Review Article

Recent Developments in the Speciation and Determination of Mercury Using Various Analytical Techniques

Table 1

Analytical parameters of reviewed research papers about the speciation and determination of mercury by spectrometric instruments (AAS, ICP-OES, AES, MS, and AFS).

S. numberAnalyteAnalytical instrument used for the detectionMethodLimit of detection (LOD)#Linearity rangeAnalyzed samplesInterference studySupporting mediaReference

1Total HgCV-AAS and ICP-AESMicrowave acid digestion4.83 × 10−10 MFish samplesCadmium and lead also analyzed along with mercury[7]

2Hg(II)CV-AASPreconcentration1.79 × 10−10 MWater and human hairRecovery of Hg2+ is in the range of 95.6–104.9% in presence of Cu2+, Co2+, Zn2+, Ni2+, Cd2+, Mn2+, Ba2+, Pb2+, Fe3+, Cr3+, Al3+, Ag+, K+, Na+, , Mg2+, and Ca2+ ions, from 750 to 2500-foldDithizone[8]

3Total HgCV-AASUltrasound extraction6.98 × 10−11 MAlcohol vinegar[9]

4Total HgCV-AASSPE14.98 × 10−11 MRice, canned fish, and tea leavesThe tolerance limit for Na+, K+, Mg2+, and Ca2+ is 4000-fold, for Ba2+ and Zn2+ is 40-fold, for Fe3+, Cr3+, Co2+, and Ni2+ is 10-fold, and for Al3+ is 200-fold compared to Hg2+Fe3O4 nanoparticles[10]

5Hg(II)CV-AASSPE9.97 × 10−12 MUp to 500 μg L−1Water samplesAs, Al, Fe, Mo, and Sb are depressed the Hg signal Carbon nanotubes[11]

6Total HgCV-AASAcid digestion3.6 × 10−9 M Marine fish [12]

7Total HgCV-AASWet digestion3.0 × 10−9 MGreen tiger shrimpArsenic also determined along with mercury[13]

8Total HgCV-AASAlkaline fusion digestion0.06 ng g−10.006–4000 ng g−1Phosphate rock[14]

9THgAASAcid digestion4.98 × 10−12 MFish muscle tissuesCadmium and lead also detected along with mercury[15]

10Hg(II)CV-AASSPE1.19 × 10−11 M0.01–2.30 μg L−1Water samplesFe3+, Cu2+, Zn2+, Cd2+, Co2+, and Mn2+ are not interfered up to 5 mg L−1 and and Tl3+ are not interfered up to 1 mg L−1Polymer supported ionic liquid[16]

11Hg(II)CV-AASSPE9.97 × 10−11 M 0.07–2.00 μg L−1Water samplesTolerable amount of major metals is limited up to 50 μg L−1Polytetrafluoroethylene[17]

12Total HgCV-AASDigestion3.98 × 10−10 M 2.5–10.0 μg L−1Biological samplesCold finger[18]

13Total HgCV-AASCombustion2.99 × 10−13 M Water and fishArsenic and selenium also determined along with mercury[19]

14Total HgAASAmalgamation0.2 ng/g for hair and 0.02 ng/g for bloodHair and blood samplesArsenic and selenium also determined along with mercury[20]

15Total HgCV-AAS (total Hg) and GC-ICPMS (MeHg)Cold-vapor reduction with NaBH45.98 × 10−11 M (total Hg) and 2.3 × 10−9 M (MeHg)Blood of birdsSelenium also determined along with mercury and methylmercury[21]

16Total Hg and MeHgCV-AAS (total Hg) and CV-AFS (MeHg)Digestion0.03–0.1 ng/gFish, vegetables, and mushroomsSelenium and cadmium also determined with mercury species[22]

17Hg speciationCV-AAS (total Hg) and CV-AFS (MeHg)Acid digestionWater samples[23]

18Hg speciationCV-AASLLME21.49 × 10−10 M (Hg2+) and
1.8 × 10−9 M (MeHg)
0.5–100 ng mL−1Water samples and CRMsThe recovery of Hg2+ in presence of foreign ions is 95–105 and for MeHg is 96–106%[24]

19Total HgGF-AASAcid mineralization6.97 × 10−11 MFish muscle samplesCopper nitrate[25]

20GEMAASAmbient air[26]

21Total HgCV-AASAcid digestion0.0006 μg g−1Freshwater fish samplesStannous chloride[27]

22Total HgAASCombustion0.01 ngSoil samplesInterference of various heavy metals was overcome by using sample pretreatment[28]

23Hg speciationAAS (THg) and ICP-MS-HPLC (MeHg)Hydride generation5.33 × 10−14 M20 μg L−1Fish samplesCd, Pb, As, and Sn also measured along with Hg[29]

24THgHG-AASHydride generation98.4% (accuracy)Irrigation water wellsAlong with mercury Pb, Cd, and Al Cr also measured[30]

25THgCV-AAS and AASThermal decomposition and amalgamation1.34 × 10−9 M (TD-amalgamation AAS) and 3.14 × 10−9 M (CV-AAS), Soil samples[31]

26Total Hg speciationHV-AAS and
HPLC-CV-AFS
ExtractionAqueous solutions and fish tissueMultiwalled carbon nanotubes[32]

27Total HgCV-AAS (DMA)Microwave oven digestionCanned fishSelenium and tin also measured along with mercury[33]

28THgAMA (AAS)AAS principles and without digestion processFish red muscle and
white muscle
[34]

29THgAESLIBS and SIBS2 × 10−3 M (LIBS) and 9.97 × 10−5 M (SIBS)Soil samples At 534.074 nm has less spectral interference[35]

30Hg speciationCV-AFSExtraction1.0 (total Hg) and 0.01 MeHg ng g−1Sea water and sediments[36]

31Hg speciationCV-AFSExtraction0.01 × 10−12 M (Hg0) and 0.002 × 10−12 M (DM Hg)Sea waters[37]

32Total HgCV-AFSMicrowave assisted digestion3.98 × 10−13 MNutsInterference of fat in nuts is removed by treatment with chloroform and methanol[38]

33Hg(II)AFSFluorescence optical sensor9.57 × 10−12 M 2.27 × 10−11–1.13 × 10−3 MHuman hair, urine, and
well water samples
Most of the alkali, alkaline, and transition metal ions did not interfere in the determination of Hg2+N-(2-Hydroxy phenyl)-N-(2-mercapto phenyl)-o-phthalylidene[39]

34GEMCV-AFSGold amalgamation0.0002 ngTotal suspended particulatesQFF (quartz fiber filters)[40]

35MeHgAAS and CV-AFSAcid digestion0.005 μg/gWater, soil, sediments, and foodstuffs[41]

36Total HgCV-AFSMicrowave assisted digestion0.5 ng g−1SedimentsSequential injection system[42]

37Total HgCV-AFSAcid digestion0.48 ng g−1RiceInterference of other metal ions is eliminated by acid wash and kept storage of samples for 24 hMultisyringe flow injection analysis[43]

38Hg speciationHPLC-AFSUV-induced atomization1.9 × 10−9 (Hg2+), 1.9 × 10−9 (MeHg), and 2.0 × 10−9 (EtHg) M CRMs[44]

39Hg(II)UV-AFSSPE1.49 × 10−13–3.98 × 10−13 M1–5000 ng L−1Natural waters10 mg L−1 of Fe2+, Fe3+, Cu2+, Pb2+, and As3+ and 10 g L−1 of Na+, K+, and Ca2+ did not interfere in the determination of 100 ng L−1 of Hg2+Sodium diethyldithiocarbamate[45]

40Hg(II)AFSMicro-SPE5.98 × 10−11 MUp to 5 μg L−1Water samplesMesofluidic platform[46]

41Hg speciationEX-AFS0.5 ng g−1 (total Hg)Waste calcines[47]

42Hg speciationCV-AFSExtraction~0.5 pgAtmospheric airPTFE filter papers[48]

43MeHgGC-AFSSPE12 ng g−1Up to 1.5 ng mL−1Biological samples[49]

44Hg speciationHPLC-AFSLiquid-liquid microextraction1.54 × 10−10 (Hg2+), 7.42 × 10−11 (MeHg), 1.045 × 10−10 (EtHg), and 3.31 × 10−10 M (PhHg) 0.0–20 μg L−1Environmental watersNo interference from other metal ions1-Octyl-3-meth-l imidazolium hexafluorophosphate[50]

45MeHgCV-AFSExtraction0.515 ng g−1PetroleumTMAH3, KOH/CH3OH, HCl, and acidic CuSO4/KBr[51]

46GEMCV-AFSAmbient air[52]

47Hg(II)AFSFluorescence 0.07  10−6 M0.1–4.5 μMAqueous solutionsLonger excitation and emission wavelength could shield the interferenceFe3O4 magnetic nanoparticles[53]

48Hg speciationCV-AFSThermal decompositionFish liverMethod validity is tested with CRM[54]

49THgAFS<4.98 × 10−12 MSnowK2Cr2O7/SnCl2[55]

50Atmospheric HgCV-AFSExtractionParticulate matter[56]

51THgCV-AFSFlow injection mercury systemHerbal productsProtease papain[57]

52Hg speciationLC-UV-CV-AFSMicrowave digestion4.98 × 10−12 (total Hg), 1.39 × 10−12 (MeHg), and 1.99 × 10−12 (Hg2+) MSea foodSimultaneously determined both Hg(II) and MeHg[58]

53MeHg and total HgCV-AASDigestion0.088 (MeHg) and 0.005 (total Hg) μg g−1Hair and milk of mothers[59]

54Hg(II)ICP-MSMicrofluidic 3.49 × 10−10 M 0.2–4.0 μg L−1Aqueous samplesThe recovery of Hg2+ in the presence of 100 μg L−1 of Ca2+, Cd2+, Co2+, Cr3+, Cu2+, K+, Mg2+, Na+, Ni2+, Pb2+, and Zn2+ is in the range of 97.5–101.7%Gold nanoparticles[60]

55Total HgICP-MSAcid digestion0.053–0.01 μg g−1Pharmaceutical ingredientsLow residual carbon content in digests is desirable to minimize some interference[61]

56Hg(II)ICP-MSAdsorptionWastewatersMultiwalled carbon nanotubes[62]

57Hg(II)ICP-OESExtraction1.49 × 10−11 MFish samplesSelective in presence of Na+, K+, Cs+, Ca2+, Mg2+, Zn2+, Fe2+, Cu2+, Co2+, Ni2+, Mn2+, Cd2+, and Pb2+ into 1 mg L−1 solutions of Hg(II) in pH 8Ion imprinted polymer[63]

58Total HgCV-ICP-MSMicrowave digestion3 ng g−1Plants and soil[64]

59Total HgICP-MSMicrowave assisted digestionRice[65]

60GEMCV-ICP-MSThermal analysis20 × 10−15 gAtmospheric particulates[66]

61Hg(II) and MeHgHPLC-ICPMSHF-LPME45.48 × 10−10  (Hg2+) and 1 × 10−9  (MeHg) MUp to 50 μg L−1Tap, river, and estuarine watersSimultaneously selenium also determined along with mercury[67]

62Hg speciationICP-MSIon exchange chromatography9.47 × 10−11  (Hg2+), 1.25 × 10−10  (MeHg), 1.35 × 10−10  (EtHg), and 7.92 × 10−10  (PhHg) M0.1–100 μg L−1 (all Hg species)Sea water and marine fishL-Cysteine or thiourea[68]

63Hg speciationGC-ICP-MSPreconcentration27 (Hg2+) and 12 ng g−1 (MeHg)Human hair[69]

64Total HgMC-ICPMSIsotope ratio analysis0.1–0.2 disintegrations per minuteSediment coreMercury and mercury isotope compositions are determined[70]

65Hg(II) and MeHgCVG-ICP-MSExtraction1.7 (Hg(II)) and 2.3 ng g−1 (MeHg)Fish samples[71]

66MeHg, Hg(II), and
EtHg
HPLC-CV-ICPMSExtraction and separation5.98 × 10−11 (Hg(II)), 2.17 × 10−11 (EtHg), and 1.8 × 10−8 (MeHg) MPlasma/serum samples[72]

67Total HgICP-MSMicrowave assisted digestionFreshwater fish samples[73]

68Total HgICP-MSIsotope dilution and UV-photochemical vapor generation0.5 pg g−1Biological tissuesPolyatomic interference is not detectableFormic acid[74]

69Total HgICP-MSCalcination-isotope dilution2 × 10−15 MDiploria specimensNo isobaric interference was found[75]

70Hg speciationICP-MSAnion exchange chromatographic separation3.98 × 10−11 (Hg2+), 1.11 × 10−10 (MeHg), 1.26 × 10−10 (EtHg), and 1.22 × 10−10 (PhHg) M Fish samples3-Mercapto-1-propanesulfonate[76]

71Total HgICP-MSUltrasonic slurry sampling electrothermal vaporization 0.2 ng g−1Herbal samplesAs, Cd, and Pb also determined along with Hg8-Hydroxyquinoline[77]

72Total HgICP-MSElectrothermal vaporization5.98 × 10−11 MWater associated with crude oil productionBy preconcentration of analyte interference is avoided[78]

73THgICP-MSIsotope dilution equation4.98 10−11 M for THg0.0005–1.321 mg/kg for MeHgArctic cod[79]

For the conversion of limit of detection values into moles per liter (M) the atomic weight of Hg is taken as 200.59 g, MeHg as 215.59 g, EtHg as 229.59 g, and PhHg as 277.59 g.
1Solid-phase extraction; 2LLME: liquid-liquid microextraction; 3TMAH: tetramethylammonium hydroxide; 4HF-LPME: hallow fiber liquid phase microextraction.
Analytical instruments: CV-AAS: cloud vapor atomic absorption spectrometer; HG-AAS: hydride generation AAS; GF-AAS: graphite furnace AAS; ICP-OES: inductively coupled plasma optical emission spectrometer; ICP-MS: ICP-mass spectrometer; ICP-AES: ICP-atomic emission spectrometer; HPLC: high performance liquid chromatography; AFS: atomic fluorescence spectrometer; AMA: automatic mercury analyzer; DMA: direct mercury analyzer.