation-atomic absorption spectrometry |
HPLC-HG-AFS | high-performance liquid chromatography or solid-phase cartridge separation combined with hydride generation-atomic fluorescence spectrometry |
HPLC-ICP-MS | high-performance liquid chromatography-inductively coupled plasma-mass spectrometry |
SPE | solid phase extraction |
IE | ion exchange |
SBAE | strong base anion exchange resin |
HY | hybrid resin |
EC | electrocoagulation |
RO | reverse osmosis |
NF | nanofiltration |
UF | ultrafiltration |
MF | microfiltration |
MST | membrane separation technologies |
© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution 3.0 License , which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Edited by Margarita Stoytcheva
Published: 25 July 2018
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Reportedly, 300 million people worldwide are affected by the consumption of arsenic contaminated groundwater. India prominently figures amongst them and the state of Bihar has shown an upsurge in cases affected by arsenic poisoning. Escalated arsenic content in blood, leaves 1 in every 100 human being highly vulnerable to being affected by the disease. Uncontrolled intake may lead to skin, kidney, liver, bladder, or lung related cancer but even indirect forms of cancer are showing up on a regular basis with abnormal arsenic levels as the probable cause. But despite the apparent relation, the etiology has not been understood clearly. Blood samples of 2000 confirmed cancer patients were collected from pathology department of our institute. For cross-sectional design, 200 blood samples of subjects free from cancer from arsenic free pockets of Patna urban agglomeration, were collected. Blood arsenic levels in carcinoma patients as compared to sarcomas, lymphomas and leukemia were found to be higher. The geospatial map correlates the blood arsenic with cancer types and the demographic area of Gangetic plains. Most of the cancer patients with high blood arsenic concentration were from the districts near the river Ganges. The raised blood arsenic concentration in the 2000 cancer patients strongly correlates the relationship of arsenic with cancer especially the carcinoma type which is more vulnerable. The average arsenic concentration in blood of the cancer patients in the Gangetic plains denotes the significant role of arsenic which is present in endemic proportions. Thus, the study significantly correlates and advocates a strong relation of the deleterious element with the disease. It also underlines the need to address the problem by deciphering the root cause of the elevated cancer incidences in the Gangetic basin of Bihar and its association with arsenic poisoning.
Aggregated cumulative county arsenic in drinking water and associations with bladder, colorectal, and kidney cancers, accounting for population served, introduction.
An estimated 300 million people worldwide are affected with arsenic poisoning leading to health hazards 1 , 2 . The contamination of groundwater with arsenic occurs either through anthropogenic or geogenic sources. People residing in different countries are exposed to increased doses of arsenic via consumption of arsenic-rich groundwater 3 . Worldwide, major arsenic hotspots have been identified in Taiwan, Chile, Mexico, China, Bangladesh, India and Argentina. Other incidents involving smaller population groups have been reported in Poland, Hungary, Japan, Canada and USA 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 .
Bihar, a state in Eastern India, located in Ganga-Meghna-Brahmaputra (GMB) basin faces problems of arsenic contamination in groundwater. Groundwater is the main source of drinking water which caters more than 80 per cent of drinking source in rural Bihar, hence the size of population exposed to adverse effects of arsenic is very high. The other sources of drinking water such as dug well, pond, surface water like lakes and rivers have lesser or no incidence of arsenic contamination, but these sources are not commonly utilized for the drinking purpose. Before 1980s, the open well water as ground water source were considered safe for drinking water but in recent years, due to increased anthropogenic activities and geogenic reasons, the arsenic contamination in the Gangetic plains has increased many folds. Out of 38 districts of the state of Bihar, 18 districts have been reported high arsenic contamination in groundwater 12 . It is estimated that more than 10 million people in Bihar are drinking water with arsenic concentration greater than the WHO/BIS permissible limit of 10 μg/L 13 . According to Ministry of Water Resources, Government of India, 1600 habitations from 67 blocks of 18 districts of the states are severely affected with arsenic poisoning. This has caused threat to an estimated 50 million population of the state out of which 13.85 million people are drinking arsenic contaminated water above 10 μg/L 14 . Hence, the existence of arsenic menace among the population is presently more than the estimated survey. In Bihar, the problem of arsenic poisoning in ground water was reported for the first time in Simaria Ojhapatti village of Bhojpur district. The exposed population was so severely affected, that most of the village people evacuated their households. The subjects exhibited typical symptoms of arsenicosis along with other internal diseases as well 15 . In the recent reports, it has been found that the districts of Bihar like Buxar, Bhojpur, Patna, Saran, Vaishali, Samastipur, Begusarai, Khagaria, Munger, Bhagalpur etc. lying close to the banks of Ganga river are severely affected by arsenic 13 , 16 . The use of arsenic contaminated drinking water is the major cause for skin, lung, bladder, kidney cancer as well as other adverse health effects such as skin manifestations, gastrointestinal disorders, neurological effects, hormone disruption and infertility, posing a global health concern 17 , 18 , 19 , 20 . Basically, the arsenic enters the body through drinking and passes through the gastrointestinal tract and reaches the blood which reaches the vital organs of the body and causes organ toxicity which in turn disrupts the metabolic function of the body causing disease in them 21 , 22 , 23 , 24 , 25 .
According to Globocan 2018, 18.0 million new cancer cases, 9.5 million death and 43.8 million relapses (within 5 year of survival) was reported 26 . According to the national data of National Cancer Registry Programme of the Indian Council of Medical Research (ICMR), India has reported 3.9 million cancer cases in 2016. The worst cancer affected states were Uttar Pradesh with 674,386 cases, followed by Maharashtra with 364,997 and Bihar with 359,228 while in south India, Tamil Nadu recorded 222,748 cases, Karnataka 202,156, Andhra Pradesh 159,696, Telangana 115,333 and Kerala 115,511 cases of cancer 27 .
The increased incidences of cancer in the state of Bihar has been a major challenge for the Government. The etiology of cancer incidences in this area has not been revealed properly. Hence, the present study is an approach to decipher the root cause of the cancer incidences in the Gangetic basin of Bihar and its association with arsenic.
The study was conducted at Mahavir Cancer Sansthan and Research Centre, Patna, Bihar. Altogether, 2000 cancer patients were identified and their blood samples were collected for the study. For the cross-sectional design, 200 blood samples of subjects free of cancer from arsenic free pockets of Patna urban agglomeration, Bihar were also collected as control.
Cancer patients: In our cancer institute, approximately 15,000 confirm cancer cases are reported annually. For the present study, 2000 cancer confirm patients were randomly selected from the year 2017 to 2019. The selection of the patients was carried out randomly in the OPD of the institutes. For the diagnosis of the disease, various tests were carried out and after the confirmation of malignancy, they were recommended for the present study and their blood samples were collected.
Control subjects: For the cross-sectional study, 200 subjects of urban Patna district of Bihar were selected as the control subjects. These subjects were from non- arsenic hit area of the district. These control subjects were taken in the study to compare the blood arsenic concentration between a normal subject versus cancer patients.
In the collection procedure, 5 ml of blood by volume was taken from the peripheral vein of the arm using disposable syringes and transferred to heparinised vaccutainer as per the guidelines of IUPAC 28 .
After the collection, all the blood samples were double digested using concentrated HNO 3 on hot plate under fume hood and estimated as per the protocol of (NIOSH) 29 through Graphite Furnace Atomic Absorption Spectrophotometer (Pinnacle 900T, Perkin Elmer, Singapore).
The patient based epidemiological data like patient’s age, gender, demographic area, cancer disease type, cancer stage etc. were collected from the patient files in the record room of MCSRC.
The data of arsenic concentration in blood samples of the subjects were taken as input in Arc-GIS 10 software for spatial analysis, correlation, exposure rate and to visualize a synoptic view of the district-wise exposure rate. Concentrations of arsenic in blood data of the cancer patients were analysed with generation of statistical data in form of map and categorization therein. The arsenic background status map of Bihar was used for visualizing the exposure rate. All the layers were analysed using ArcGIS environment. The final output was generated as a thematic map. The software used in the map layer generation is ArcMap10.5.1, ESRI, ArcGIS Desktop 10.5.1 licensed at TU Delft Faculty of Civil Engineering and Geosciences. All the shapefiles were created in the ArcGIS environment for which base map was extracted from OpenStreetMap data downloaded from the link " http://download.geofabrik.de/asia/india.html ". (OpenStreetMap contributors. (2017). Planet dump retrieved from https://planet.osm.org , https://www.openstreetmap.org ).
The data was reported to the Mahavir Cancer Sansthan and Research Centre which brought to light significant findings in regards to the study.
Data were analyzed with statistical software (Graph Pad Prism 5) and values were expressed as mean ± SEM. Differences between the groups were statistically analyzed by one-way analysis of variance (ANOVA) using the Dunnett’s test. The scattered graphs were plotted through another statistical software SPSS-16.0 using linear regression analysis model as earlier used 30 .
Ethical approval was obtained from the Institutional Ethics Committee (IEC) of Mahavir Cancer Sansthan and Research Centre with IEC No. MCS/Research/2015-16/2716, dated 08/01/2016.
The present study shows significant epidemiological information of 2000 cancer patients and 200 control subjects. The factors of age, gender, cancer type, blood arsenic concentration in blood of cancer patients and control subjects were given cognizance. Correlation coefficients of arsenic in blood and cancer subjects age, geospatial distribution of cancer patients and cancer type details were accounted.
Gender wise—Cancer patients vs control subjects: Total 2000 blood samples of patients were analysed, out of which n = 1213 patients were cancer female patients while n = 787 subjects were male cancer patients. In the total studied 200 control subjects, n = 112 were the female subjects, while n = 88 were the male subjects (Fig. 1 ).
Age wise in female cancer patients: In total n = 1213 female cancer patients, the maximum cancer incidences were observed in the patient’s age group between 31–70 years. In the control female subjects n = 112, the maximum studied groups were between 21–70 years of age group. The age group between 21–30 had the highest number of the studied subjects n = 56 (Fig. 2 ).
Age wise in male cancer patients: In total n = 787 male cancer patients, the maximum cancer incidences were observed in the patient’s age group between 21–70 years. In the control male subjects n = 88, the maximum studied groups were between 21–70 years of age group. The age group between 21–30 had the highest number of the studied subjects n = 44 (Fig. 3 ).
Type of cancer in female and male cancer patients: Out of n = 1213 females, n = 1088 cases were of solid tumours while, n = 125 females were of haematolymph cases while, out of n = 787 males, n = 644 cases were of solid tumours while, n = 143 males represented haematolymph cases (Fig. 4 ).
Blood arsenic concentration in female cancer patient’s vs female control subjects: Out of total n = 2000 blood samples of cancer patients analysed, n = 1213 (60%) blood samples were of female patients and the maximum arsenic concentration in their blood sample reported was 2048 μg/L. The minimum value of arsenic in blood was observed to be between 0-10 μg/L. In the present data, n = 523 (43.11%) blood samples were in the minimum range between 0–10 μg/L, out of which n = 395 patients had their blood arsenic concentration values less than 1.0 μg/L. The n = 102 subjects had the blood arsenic concentration between the range 11–20 μg/L. The rest n = 588 (48.47%) patients had the blood arsenic concentration more than the minimum range. In the control female subjects n = 112, maximum subject n = 98 (87.5%) had the blood arsenic concentration with in the minimum range 0–10 μg/L, the rest n = 14 (12.5%) had mild blood arsenic concentration in their bloods in the range between 11–20 μg/L. The maximum arsenic concentration in their blood sample reported was 19.4 μg/L (Fig. 5 ).
Blood arsenic concentration in male cancer patient’s vs male control subjects: Out of total n = 2000 blood samples of cancer patients analysed, n = 787 (40%) blood samples were of male patients and the maximum arsenic concentration in their blood sample reported was 2432 μg/L. The minimum value of arsenic in blood was observed to be between 0–10 μg/L. In the present data, n = 323 (41.04%) blood samples were in the minimum range between 0–10 μg/L, out of which n = 236 patients had their blood arsenic concentration values less than 1.0 μg/L. The n = 77 subjects had the blood arsenic concentration in the range 11–20 μg/L. The rest n = 387 (49.17%) patients had the blood arsenic concentration more than the minimum range. In the control male subjects n = 88, maximum subject n = 79 (89.7%) had the blood arsenic concentration with in the minimum range 0–10 μg/L, the rest n = 9 (10.2%) had mild blood arsenic concentration in their bloods in the range between 11–20 μg/L. The maximum arsenic concentration in their blood sample reported was 19.6 μg/L (Fig. 6 ).
Correlation coefficient between blood arsenic levels and age of the female and male cancer patients: The study showed significant increase in blood arsenic levels in the female cancer patients (r = 0.005 and P < 0.05) and male cancer patients (r = 0.003 and P < 0.05) (Fig. 7 ).
Correlation coefficient between blood arsenic levels and age of the female breast cancer patients: The study showed significant increase in the blood arsenic levels in the female breast cancer patients n = 401; (P < 0.05) (Fig. 8 ).
Correlation coefficient between blood arsenic levels and age of the female ovarian and cervical cancer patients: The study showed significant increase in the blood arsenic levels in the female ovarian (n = 39) and cervical (n = 203) cancer patients (P < 0.05) (Fig. 9 ).
Correlation coefficient between blood arsenic levels and age of the Gall bladder Cancer—female vs male patients: The study showed significant increase in the blood arsenic levels in the female (n = 93) vs male (n = 82) gallbladder cancer patients; (P < 0.05) (Fig. 10 ).
Correlation coefficient between blood arsenic levels and age of the Gastrointestinal Cancer—female vs male patients: The study showed significant increase in the blood arsenic levels in the female (n = 96) vs male (n = 88) gastrointestinal cancer patients (P < 0.05). This includes total gastrointestinal cancer cases (n = 184). Out of which the cancer of stomach was (n = 90), esophagus (n = 18), iliac (n = 09), colon (n = 21), rectum (n = 29) and anus (n = 17) (Fig. 11 ).
Correlation coefficient between blood arsenic levels and age of the Liver Cancer—female vs male patients: The study showed significant increase in the blood arsenic levels in the female (n = 64) vs male (n = 54) liver cancer patients; (P < 0.05) (Fig. 12 ).
Correlation coefficient between blood arsenic levels and age of the Lung Cancer—female vs male patients: The study showed significant increase in the blood arsenic levels in the female (n = 27) vs male (n = 37) lung cancer patients; (P < 0.05) (Fig. 13 ).
Correlation coefficient between blood arsenic levels and age of the Head and Neck Cancer—female vs male patients: The study showed significant increase in the blood arsenic levels in the female (n = 75) vs male (n = 268) head and neck cancer patients; (P < 0.05) (Fig. 14 ).
Correlation coefficient between blood arsenic levels and age of the Urinary bladder and Kidney Cancer—female vs male patients: The study showed significant increase in the blood arsenic levels in the female (n = 10) vs male (n = 18) urinary bladder and kidney cancer patients; (P < 0.05) (Fig. 15 ).
Correlation coefficient between blood arsenic levels and age of the female and male genital cancer patients: The study showed significant increase in the blood arsenic levels in the female (n = 73) genital cancer patients (P < 0.05). The female genital cancer cases included cancer of vagina, vault and uterus. The study also showed significant increase in the blood arsenic levels in the male (n = 42) genital cancer patients (P < 0.05). The genital cancer cases included cancer of prostate, testis, penis, seminal vesicle and scrotum (Fig. 16 ).
Geospatial Cancer distribution Map of 2000 Cancer patients with Average Blood Arsenic concentration—district wise: The district wise map shows the geospatial distribution of 2000 cancer patients with average blood arsenic concentration (Fig. 17 ).
Cancer types: The cancer types have been primarily categorised into 04 major parts—leukaemia’s, lymphomas, sarcomas and carcinomas. They have been further categorised into 18 subtypes. All the data have been correlated with blood arsenic concentration and their age. In carcinomas, the maximum number observed were of Breast cancer (n = 401), Head and Neck cancer (n = 343), Cervical cancer (n = 203), Gastro intestinal cancer (n = 184), Gall bladder cancer (n = 175), Liver cancer (n = 118) and the remaining types had their numbers less than 100. (Table 1 ).
Geospatial distribution of Cancer types: The maps show the district wise geospatial distribution of cancer types with average blood arsenic concentration. The district wise distribution with average blood arsenic is very significant with the level of arsenic exposure in Carcinoma (Fig. 18 A), Lymphoma (Fig. 18 B), Leukemia (Fig. 18 C), Sarcoma Fig. 18 D).
Skin cancer patient with arsenicosis symptoms : The studied patient was having skin cancer—squamous cell of carcinoma, drinking arsenic contaminated water of 322 μg/L and his blood arsenic concentration was 86.4 μg/L (Fig. 19 ).
Graph showing number of patients (gender wise) in cancer patients and control subjects (ANOVA-Dunnett’s Test, P < 0.05).
Graph showing age wise distribution of female cancer patients and control female subjects. (ANOVA-Dunnett’s Test, P < 0.05).
Graph showing age wise distribution of male cancer patients (ANOVA-Dunnett’s Test, P < 0.05).
Graph showing type of cancer in female and male patients (ANOVA-Dunnett’s Test, P < 0.05).
Arsenic concentration in blood samples of female patients were analyzed through GF-AAS (ANOVA-Dunnett’s Test, P < 0.05).
Arsenic concentration in blood samples of male patients were analyzed through GF-AAS (ANOVA-Dunnett’s Test, P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female (n = 1213) (r = 0.005 and P < 0.05) and male (n = 787) cancer patients (in years) (r = 0.003 and P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female breast cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female ovarian and cervical cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female vs male gallbladder cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female vs male gastrointestinal cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female vs male liver cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female vs male lung cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female vs male head and neck cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female vs male urinary bladder and kidney cancer patients (P < 0.05).
The correlation coefficient between blood arsenic levels and age of the female vs male genital cancer patients (P < 0.05).
Geospatial Cancer distribution Map of 2000 Cancer patients with Average Blood Arsenic concentration—district wise [Base map extracted from OpenStreetMap—( http://download.geofabrik.de/asia/india.html ) using ArcMap10.5.1].
( A ) Geospatial distribution of Carcinoma Cancer patients with Average Blood Arsenic Concentration [Base map extracted from OpenStreetMap—( http://download.geofabrik.de/asia/india.html ) using ArcMap10.5.1]. ( B ) Geospatial distribution of Lymphoma Cancer patients with Average Blood Arsenic Concentration [Base map extracted from OpenStreetMap—( http://download.geofabrik.de/asia/india.html ) using ArcMap10.5.1]. ( C ) Geospatial distribution of Leukemia Cancer patients with Average Blood Arsenic Concentration. [Base map extracted from OpenStreetMap—( http://download.geofabrik.de/asia/india.html ) using ArcMap10.5.1]. ( D ) Geospatial distribution of Sarcoma Cancer patients with Average Blood Arsenic Concentration. [Base map extracted from OpenStreetMap—( http://download.geofabrik.de/asia/india.html ) using ArcMap10.5.1].
Showing a cancer patient with skin cancer (squamous cell of carcinoma) in his palm with typical arsenicosis symptoms in sole and palm.
A detail assessment of incidence of arsenic in groundwater has been attempted in the middle Ganga plain in the Bhojpur and Patna districts of Bihar to study the distribution pattern and controlling factors of its occurrence. Groundwater samples were tested with field kit for arsenic, 3D surface maps were prepared at different depth levels and a positive correlation of geomorphology and depth with incidence of arsenic was worked out. It was observed that while the older alluvium surface in the area is free from hazardous incidence of arsenic, the older/present day flood plain surface has several localized pockets of higher incidence of arsenic (50 to > 500 μg/L). There is a specific depth control observed where the aquifer within 12–75 m depth range is yielding arsenic. Since, older alluvium (Peninsular origin) is free from hazardous incidences of arsenic in ground water, the source of arsenic contamination in the ground water appears to be associated with the holocene sediments of the Himalayan provenance brought down by the river Ganga and its tributaries of extra peninsular (Himalayan) origin 31 .
Ethical approval was obtained from the Institutional Ethics Committee (IEC) of Mahavir Cancer Sansthan and Research Centre with IEC No. MCS/Research/2015-16/2716, dated 08/01/2016. Furthermore, it is also certified that the informed consent was taken from the individuals who voluntarily participated in this study while the minor’s parents provided us the informed consent for this particular study.
In the human metabolic system, inorganic arsenic through drinking water reaches the blood through gastrointestinal tract. It is easily converted into organic form which in excess is primarily eliminated through urine. In the blood it remains for 2–6 hours and is mostly eliminated through the renal system 32 , 33 . It is also deposited in the keratin of skin, hair and nails and alters the epidermal keratinocytes causing keratosis, melanosis, rain drop pigmentation or other skin manifestations 34 . The arsenic adversely effects the epidermal system, the vascular system and the nervous system of human beings. The acute poisoning causes vomiting, diarrhea, abdominal pain, general body weakness, vertigo, nausea, muscle cramps etc. The long duration arsenic exposure causes skin manifestations like keratosis, melanosis in sole and palm along with rain drop pigmentation all over the body. Further, it also causes peripheral neuropathy, renal failure, gastrointestinal disruption, hypertension, diabetes, conjunctivitis, anaemia, loss of appetite, breathlessness, mental disability, hormonal imbalances, suppression of bone marrow and cardiovascular diseases 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 . The trivalent arsenic is more toxic than the pentavalent arsenic hence is known to be a carcinogen 4 , 10 , 45 , 46 . There are mainly three ways by which humans are exposed to arsenic—drinking arsenic contaminated groundwater, food prepared with the arsenic contaminated water and food crops irrigated with high arsenic contaminated groundwater. This causes entry of arsenic into human body through various routes causing life threatening disease like cancer of the skin, bladder, lungs, kidney, liver, and prostate 47 . There is adequate evidence which states that arsenic causes carcinogenicity in humans and the International Agency for Research on cancer has classified arsenic as Category-I carcinogen 4 . The skin cancer, Bowen’s disease and squamous cell carcinoma are very common in arsenic exposed population 4 , 48 , 49 , 50 , 51 . In recent studies, it has been found that arsenic is causing reproductive health hazards as cases of spontaneous abortion, stillbirth and preterm birth. The pregnant women who are continuously drinking arsenic contaminated water are also exposing their foetus through placenta causing severe health problem for the child after birth 52 , 53 .
During the course of this study, we have observed very high arsenic concentration in ground water samples (1929 μg/L) in Buxar district of Bihar. From the same household, we have also observed the blood arsenic concentration in a subject as 664.6 μg/L which is the highest reported case in the state of Bihar showing typical symptoms of arsenicosis 12 . Similar studies have been reported by many other researchers 54 , 55 , 56 , 57 , 58 , 59 , 60 .
The blood arsenic concentration in the exposed population has been rarely studied, since it is thought to be very weak biomarker. Hence, there had been no benchmark established for the blood arsenic concentration for humans. The present comprehensive study carried out is the world’s first study which deciphers the association between arsenic and cancer through blood arsenic study. In the present study, there was significantly high arsenic concentration in the blood samples of cancer patients especially in the females in comparison to male. This denotes that there is some pathway, which makes the arsenic exposed population more vulnerable, which subsequently due to sustained exposure gets converted into a life-threatening disease like cancer. Secondly, the significant levels of arsenic concentration have a distinct correlation with the incidences of cancer patients. The cross-sectional design also correlates that the non-cancer subjects (control subjects) hardly had any arsenic exposure, as n = 135 had zero arsenic concentration, while n = 42 between 1–10 μg/L of minimum range. However, n = 23 had very mild blood arsenic concentration levels between 10–20 μg/L. This explains our observations made as a part of study. Moreover, out of 2000 studied cancer cases, in the n = 1154 (57.7%) cancer cases, the blood arsenic concentration was found to be more than the minimum range (0–10 μg/L) and while n = 846 (42.3%) were in the minimum range. The coefficient correlation also is directly proportional to higher the age of the subject, more is the blood arsenic concentration. Thus, arsenic is first weakening the immune system and then causing the health ailments like cancer. The geospatial distribution of studied cancer patients with blood arsenic concentration in their blood also correlates that the disease burden is very high in the Gangetic basin of the state where the arsenic contamination in ground water is also relatively very high 61 , 62 , 63 . In a recent study carried out by our team in Patna district, Bihar, cancer mapping in Gyaspur Mahaji village has been extensively done to establish the relation and the study strongly correlates the association 64 .
Various studies have deciphered the molecular pathway of arsenic causing cancer in the subjects from arsenic exposed area. In squamous cell carcinoma of skin, arsenic binds with the receptors and disrupts the signal transduction pathways. The arsenic affinity to bind with sulfhydryl (SH) groups causes release of Reactive Oxygen Species (ROS) which leads to cellular toxicity and metabolic dysfunction 65 , 66 . The interaction of arsenic with thiol groups is associated with 200 known human proteins. These interactions cause production of ROS which leads to activation of oncogenes, upregulation of inflammatory pathways and inhibition of the function of tumour suppressor genes 41 , 67 , 68 , 69 , 70 , 71 .
In a recent study by some researchers, it is speculated that arsenic activates the cell proliferation through Canonical Hippo Signaling pathway which causes various types of malignancies including skin cancer 72 , 73 . Furthermore, arsenic upregulates the various components of Hippo signaling including mammalian STE20-like kinase STE20-like kinase 1/2 (Mst1), Salvador homolog 1 (Sav1), large tumour suppressor kinase 1/2 (LATS1) and Mps one binder kinase activator-like 1A (MOB1). In the epithelial cell proliferation Yes-associated protein (YAP) is a responsible component is dephosphorylated by arsenic causes the control over tight/adherens junctions of the epithelium 74 , 75 . In the recent times, various cancer types and its cause due to arsenic has been established say in case of bladder cancer 76 , 77 , 78 , 79 , 80 , 81 , 82 , for lung, kidney and laryngeal cancer 83 , 84 , 85 , 86 . In a study conducted in Brazil showed significant levels of blood arsenic in maternal chord blood with limit above 3.30 µg/L 87 . Study in another city in Brazil showed significant blood arsenic reference value as 9.87 µg/L 88 . While in a study carried out in 32 children in Yucatan, Mexico showed blood arsenic levels above 10 µg/L in 37% of the samples 89 . In a similar study conducted on 120 arsenic exposed residents (76 breast cancer cases) of Camarca Lagunera, Mexico showed the expression of Yes- Associated Protein (YAP), a tumour suppressor protein along with apoptosis inhibitor was measured. The result showed low percentage of YAP expression denotes abnormal expression of YAP in arsenic exposed breast cancer patients 90 , 91 .
Our institute (MCSRC) has registered more than 15,000 cancer cases in year 2019. The epidemiological data showed that most of the cancer cases reported were from the cities or towns which are located near the river Ganga. The most incidences of cancer cases were from the districts—Buxar, Bhojpur, Saran, Patna, Vaishali, Samastipur, Munger, Begusarai Bhagalpur etc. Various studies have reported that arsenic in the form of arsenopyrite load has reached these river basins in the form of silt from great Himalayas and has caused geogenic changes in the sediments and ground water causing health hazards to the exposed population 92 , 93 . It is evident from many studies that consumption of arsenic contaminated groundwater for drinking purposes and contaminated food has caused health related issues in the population in long duration exposure finally leading to cancer disease. Our epidemiological data also suggests that the districts located near the course of Himalayan bound river basins have more incidences in comparison to non-Himalayan river basins. Most common cancer cases recorded were of skin cancer, skin melanoma, lung cancer, bladder cancer, hepatobiliary cancer, renal cell carcinoma, breast cancer, ovarian cancer, endometrium cancer etc. with typical symptoms of arsenicosis denotes that there is a significant correlation with the arsenic. The arsenic contamination in the long duration of exposure is causing the exposed population contract the disease in primary phase and then acquiring second stage of disease, if not cured in time. It is quite possible that arsenic along with other confounding factors could be adding the disease burden. Apart from this, the cancer disease types like carcinomas are more aggressive than the other types like leukemias, lymphomas and sarcomas. The pathways related to cause of cancer in the arsenic exposed population needs further studies for the final validation and establishment of benchmark for blood arsenic concentration in humans.
The present study demonstrates the high incidence of cancer in arsenic prevalent, Gangetic basin. The study strongly correlates the association between arsenic and cancer incidence in the arsenic exposed population of Bihar in which significantly high arsenic concentration has been observed in the blood samples of cancer patients. Arsenic exposure also correlates with the high incidence of cancer disease burden in the carcinoma type of cancer in comparison to the sarcomas, lymphomas and leukemias type of cancer. This study reiterates the fact that the people living in the Gangetic basin are getting exposed to the continued arsenic toxicity leading to the development of several types of cancers. More systematic study is further required to understand the molecular mechanisms of arsenic toxicity in incidences of cancer and its progression and to establish the correlation by deciphering the signaling pathways for arsenic exposed human cancer. All this effort will eventually lead to the development of improved therapeutic approach.
The data that support the findings of this study is available from the corresponding author upon reasonable request.
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The authors are thankful to the institute (MCSRC) for providing all necessary infrastructures required for this particular study. The financial assistance for the study was provided by the institute itself.
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Arun Kumar, Mohammad Ali, Mukesh Kumar, Prity Sagar, Ritu Kumari Pandey, Vivek Akhouri, Vikas Kumar, Gautam Anand, Pintoo Kumar Niraj, Rita Rani & Ashok Kumar Ghosh
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A.K. and A.K.G. Conceptualized the entire work, A.K. had the major contributions in writing the manuscript but support was also provided by A.K.G., D.K., and A.B., literature search was done by V.A. and V.K., data were collected by M.K., G.A., R.K.P. and P.S., experimental work and data analysis were done by M.K., P.K.N. and P.S., data interpretation was carried out by A.K., M.A., R.K., D.K., A.B., and R.R., final figures were designed by A.K. and S.K.. All authors read and approved the final paper.
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Kumar, A., Ali, M., Kumar, R. et al. Arsenic exposure in Indo Gangetic plains of Bihar causing increased cancer risk. Sci Rep 11 , 2376 (2021). https://doi.org/10.1038/s41598-021-81579-9
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The purpose of this American Council on Science and Health report is to review issues and sources of uncertainty affecting assessment of potential health risks related to drinking water in the United States. Some background is included on how these issues arose, as is a review of the 1999 National Research Council report (with references to an updated version), to formulate a position based on the current science concerning how much of a risk of adverse health effects actually exists from arsenic in drinking water in the United States. ACSH concludes that there is clear evidence that chronic exposure to inorganic arsenic at concentrations of at least several hundred micrograms per liter may cause: (1) cancer of skin, bladder, lung (and possibly several other internal organs, including kidney, liver, and prostate), and (2) noncancer effects, including classic cutaneous manifestations that are distinctive and characteristic of chronic arsenic poisoning (diffuse or spotted hyperpigmentation and palmar-plantar hyperkeratoses). Noncancer effects may be multisystemic, with some evidence of peripheral vascular, cardiovascular, and cerebrovascular disease, diabetes, and adverse reproductive outcomes. Further study is needed to know if beneficial effects of arsenic in animal studies apply to humans. ACSH concludes that there is little, if any, evidence of a detrimental health effect in humans from inorganic arsenic in drinking water at the current maximum contaminant level (MCL) of 50 microg/L or below, either in the United States or elsewhere. As noted in the 1999 NRC report, "No human studies of sufficient statistical power or scope have examined whether consumption of arsenic in drinking water at the current MCL results in an increased incidence of cancer or noncancer effects" (NRC, 1999, p. 7). Based on our review, described in this article, ACSH finds that the limitations of the epidemiological data available and the state-of-the-science on the mode-of-action of arsenic toxicity, including can cer, are inadequate to support the conclusion that there are adverse health effects in the United States from arsenic in drinking water at or below the limit of 50 microg/L.
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In terms of its impact on human health, arsenic is unique in that most of the evidence linking it to diseases comes from epidemiological work; animal studies have not provided good models. It is also unique in causing a large number of different damaging effects and, as more studies are conducted, more such effects are found. To date, we know that arsenic from drinking water can cause severe skin diseases including skin cancer; lung, bladder, and kidney cancers, and perhaps other internal tumors; peripheral vascular disease; hypertension; and diabetes. It also seems to have a negative impact on reproductive processes (infant mortality and weight of newborn babies). The toxicology of arsenic involves mechanisms that are still not completely understood, but it is clear that a number of factors can affect both individual and population-level susceptibility to the toxic effects of arsenic-contaminated drinking water. Current research is addressing some of these, including genetic susceptibility and lifestyle factors that may increase arsenic's toxic effects, such as smoking, diet, and concurrent exposure to other substances. The reversibility of some effects upon cessation of exposure is also being investigated.
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Arsenic (As) is very common pollutant of the environment categorized as class-I human carcinogen. Rice crop is inherently efficient at accumulating As that is also triggered by conventional cropping methods (flooded conditions). A pot experiment was conducted with the objectives to (i) determine the accumulation of As in rice grains and shoots and As species in rice grains, (ii) determine the effect of As concentrations on physiological and agronomic characteristics of the rice crop, and (iii) assess the changes in fractions of As within the soil under different water regimes. Water regimes included flooding, intermittent, intermittent + aerobic, and aerobic irrigation. Grain As concentration from flood-irrigated rice was significantly ( P ≤ 0.05 ) reduced in rice grown in 10 and 50 mg kg −1 As-contaminated soil with less applied irrigation. Water management techniques have influenced As speciation in rice grains. As the irrigation techniques were shifted from flooding to intermittent, intermittent + aerobic, and aerobic irrigation, a significant decrease in concentration of inorganic species (11.98–76.81% at 10 mg kg −1 and 66.04–93.61% at 50 mg kg −1 ) was observed. Aerobic irrigation has effectively reduced the concentration of arsenic in rice grain as compared to other irrigation techniques in both the As-contaminated soils. This study indicated that irrigation management techniques other than flood irrigation have significantly affected the As (total and speciation) concentration within the rice grains and non-significantly affecting crop yield and this must be considered if regulations are based on inorganic As percentage of total As concentration.
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Arsenic uptake, accumulation and toxicity in rice plants: possible remedies for its detoxification: a review, effect of selenium application on arsenic uptake in rice (oryza sativa l.), data availability.
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We, the authors, are very thankful to the Higher Education Commission (HEC), Islamabad, for providing funds to conduct this research in Pakistan under the HEC-5000 Indigenous Program and to perform analytical work at Global Centre for Environmental Remediation, University of Newcastle, Australia, under its International Research Support Initiative Program (IRSIP).
Higher Education Commision,Pakistan,417-55070-2AG4-001,Muhammad Tahir Shehzad,IRSIP 38 Agri 14,Muhammad Tahir Shehzad
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Muhammad Tahir Shehzad, Muhammad Sabir & Saifullah
Global Centre for Environmental Remediation (GCER), College of Engineering, Science and Environment, The University of Newcastle, Callaghan, NSW, 2308, Australia
Abu Bakkar Siddique, Mohammad Mahmudur Rahman & Ravi Naidu
Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC-CARE), The University of Newcastle, Callaghan, NSW, 2308, Australia
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Dr. M. T. Shehzad, has collected, prepared, and analyzed the samples and performed statistical data analysis and written a manuscript. Dr. M. Sabir has supervised the whole research. Dr. Saifullah, Mr. A. B. Siddique, and Dr. M. M. Rahman have helped in writing and critically reviewing the manuscript. Samples were analyzed at Global Centre for Environmental Remediation, University of Newcastle, Australia, under the supervision of Prof. Ravi Naidu.
Correspondence to Muhammad Tahir Shehzad or Muhammad Sabir .
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• Arsenic (As), class-A human carcinogen, is ubiquitously present in the environment.
• Rice crops are inherently efficient at accumulating As triggered by continuous flooding.
• Aerobic irrigation effectively reduces the concentration of arsenic in rice grains.
• Arsenic levels were determined using an inductively coupled plasma–mass spectrometer.
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Shehzad, M.T., Sabir, M., Saifullah et al. Impact of Water Regimes on Minimizing the Accumulation of Arsenic in Rice ( Oryza sativa L.). Water Air Soil Pollut 233 , 383 (2022). https://doi.org/10.1007/s11270-022-05856-7
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DOI : https://doi.org/10.1007/s11270-022-05856-7
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Muhammad Tauseef Azam , Asif Ahmad , Anwaar Ahmed , Azeem Khalid , Samreen Saleem; Health risk assessment of arsenic and lead contamination in drinking water: A study of Islamabad and Rawalpindi, Pakistan. Water Supply 2024; ws2024135. doi: https://doi.org/10.2166/ws.2024.135
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The present research study explores the drinking water quality of Rawalpindi and Islamabad to identify the potent dissolved contaminants and carry out a health risk assessment as the study area houses more than 3 million people. Drinking water samples were collected from 95 union councils of the selected study area and were investigated for 12 physicochemical water quality indicators. The collected datasets were interpreted using general statistics, principal component analysis and spatial analysis for knowing the variations among the collected samples. The results revealed that overall 51.57% of the drinking water samples were unsatisfactory for human consumption. The rate of physicochemical contamination was 87.27% in the rural and unauthorized housing societies. Arsenic (As) and lead (Pb) were the potent contaminants in the drinking water samples. The health risk assessment uncovered that 31.57 and 10.45% of samples had a hazard quotient (HQ) >1 for arsenic and lead, respectively. Collectively, 41 drinking water sources were identified as potential health risk sources for the residents.
Planned sampling from 95 locations was carried out from in-use drinking water sources from the capital city Islamabad and Rawalpindi, Pakistan.
Assessment of health risks for arsenic and lead was carried out using the standard guidelines of USEPA.
The combination of spatial analysis with water quality indicators provides disseminated research findings to the general public along with scientific researchers.
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Ph.D. Candidate in Environmental Health Sciences, Florida International University
Assistant Professor of Environmental Health Sciences, Florida International University
Diana Azzam receives funding from the Florida Department of Health and the National Institute of Health.
Cristina Andrade-Feraud does not work for, consult, own shares in or receive funding from any company or organisation that would benefit from this article, and has disclosed no relevant affiliations beyond their academic appointment.
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Arsenic is a naturally occurring element found in the Earth’s crust. Exposure to arsenic, often through contaminated food and water, is associated with various negative health effects, including cancer .
Arsenic exposure is a global public health issue. A 2020 study estimated that up to 200 million people wordwide are exposed to arsenic-contaminated drinking water at levels above the legal limit of 10 parts per billion set by the U.S. Environmental Protection Agency and World Health Organization. More than 70 countries are affected, including the United States, Spain, Mexico, Japan, India, China, Canada, Chile, Bangladesh, Bolivia and Argentina.
Since many countries are still affected by high levels of arsenic, we believe arsenic exposure is a global public health issue that requires urgent action. We study how exposure to toxic metals like arsenic can lead to cancer through the formation of cancer stem cells .
Your body can absorb arsenic through several routes , such as inhalation and skin contact. However, the most common source of arsenic exposure is through contaminated drinking water or food.
People who live in areas with naturally high levels of arsenic in the soil and water are at particular risk. In the U.S., for example, that includes regions in the Southwest such as Arizona, Nevada and New Mexico. Additionally, human activities such as mining and agriculture can also increase arsenic in food and water sources.
High levels of arsenic can also be found in food and drink products , particularly rice and rice-based products like rice cereals and crackers. A 2019 Consumer Reports investigation even found that some brands of bottled water sold in the U.S. contained levels of arsenic that exceeded the legal limit. Alarmingly, multiple studies have also found that several popular baby food brands contained arsenic at concentrations much higher than the legal limit.
Chronic exposure to arsenic increases the risk of developing multiple types of cancer .
The mechanisms by which arsenic causes cancer are complex and not yet fully understood. However, research suggests that arsenic can damage DNA , disrupt cell signaling pathways and impair the immune system , all of which can contribute to cancer development.
Scientists have also linked chronic arsenic exposure to the development of cancer stem cells . These are cells within tumors thought to be responsible for cancer growth and spread. Like normal stem cells in the body, cancer stem cells can develop into many different types of cells. At what stage of cellular development a stem cell acquires the genetic mutation that turns it into a cancer stem cell remains unknown.
Our research aims to identify what type of cell arsenic targets to form a cancer stem cell. We are currently using cell cultures obtained from the same organ at different stages of cellular development to examine how the origins of cells affect the formation of cancer stem cells.
Preventing chronic arsenic exposure is critical to reducing the burden of arsenic-related health effects. Further research is needed to understand arsenic-induced cancer stem cell formation and develop effective strategies to prevent it. In the meantime, continued monitoring and regulation of this toxic metal in food and water sources could help improve the health of affected communities.
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Extramural By Adeline Lopez
NIEHS-funded researchers revealed how arsenic and cadmium may interact inside the human body, potentially altering their toxicity. The two metals frequently occur together in contaminated soil, but little is known about how combined exposure may affect health.
Using an simulated gastrointestinal (GI) tract in the lab, the team measured arsenic and cadmium bioaccessiblity, which is the amount of arsenic or cadmium that could be released during digestion and absorbed into the bloodstream. They exposed the artificial GI tract to cadmium only, arsenic only, or to a mixture of both metals. They also explored the effects of ferrihydrite, an iron mineral commonly found in dust, and pepsin, an enzyme responsible for protein digestion, to better replicate conditions inside the human body.
The team reported that cadmium bioaccessibility increased when arsenic was present. Arsenic bioaccessibility decreased with the addition of cadmium, but the arsenic present was transformed into a more toxic form. Both metals formed complexes with ferrihydrite, which promoted the release of cadmium but inhibited the release of arsenic. Pepsin formed soluble complexes with both metals, increasing their bioaccessibility.
According to the authors, these findings highlight the importance of understanding how exposure to contaminant mixtures affects their potential toxicity and may inform more protective regulatory strategies for soil and dust when cadmium and arsenic are both present.
Citation : Bai B, Kong S, Root RA, Liu R, Wei X, Cai D, Chen Y, Chen J, Yi Z, Chorover J. 2024. Release mechanism and interactions of cadmium and arsenic co-contaminated ferrihydrite by simulated in-vitro digestion assays . J Hazard Mater 467:133633.
An NIEHS-funded study found that glyphosate exposure during pregnancy may alter early brain development in children. According to the authors, this is one of the first studies to examine the relationship between exposure to the common herbicide before birth and neurodevelopment in young children.
The scientists studied 143 mother-baby pairs from Puerto Rico. To assess exposure, they collected urine samples from the mothers during pregnancy and measured levels of glyphosate and a common breakdown product of the herbicide. Then, they evaluated the children’s brain development at 6, 12, and 24 months using the Battelle Developmental Inventory. This test measures how well babies communicate, move, learn, and socialize. Using statistical models, they assessed potential links between the levels of glyphosate and the breakdown product in the mothers’ urine and their children’s performance on the test.
Children of mothers with higher glyphosate exposure scored lower in communication skills at 12 and 24 months. At 24 months, children with higher prenatal glyphosate exposure also scored lower in other areas, such as the ability to adapt to and understand new situations, attention, and memory.
These findings suggest that exposure to glyphosate during pregnancy may affect early neurodevelopment, with more pronounced delays by the time children reach 24 months, according to the authors. Because glyphosate is widely used, they noted that more research is needed to fully understand potential impacts on children’s neurodevelopment as they grow older.
Citation : Jenkins HM, Meeker JD, Zimmerman E, Cathey A, Fernandez J, Montañez GH, Park S, Pabón ZR, Vélez Vega CM, Cordero JF, Alshawabkeh A, Watkins DJ. 2024. Gestational glyphosate exposure and early childhood neurodevelopment in a Puerto Rico birth cohort . Environ Res 246:118114.
NIEHS-funded researchers discovered that the length of a mother’s telomeres and the sex of her child complicate the effects of prenatal air pollution exposure on birthweight. Telomeres are regions of repetitive DNA sequences at the end of chromosomes that shorten with age. Several factors, including stress and exposure to environmental contaminants, can accelerate telomere shortening and biological aging.
The researchers explored whether premature aging of the placenta, reflected by telomere length, modifies the relationship between air pollution exposure and birthweight. Abnormal birthweight is associated with higher risk for health problems later in life. They looked at data from 306 mothers and their babies who participated in an urban health study in the Northeast U.S. Using mathematical models, the team assessed the effects of air pollution exposure during pregnancy and placental telomere length at delivery on birthweight while accounting for the length of the pregnancy and the baby’s sex.
Results differed by exposure window, air pollutant, sex, and placental telomere length. For boys, exposure to fine particulate matter during the third trimester was associated with lower birthweight if their mothers had longer telomeres. In contrast, exposure to ozone during the first trimester or nitrogen dioxide in the third trimester was associated with higher birthweight if mothers had shorter telomeres. For girls, exposure to a mix of pollutants during the second trimester was associated with lower birthweight if their mothers had longer placental telomeres.
According to the authors, the results suggest that exploring the complex relationships between exposure timing, air pollutant exposure, placental telomere length, and a baby’s sex may help researchers identify women at higher risk for adverse birth outcomes, informing targeted interventions.
Citation : Zhang X, Colicino E, Cowell W, Enlow MB, Kloog I, Coull BA, Schwartz JD, Wright RO, Wright RJ. 2024. Prenatal exposure to air pollution and BWGA Z-score: Modifying effects of placenta leukocyte telomere length and infant sex . Environ Res 246:117986.
A strategy developed by NIEHS-funded scientists may trap PFAS in soil and prevent the chemicals from spreading to plants or water. Immobilizing the chemicals in soil is one remediation strategy to reduce human exposure.
The scientists evaluated the ability of six different sorbent materials, made up of activated carbon or specialized clays, to trap four PFAS chemicals in soil. They measured how much PFAS solution leaked out of soil — a proxy for how much could be absorbed by plants or animals, called bioavailability — when each sorbent was added. They also explored how changes in PFAS bioavailability translated to toxicity by exposing worms and aquatic plants to soil or water following extraction.
Overall, adding any of the sorbent materials reduced PFAS bioavailability in soil by 58-97%. Activated carbon was the most effective at trapping PFAS, reducing the bioavailable amount by 73-97%, depending on the amount of sorbent used. Their method was effective in trapping PFAS for up to 21 days, even when the soil samples were exposed to different conditions, including simulations of acid rain, fresh water, and brackish water. Mirroring the reduced bioavailability of PFAS, the team reported a dose-dependent decrease in toxicity to plants and worms in the presence of any of the six individual sorbents — some modified clays promoted plant growth due to added nutrients.
According to the authors, adding a combination of activated carbon and modified clays is a practical approach to help reduce the spread of PFAS in soils while protecting surrounding plants and animals.
Citation : Wang M, Rivenbark KJ, Nikkhah H, Beykal B, Phillips TD. 2024. In vitro and in vivo remediation of per- and polyfluoroalkyl substances by processed and amended clays and activated carbon in soil . Appl Soil Ecol 196:105285.
(Adeline Lopez is a science writer for MDB Inc., a contractor for the NIEHS Division of Extramural Research and Training.)
Read the current Superfund Research Program Research Brief . New issues are published on the first Wednesday of every month.
Heavy metals and pathogens from contaminated water sources may undoubtedly be removed by creating an efficient bio-adsorbent based on functional spots. Thus, the goal of this work was to produce chitosan (Ch)-polyvinyl alcohol (PVA) biofilm decorated with graphene oxide (GO) sheets doped with silver nanoparticles (AgNPs). The nanostructure of prepared GO/Ag nanosheets is examined by transmission electron microscope (TEM). The fabricated film (GO/Ag Ch-PVA) is compared by the control films (Ch, PVA and Ch-PVA). Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and tensile strength are used to study the films' structure. Also, the antimicrobial activity was assessed for the films. After doping the polymer matrix with GO/Ag, it was discovered that the tensile strength increased to about 46.18 MPa. Moreover, adsorption experiment for arsenic As (III) ions is explored by the prepared film at different operating conditions. The obtained results validated the enhanced adsorption ability of the GO/Ag Ch-PVA film towards As (III) with the highest adsorption capacity of 54.3 mg g ‑1 obtained from the isotherm model of Langmuir. Moreover, kinetic mathematical models for the adsorption effectiveness of GO/Ag Ch-PVA film are assessed. The results gathered demonstrated that GO/Ag Ch-PVA film is a potentially useful material for eliminating As (III) and microbial strains from essential water resources.
Potential use of arbuscular mycorrhizal fungi for simultaneous mitigation of arsenic and cadmium accumulation in rice., deficit irrigation and organic amendments can reduce dietary arsenic risk from rice: introducing machine learning-based prediction models from field data, arsenic behavior across soil-water interfaces in paddy soils: coupling, decoupling and speciation., health risk assessment of co-occurrence of toxic fluoride and arsenic in groundwater of dharmanagar region, north tripura (india), predicting the modifying effect of soils on arsenic phytotoxicity and phytoaccumulation using soil properties or soil extraction methods., arsenic retention in cooked rice: effects of rice type, cooking water, and indigenous cooking methods in west bengal, india., arsenic speciation dynamics in paddy rice soil-water environment: sources, physico-chemical, and biological factors - a review., arsenic accumulation in rice (oryza sativa l.) is influenced by environment and genetic factors., diffusive gradients in thin films reveals differences in antimony and arsenic mobility in a contaminated wetland sediment during an oxic-anoxic transition., arsenic accumulation in rice and probable mitigation approaches: a review, related papers.
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Effects of foliar spraying of dicarboxylicdimethylammonium chloride on cadmium and arsenic accumulation in rice grains.
Fu, L.; Deng, J.; Lao, D.R.; Zhang, C.; Xue, W.; Deng, Y.; Luo, X. Effects of Foliar Spraying of Dicarboxylicdimethylammonium Chloride on Cadmium and Arsenic Accumulation in Rice Grains. Toxics 2024 , 12 , 418. https://doi.org/10.3390/toxics12060418
Fu L, Deng J, Lao DR, Zhang C, Xue W, Deng Y, Luo X. Effects of Foliar Spraying of Dicarboxylicdimethylammonium Chloride on Cadmium and Arsenic Accumulation in Rice Grains. Toxics . 2024; 12(6):418. https://doi.org/10.3390/toxics12060418
Fu, Lin, Jiawei Deng, Dayliana Ruiz Lao, Changbo Zhang, Weijie Xue, Yun Deng, and Xin Luo. 2024. "Effects of Foliar Spraying of Dicarboxylicdimethylammonium Chloride on Cadmium and Arsenic Accumulation in Rice Grains" Toxics 12, no. 6: 418. https://doi.org/10.3390/toxics12060418
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cies in water are coupled techniques including chromatography, optical methods and. mass spectrometry. Determination of arsenic species is of crucial importance for selec-. tion of arsenic removal ...
1. Introduction. Arsenic (As) is a common drinking water contaminant that is often found in groundwater wells [1-6].Even at very low concentrations, chronic consumption of As in drinking water has been strongly associated with a variety of cancers and other adverse health effects in humans [7-13].At least 226 million people in 56 countries are exposed to unsafe concentrations of As in ...
The WHO has published a guideline value for arsenic in its Guidelines for drinking-water quality and arsenic is on their list of 10 chemicals of major public health concern. 4 Presently, more than 230 million people worldwide are affected by arsenic toxicity. 5 Acute arsenic toxicity has been reported to cause acute paralytic syndrome (APS) and ...
Arsenic contamination in groundwater is a global public health concern. Dissolved arsenic is typically in the form of arsenate and arsenite ions, together referred to as "inorga Health issues related to arsenic in groundwater are most widespread in South and Southeast Asia, where over 100 million people are exposed to unsafe arsenic levels via drinking contaminated water.
The elevated cases of arsenic contamination reported across the globe have made its early detection and remediation an active area of research. Although, the World Health Organisation has set the maximum provisional value for arsenic in drinking water at 10 parts per billion, yet concentrations as high as 5000 parts per billion are still reported.
It is classified as carcinogen, mutagens, and teratogen. IARC (International Agency for Research on Cancer) has classified As is a class1 human carcinogen. In natural water bodies arsenic mostly found in two states trivalent arsenic (As 3+, Arsenite) and pentavalent arsenic (As 5+) both forms are highly toxic inorganic species (Fendorf et al ...
Several papers have been published previously which demonstrated the applications of novel materials in arsenic treatment. ... Research efforts are ongoing to bridge the gap between laboratory-scale success and real-world field conditions, bringing these promising nanostructured materials closer to practical and effective arsenic removal ...
In view of the deleterious environmental and health effects associated with arsenic (As) in water, a number of technologies have been developed to forewarn and assess its concentration. These methodologies range from colorimetric methods to sophisticated biosensors.
The total concentration of arsenic in drinking water can be detected by simple Gutzeit method, and some similar colorimetric methods of comparing stains produced on treated paper strips. Although its minimum detectable concentration is 1.0·μ L −1 , these tests should be used when only a qualitative or semiqualitative detection is needed.
The elevated cases of arsenic contamination reported across the globe have made its early detection and remediation an active area of research. Although, the World Health Organisation has set the maximum provisional value for arsenic in drinking water at 10 parts per billion, yet concentrations as high as 5000 parts per billion are still reported.
The results showed that the papers related to FAP research during 2000-2020 were published in 1077 journals. ... Abejon, R., & Garea, A. (2015). A bibliometric analysis of research on arsenic in drinking water during the 1992-2012 period: An outlook to treatment alternatives for arsenic removal. Journal of Water Process Engineering, 6, ...
Because dramatic cases of arsenic contamination of water resources, soils, vegetables, humans and animals increase, this review has focussed on the fate and behaviour of this element and what kind of health impacts are related with its release in surface or ground waters. In a first part, we point out how the primary minerals can lead to As mobilization and exportation by surface waters and ...
Arsenic cannot be seen, tasted or smelled and can vary in concentration between water wells, even in neighboring areas. 3 The variability in arsenic concentration in ground water is due to the arsenic content of the aquifer materials and the varying processes that dissolve arsenic from surrounding sediment into the water. 4
The use of arsenic contaminated drinking water is the major cause for skin, lung, bladder, kidney cancer as well as other adverse health effects such as skin manifestations, gastrointestinal ...
In recognition of the extent and severity of arsenic poisoning in most countries worldwide, the International Journal of Environmental Research and Public Health devotes this Special Issue to recent findings on "Arsenic in drinking water: current perspectives". A wide range of topics will be included in this issue.
Water Pollutants, Chemical. Arsenic. The purpose of this American Council on Science and Health report is to review issues and sources of uncertainty affecting assessment of potential health risks related to drinking water in the United States. Some background is included on how these issues arose, as is a review of the 1999 National R ….
The toxicology of arsenic involves mechanisms that are still not completely understood, but it is clear that a number of factors can affect both individual and population-level susceptibility to the toxic effects of arsenic-contaminated drinking water. Current research is addressing some of these, including genetic susceptibility and lifestyle ...
Arsenic is a very common class-1 (non-threshold) human carcinogen, a pollutant of the environment (Int. Agency Res. Cancer., 2004).Its presence is ubiquitous in soil, sediments, and water (Bhattacharya et al., 2007).It bioaccumulates in living organisms by entering the biological system through air, water, or food (Adokoh et al., 2011).Smedley and Kinniburgh reported that As whose ...
The most relevant research aspects of the four main technologies applied to arsenic removal from drinking water (coagulation, flocculation and precipitation followed by filtration; adsorption and ion exchange; membrane-based processes and biological treatments) were summarized in this paper, with adsorption appearing to be the alternative that ...
Arsenic (As) and lead (Pb) were the potent contaminants in the drinking water samples. The health risk assessment uncovered that 31.57 and 10.45% of samples had a hazard quotient (HQ) >1 for arsenic and lead, respectively. Collectively, 41 drinking water sources were identified as potential health risk sources for the residents.
ultimately reach and affect our ecology as a whole. This paper presents an overview of the highly toxic arsenic existence in drinking water around the globe with a detailed view of India and the various treatment techniques followed by remedial measures along with their advancement. Keywords: arsenic contamination, water resources, India, treatment
Photocatalytic oxidation-adsorption synergistic treatment of organic arsenic pollutants is a promising wastewater treatment technology, which not only degrades organic arsenic pollutants by photocatalytic degradation but also removes the generated inorganic arsenic by adsorption. This paper compares the results of photocatalytic oxidation-adsorption co‑treatment of organic arsenic ...
A 2020 study estimated that up to 200 million people wordwide are exposed to arsenic-contaminated drinking water at levels above the legal limit of 10 parts per billion set by the U.S ...
Several factors, including stress and exposure to environmental contaminants, can accelerate telomere shortening and biological aging. The researchers explored whether premature aging of the placenta, reflected by telomere length, modifies the relationship between air pollution exposure and birthweight. Abnormal birthweight is associated with ...
Heavy metals and pathogens from contaminated water sources may undoubtedly be removed by creating an efficient bio-adsorbent based on functional spots. Thus, the goal of this work was to produce chitosan (Ch)-polyvinyl alcohol (PVA) biofilm decorated with graphene oxide (GO) sheets doped with silver nanoparticles (AgNPs). The nanostructure of prepared GO/Ag nanosheets is examined by ...
DOI: 10.17221/470/2023-pse Corpus ID: 270292359; Mitigation of arsenic toxicity in rice grain through soil-water-plant continuum @article{Devi2024MitigationOA, title={Mitigation of arsenic toxicity in rice grain through soil-water-plant continuum}, author={Okram Ricky Devi and Bibek Laishram and Abhijit Debnath and Gangadhara Doggalli and Nayanjyoti Ojha and Smita Agrawal and Kahkashan Perveen ...
A field experiment with double cropping rice was carried out to study the foliar application effects of dicarboxylicdimethylammonium chloride (DDAC) on cadmium (Cd) and arsenic (As) accumulation in rice grains. The results showed that the spraying of DDAC could significantly reduce the accumulation of Cd and As in rice grains. The highest reductions in Cd and As content were observed when 1.5 ...