Validation of a hydride generation atomic absorption spectrometry methodology for determination of mercury in fish designed for application in the Brazilian national residue control plan

In the present study, a method for the determination of mercury (Hg) in fish was validated according to ISO/IEC 17025, INMETRO (Brazil), and more recent European recommendations (Commission Decision 2007/333/EC and 2002/657/EC) for implementation in the Brazilian Residue Control Plan (NRCP) in routine applications. The parameters evaluated in the validation were investigated in detail. The results obtained for limit of detection and quantification were respectively, 2.36 and 7.88 μg kg^?1 of Hg. While the recovery varies between 90–96%. The coefficient of variation was of 4.06–8.94% for the repeatability. Furthermore, a comparison using an external proficiency testing scheme was realized. The results of method validated for the determination of the mercury in fish by Hydride generation atomic absorption spectrometry were considered suitable for implementation in routine analysis.     

Method validation for control determination of mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry

A method for the determination of total mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) has been validated following international foodstuff protocols in order to fulfill the Brazilian National Residue Control Plan. The experimental parameters have been previously studied and optimized according to specific legislation on validation and inorganic contaminants in foodstuff. Linearity, sensitivity, specificity, detection and quantification limits, precision (repeatability and within-laboratory reproducibility), robustness as well as accuracy of the method have been evaluated. Linearity of response was satisfactory for the two range concentrations available on the TDA AAS equipment, between approximately 25.0 and 200.0 μg kg^?1 (square regression) and 250.0 and 2000.0 μg kg^?1 (linear regression) of mercury. The residues for both ranges were homoscedastic and independent, with normal distribution. Correlation coefficients obtained for these ranges were higher than 0.995. Limits of quantification (LOQ) and of detection of the method (LDM), based on signal standard deviation (SD) for a low-in-mercury sample, were 3.0 and 1.0 μg kg^?1, respectively. Repeatability of the method was better than 4%. Within-laboratory reproducibility achieved a relative SD better than 6%. Robustness of the current method was evaluated and pointed sample mass as a significant factor. Accuracy (assessed as the analyte recovery) was calculated on basis of the repeatability, and ranged from 89% to 99%. The obtained results showed the suitability of the present method for direct mercury measurement in fresh fish and shrimp samples and the importance of monitoring the analysis conditions for food control purposes. Additionally, the competence of this method was recognized by accreditation under the standard ISO/IEC 17025.     

微波消解-氢化物发生原子荧光光度法测定土壤中的汞

建立了微波消解-氢化物发生原子荧光光度法测定土壤中汞的方法。对微波消解条件、样品粒度等进行了优化,用3 mL硝酸和2 mL盐酸的混合酸作消解溶剂,在设定的微波条件下汞提取完全。用3%的盐酸作为反应载流,0.01%硼氢化钾与0.5%氢氧化钠的混合液为还原剂,直接定容后应用HG-AFS测定,通过测定国家标准参考物质和加标回...     

Seasonal variation in dissolved gaseous mercury and total mercury concentrations in Juam Reservoir, Korea

Dissolved gaseous mercury (DGM) and total mercury (TM) concentrations were measured in Juam Reservoir, Korea. DGM concentrations were higher in spring (64+/-13pgL(-1)) and summer (109+/-15pgL(-1)), and lower in fall (20+/-2pgL(-1)) and winter (23+/-6pgL(-1)). In contrast, TM concentrations were higher in fall (3.2+/-0.1ngL(-1)) and winter (3.3+/-0.1ngL(-1)) than in spring (2.3+/-0.1ngL(-1)) and summer (2.2+/-0.4ngL(-1)). DGM concentrations were correlated with water temperature (p<0.0001), ORP (p<0.0001), UV intensity (UV-A: p=0.008; UV-B: p=0.003), and DOC concentration (p=0.0107). DGM concentrations varied diurnally with UV intensity. The average summer DGM (109+/-15pgL(-1)) and TM (2.2+/-0.4ngL(-1)) concentrations in Juam Reservoir were higher than the averages for North American lakes (DGM=38+/-16pgL(-1); TM=1.0+/-1.2ngL(-1)), but lower than levels reported for Baihua Reservoir in China.     

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.     

4种重金属离子对间接火焰原子吸收光谱法测定铝的干扰

空气-乙炔间接火焰原子吸收法是我国目前运用较多且易于推广的铝检测方法,研究了Mg2+、Ca2+、Zn2+和Ni2+4种离子对此法测定0.40 mg/L Al3+ 的干扰情况。得出如下结论:(1)在±5% 误差范围内,15.10 mg/L Mg2+、105.00 mg/L Ca2+、0.23 mg/L Zn2+、0.88 mg/L Ni2+对0.40 mg/L Al3+ 无干扰。(2)本方法虽然操作复杂,但成本较低、灵敏度高,检测的浓度范围宽、稳定性好,加标回收率为96%~99%,检出限为0.04 mg/L,适宜测定范围为0.05~100.00 mg/L,适用于饮用水、河水及地下水中Al3+ 的测定。     

A summary of total mercury concentrations in flora and fauna near common contaminant sources in the Gulf of Mexico

Total mercury concentrations are summarized for environmental media and biota collected from near-coastal areas, several impacted by contaminant sources common to the Gulf of Mexico. Water, sediment, fish, blue crabs, oysters, clams, mussels, periphyton and seagrasses were collected during 1993–2002 from targeted areas affected by point and non-point source contaminants. Mean concentrations in water and sediment were 0.02 (±1 standard deviation = 0.06) μg l⁻¹ and 96.3 (230.8) ng g⁻¹ dry wt, respectively. Mean total mercury concentrations in fish, blue crabs, brackish clams and mussels were significantly greater than those in sediment, seagrass, colonized periphyton and oysters. Concentrations (ng g⁻¹ dry wt) averaged 23.1 (two seagrass species), 220.1 (oysters), 287.8 (colonized periphyton), 604.0 (four species of freshwater mussels), 772.4 (brackish clam), 857.9 (blue crabs) and 933.1 (nine fish species). Spatial, intraspecific and interspecific variability in results limited most generalizations concerning the relative mercury contributions of different stressor types. However, concentrations were significantly greater for some biota collected from areas receiving wastewater discharges and golf course runoff (fish), agricultural runoff (oysters) and urban stormwater runoff (colonized periphyton and sediment). Marine water quality criteria and proposed sediment quality guidelines were exceeded in 1–12% of total samples. At least one seafood consumption guideline, criteria or screening value were exceeded in edible tissues of blue crabs (6% total samples) and nine fish species (8–33% total samples) but all residues were less than the US Federal Drug Administration action limit of 1.0 ppm and the few reported toxic effect concentrations available for the targeted biota.     

基于王水石墨密封消解体系-原子荧光法测定土壤和沉积物中汞、砷

为解决土壤和沉积物样品中的汞、砷前处理中的一些问题,如耗时长、清洗流程复杂及汞污染等,建立了一种基于王水石墨密封消解体系的前处理新方法,结合原子荧光可用于土壤和沉积物中Hg和As的测定。在最优条件下,2种重金属元素测定结果表明,本方法具有较低的相对误差 (Hg, -9.3%~9.3%; As,-7.0%~5.1%) ,较高的加标回收率 (Hg, 93.2%~104.5%; As, 95.9%~103.5%) 。此外,本方法相关性能指标均优于现行标准方法,具有稳定性好、精密度好、准确度高等优点。更重要的是,本方法因采用成本低廉的一次性塑料管,无需消解管清洗,避免了汞的污染。而且,消解过程无需其它操作,消解液用量少,具有操作简单、成本低、无汞污染等优点,可用于大通量土壤和沉积物Hg、As含量的测定。     

The determination of heavy metals (Al,Mn, Fe,Ni, Cu,Zn, Cd and Pb) in urban snow using an atomic absorption graphite furnace

The concentrations of eight metals (Al, Mn, Fe, Ni, Cu, Zn, Cd and Pb) in snow from the island of Montréal were determined in quantities of nanogram per gram using an atomic absorption graphite furnace. An overall precision of 10% was achieved for all elements. Enrichment factors calculated indicated that Ni, Cu, Zn, Cd and Pb are most probably anthropogenically derived.     

Tissue distribution of inorganic mercury, methylmercury and cadmium in the Asiatic clam (Corbicula fluminea) in relation to the contamination levels of the water column and sediment

The comparative experimental study of inorganic mercury (HgII), methylmercury (MeHg) and cadmium (Cd) bioaccumulation in the Asiatic clam Corbicula fluminea was based on a 14 days' exposure to the water column or sediment compartments, as initial contamination sources. For each contaminant and exposure source, a five-point concentration range was set up in order to quantify the relationships between the contamination pressure and bioaccumulation capacity, at the whole soft body level and in five organs: gills, mantle, visceral mass, kidney and foot. Hg and Cd bioaccumulation at the whole organism level was proportional to the metal concentrations in the water column or sediment. For similar exposure conditions, the average ratios between the metal concentrations in the bivalves - [MeHg]/[HgII] and [MeHg]/[Cd] - were close to 10 and 5 for the sediment source and 8 and 15 for the water column source. Metal distribution in the five organs revealed strong specificities, according to the different contamination modalities studied: kidney and gills were clearly associated with Cd exposure, mantle and foot with MeHg exposure and the visceral mass with inorganic Hg exposure.